-
Volume 42:Organophosphorus Compounds(incl. RO—P and RN—P)
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . V
Volume Editor�s Preface . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII
Table of Contents . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
XI
IntroductionF. Mathey . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 1
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene
ComplexesJ. C. Slootweg and K. Lammertsma . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 15
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and
Iminophosphinesand DiphosphenesM. Yoshifuji . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 37
42.3 Product Class 3: Phosphenium SaltsM. Yoshifuji . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 63
42.4 Product Class 4: AlkylphosphinesE. Hey-Hawkins and A. A.
Karasik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . 71
42.5 Product Class 5: Bis(alkylphosphino)- and
Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P
BondE. Hey-Hawkins and A. A. Karasik . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 109
42.6 Product Class 6: Cyclic PhosphinesD. Gudat . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 155
42.7 Product Class 7: Dialkylphosphinous Acids and DerivativesK.
M. Pietrusiewicz and M. Stankevič . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 221
42.8 Product Class 8: Alkylphosphonous Acids and DerivativesK.
M. Pietrusiewicz and M. Stankevič . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 243
42.9 Product Class 9: Phosphorous Acid and DerivativesM.
Stankevič and K. M. Pietrusiewicz . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 275
42.10 Applications of Tricoordinated Phosphorus Compoundsin
Homogeneous Catalysis
42.10.1 General Catalytic MethodsM. Toffano . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . 347
42.10.2 Enantioselective Catalytic MethodsJ.-C. Fiaud and A.
Marinetti . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . 391
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42.11 Applications of Tricoordinated Phosphorus Compounds
inOrganocatalysisJ. L. Methot and W. R. Roush . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
469
42.12 Product Class 12: Alkylphosphonium SaltsD. Virieux, J.-N.
Volle, and J.-L. Pirat . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 503
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides,
Selenides,Tellurides, and ImidesN. L. Kilah and S. B. Wild . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . 595
42.14 Product Class 14: Dialkylphosphinic Acids and
DerivativesJ. Drabowicz, J. Lewkowski, C. V. Stevens, D. Krasowska,
and R. Karpowicz . . 633
42.15 Product Class 15: Alkylphosphonic Acids and DerivativesJ.
Drabowicz, P. Kiełbasiński, P. Łyżwa, M. Mikołajczyk, and A.
Zaja̧c . . . . . . . . . 679
42.16 Product Class 16: Phosphoric Acid and DerivativesC. E.
McKenna, B. A. Kashemirov, and K. M. Błażewska . . . . . . . . . .
. . . . . . . . . . . 779
42.17 Product Class 17: PhosphazenesS. Urgaonkar and J. G.
Verkade . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 923
42.18 Product Class 18: Pentacoordinated PhosphoranesT.
Kawashima and J. Kobayashi . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 953
42.19 Product Class 19: Hexacoordinated PhosphatesD. Linder and
J. Lacour . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 977
Keyword Index . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
993
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1049
Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1121
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Table of Contents
IntroductionF. Mathey
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . 1
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene
ComplexesJ. C. Slootweg and K. Lammertsma
42.1 Product Class 1: Phosphinidenes and Terminal Phosphinidene
Complexes . 15
42.1.1 Product Subclass 1: Free Phosphinidenes . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 15
42.1.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
16
42.1.1.1.1 Method 1: Elimination . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1642.1.1.1.1.1 Variation 1: Thermal Generation . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1642.1.1.1.1.2 Variation 2: Photolytic Generation . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1642.1.1.1.2 Method 2: Reduction . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1742.1.1.1.3 Method 3: Phospha-Wittig Reagents . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . 17
42.1.1.2 Applications of Product Subclass 1 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . . 18
42.1.1.2.1 Method 1: Trapping Reactions . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
42.1.2 Product Subclass 2: Neutral Electrophilic Phosphinidene
Complexes . . . . . . 19
42.1.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
20
42.1.2.1.1 Method 1: Cheletropic Elimination . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . .
2042.1.2.1.1.1 Variation 1: From 7-Phosphanorbornadienes . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 2042.1.2.1.1.2
Variation 2: From Phosphiranes . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 2242.1.2.1.1.3
Variation 3: From Phosphirenes . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 2242.1.2.1.2 Method
2: Salt Metathesis . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 23
42.1.2.2 Applications of Product Subclass 2 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . . 24
42.1.2.2.1 Method 1: Trapping Reactions . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
42.1.3 Product Subclass 3: Cationic Electrophilic Phosphinidene
Complexes . . . . . 24
42.1.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
24
42.1.3.1.1 Method 1: Chloride Abstraction . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
42.1.4 Product Subclass 4: Nucleophilic Phosphinidene Complexes
. . . . . . . . . . . . . . 25
42.1.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
25
42.1.4.1.1 Method 1: Salt Metathesis/Elimination . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . 2542.1.4.1.1.1
Variation 1: Of Metal Hydrides . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 2642.1.4.1.1.2
Variation 2: Of Alkali Metal Phosphides . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 2642.1.4.1.1.3 Variation 3:
Of Transition Metal Phosphides . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . 2842.1.4.1.2 Method 2: Addition/Elimination
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . 2942.1.4.1.3 Method 3: Dehydrohalogenation/Ligation . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
3042.1.4.1.4 Method 4: a-Hydrogen Migration . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 3142.1.4.1.5
Method 5: Oxidation/Deprotonation . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 32
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42.1.4.2 Applications of Product Subclass 4 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . . 33
42.1.4.2.1 Method 1: Phosphinidene-Transfer Reactions . . . . .
. . . . . . . . . . . . . . . . . . . . . . 33
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and
Iminophosphines andDiphosphenesM. Yoshifuji
42.2 Product Class 2: Oxo-, Thioxo-, Selenoxo-, and
Iminophosphines andDiphosphenes . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . 37
42.2.1 Product Subclass 1: Oxophosphines . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 37
42.2.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
37
42.2.1.1.1 Method 1: Elimination Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
3742.2.1.1.2 Method 2: Cycloreversion Reactions . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 38
42.2.2 Product Subclass 2: Thioxophosphines and
Selenoxophosphines . . . . . . . . . . 39
42.2.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
40
42.2.2.1.1 Method 1: Elimination Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
4042.2.2.1.2 Method 2: Cycloreversion Reactions . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 4042.2.2.1.3
Methods 3: Miscellaneous Reactions . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 42
42.2.3 Product Subclass 3: Iminophosphines . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 44
42.2.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
44
42.2.3.1.1 Method 1: Elimination Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
4442.2.3.1.2 Method 2: Substitution Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 4542.2.3.1.3
Method 3: Cycloreversion Reactions . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 46
42.2.4 Product Subclass 4: Diphosphenes . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
42.2.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
47
42.2.4.1.1 Method 1: Elimination and/or Condensation Reactions .
. . . . . . . . . . . . . . . . . 4742.2.4.1.2 Method 2:
Rearrangement Reactions . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 5142.2.4.1.3 Method 3: Substitution
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 52
42.2.5 Product Subclass 5: Heteroatom-Substituted Diphosphenes .
. . . . . . . . . . . . . 53
42.2.6 Product Subclass 6: Stereodefined Diphosphenes . . . . .
. . . . . . . . . . . . . . . . . . . . 54
42.2.7 Product Subclass 7: Heteroatom-Substituted
Iminophosphines . . . . . . . . . . . 56
42.2.7.1 Synthesis of Product Subclass 7 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
56
42.2.7.1.1 Method 1: Elimination Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
5642.2.7.1.2 Method 2: Substitution Reactions . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 58
42.2.8 Product Subclass 8: Tetraphosphenes . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 58
42.2.8.1 Synthesis of Product Subclass 8 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
58
42.2.8.1.1 Method 1: Activation of White Phosphorus . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 58
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42.3 Product Class 3: Phosphenium SaltsM. Yoshifuji
42.3 Product Class 3: Phosphenium Salts . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 63
42.3.1 Synthesis of Product Class 3 . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
63
42.3.1.1 Method 1: Halogen Abstraction of Halophosphines . . . .
. . . . . . . . . . . . . . . . . 6342.3.1.2 Method 2: Alkylation
or Protonation of Diphosphenes . . . . . . . . . . . . . . . . . .
. 66
42.3.2 Applications of Product Class 3 in Organic Synthesis . .
. . . . . . . . . . . . . . . . . . . . . . . 67
42.3.2.1 Method 1: Reactions of Phosphenium Cations with
UnsaturatedHydrocarbons . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 67
42.4 Product Class 4: AlkylphosphinesE. Hey-Hawkins and A. A.
Karasik
42.4 Product Class 4: Alkylphosphines . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
42.4.1 Synthesis of Product Class 4 . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
72
42.4.1.1 Method 1: Synthesis from Phosphine, or Primary or
SecondaryPhosphines, and Alkyl Halides . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 73
42.4.1.1.1 Variation 1: From Phosphine and Alkyl Halides . . . .
. . . . . . . . . . . . . . . . . . . . . . . 7342.4.1.1.2
Variation 2: From Primary Phosphines and Alkyl Halides . . . . . .
. . . . . . . . . . . . 7442.4.1.1.3 Variation 3: From Secondary
Phosphines and Alkyl or Acyl Halides . . . . . . . . 7542.4.1.2
Method 2: Synthesis from Metal Organophosphides and Electrophiles .
. . 7542.4.1.2.1 Variation 1: Synthesis from Metal Organophosphides
and Alkyl Halides . . . 7542.4.1.2.2 Variation 2: Synthesis from
Metal Organophosphides and Esters . . . . . . . . . . 7942.4.1.2.3
Variation 3: Ring Opening of Tetrahydrofuran . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 8042.4.1.3 Method 3: Addition of
Phosphines to C—X Multiple Bonds . . . . . . . . . . . . . . .
8142.4.1.3.1 Variation 1: Addition to Alk-1-enes or Cyclic Alkenes
. . . . . . . . . . . . . . . . . . . . . 8142.4.1.3.2 Variation 2:
Addition to Carbonyl Groups . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . 8342.4.1.3.3 Variation 3: Mannich-Type
Reactions of Phosphines, Formaldehyde,
and Amines . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 8342.4.1.4 Method 4:
Synthesis from Halophosphines . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . 8342.4.1.4.1 Variation 1: From Phosphorus
Trihalides or Trialkyl Phosphites and
Organometallic Alkali Metal Compounds or Grignard Reagents
8342.4.1.4.2 Variation 2: From Alkyldihalophosphines and
Organometallic Alkali Metal
Compounds or Grignard Reagents . . . . . . . . . . . . . . . . .
. . . . . . . . . . 8642.4.1.4.3 Variation 3: From
Dialkylhalophosphines and Organometallic Alkali Metal
Compounds or Grignard Reagents . . . . . . . . . . . . . . . . .
. . . . . . . . . . 8742.4.1.4.4 Variation 4: From Chlorophosphines
and Other Organometallic Reagents . 9042.4.1.5 Method 5: Cleavage
of Diphosphines . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 9042.4.1.6 Method 6: Synthesis from Elemental
Phosphorus and Alkyl Halides,
Alcohols, or Alkenes . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 9142.4.1.7 Method 7: Reduction
of Halophosphines, Phosphinic Acids, Phosphinic
Acid Esters or Halides, and Trialkyl- and DialkylphosphineOxides
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . 93
42.4.1.7.1 Variation 1: Reduction of Halophosphines with Lithium
AluminumHydride or Other Metal Hydrides . . . . . . . . . . . . . .
. . . . . . . . . . . . . . 93
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42.4.1.7.2 Variation 2: Reduction of Alkylphosphonates with
Lithium AluminumHydride . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
42.4.1.7.3 Variation 3: Reduction of Dialkylphosphine Oxides,
Dialkylphosphinates,or Alkylphosphonates with Aluminum Derivatives
. . . . . . . . . . . 94
42.4.1.7.4 Variation 4: Reduction of Trialkylphosphine Oxides
with LithiumAluminum Hydride . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 97
42.4.1.7.5 Variation 5: Reduction of Dialkylphosphine Oxides,
Dialkylphosphinates,or Alkylphosphinates with Silanes . . . . . . .
. . . . . . . . . . . . . . . . . . . 97
42.4.1.8 Method 8: Reduction of Trialkylphosphine Sulfides and
P-ChiralPhosphine–Borane Complexes Bearing an Alkylsulfanyl Group
98
42.4.1.8.1 Variation 1: With Alkali Metals . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
9842.4.1.8.2 Variation 2: With Lithium Aluminum Hydride . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 9942.4.1.9 Method 9:
Synthesis from Quaternary Phosphonium Salts . . . . . . . . . . . .
. . 10042.4.1.9.1 Variation 1: Synthesis from
Tetrakis(hydroxymethyl)phosphonium
Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 10042.4.1.10 Method
10: Disproportionation of Dialkylphosphine Oxides . . . . . . . . .
. . . . 10142.4.1.11 Method 11: Addition Reactions of Unsaturated
Tertiary Vinylphosphines . 10142.4.1.12 Method 12: Enantioselective
Cleavage of a P—C Bond in Alkyldimethyl-
phosphine–Borane Complexes . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . 102
42.5 Product Class 5: Bis(alkylphosphino)- and
Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P
BondE. Hey-Hawkins and A. A. Karasik
42.5 Product Class 5: Bis(alkylphosphino)- and
Poly(alkylphosphino)alkanes,and Di- and Polyphosphines with a P—P
Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
42.5.1 Product Subclass 1: Bis(alkylphosphino)-
andPoly(alkylphosphino)alkanes . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 109
42.5.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
110
42.5.1.1.1 Method 1: Synthesis from Metal Dialkylphosphides and
AliphaticElectrophiles . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 110
42.5.1.1.1.1 Variation 1: Synthesis from Dialkylphosphides or
Dialkylphosphinesand Polyhaloalkanes . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 110
42.5.1.1.1.2 Variation 2: Synthesis from Dialkylphosphides and
Cyclic Sulfates . . . . . . . . 11542.5.1.1.1.3 Variation 3:
Synthesis from Dialkylphosphides and (Dialkylphosphino)alkyl
Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 11642.5.1.1.1.4 Variation
4: Synthesis from Dialkylphosphines and Polyhaloalkanes,
Alkylamines, and Alcohols . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . 11842.5.1.1.1.5 Variation 5: Synthesis
from Alkylphosphides and Dihaloalkanes . . . . . . . . . .
11942.5.1.1.1.6 Variation 6: Synthesis from Bis(alkylphosphides)
and Alkyl Halides . . . . . . . 12042.5.1.1.2 Method 2: Synthesis
from Metal Phosphinomethanides and
Electrophiles Containing Phosphino Groups . . . . . . . . . . .
. . . . . . 12042.5.1.1.2.1 Variation 1: Synthesis from
(Dialkylphosphino)methanides and
Dialkylhalophosphines . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 12042.5.1.1.2.2 Variation 2:
Enantioselective Synthesis from Lithium (Dialkylphosphi-
no)methanide–Borane Complexes and Alkylhalophosphines . 122
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42.5.1.1.2.3 Variation 3: Synthesis from
Poly(dialkylphosphino)methanides andDialkylhalophosphines . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
123
42.5.1.1.2.4 Variation 4: Synthesis from
[(Dialkylphosphino)methyl]silanes or-stannanes and
Dialkylhalophosphines . . . . . . . . . . . . . . . . . . . . . .
124
42.5.1.1.2.5 Variation 5: Oxidative Coupling of
(Dialkylphosphino)methanides . . . . . . . . 12542.5.1.1.2.6
Variation 6: Synthesis from (Dialkylphosphino)methanides and
Polyhaloalkanes or Analogues . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . 12742.5.1.1.3 Method 3: Synthesis from
Halophosphines and Organometallic
Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 12942.5.1.1.3.1 Variation
1: Synthesis from Dialkylhalophosphines and Dimetalated
Alkanes, Alkenes, or Alkynes . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 12942.5.1.1.3.2 Variation 2: Synthesis
from Bis(halophosphino)alkanes and
Organometallic Compounds . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . 13042.5.1.1.4 Method 4: Reduction of
Phosphine Oxides . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . 13242.5.1.1.4.1 Variation 1: Reduction of
Bis(dialkylphosphoryl)alkanes with Silanes . . . . .
13242.5.1.1.4.2 Variation 2: Reduction of
Bis(dialkylphosphoryl)alkanes with Lithium
Aluminum Hydride . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 13342.5.1.1.5 Method 5: Addition to
Double Bonds . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . 13542.5.1.1.5.1 Variation 1: Addition of Phosphines
to Polyenes and Their Heteroatom
Analogues . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 13542.5.1.1.5.2 Variation
2: Addition of Dialkylphosphines to Vinyl- or Allylphosphines . . .
13742.5.1.1.5.3 Variation 3: Addition of Polyphosphinoalkanes to
C=C or C=X Bonds . . . . 13942.5.1.1.5.4 Variation 4: Addition of
Diphosphines to Alkynes . . . . . . . . . . . . . . . . . . . . . .
. . 14142.5.1.1.6 Method 6: Decomposition of Phosphonium Salts . .
. . . . . . . . . . . . . . . . . . . . 14242.5.1.1.6.1 Variation
1: Reductive Cleavage of Quaternary Phosphonium Salts . . . . . . .
14242.5.1.1.6.2 Variation 2: Alcoholysis of Quaternary Phosphonium
Salts . . . . . . . . . . . . . . . 14342.5.1.1.7 Method 7:
Interconversion of Poly(alkylphosphino)alkanes . . . . . . . . . .
. . . 14342.5.1.1.7.1 Variation 1: From Diphosphinomethanides . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 14342.5.1.1.8
Method 8: Di- and Oligomerization by Interaction of Functional
Groups of Phosphines . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 14442.5.1.1.8.1 Variation 1: Di-
and Oligomerization of Phosphino Alcohols . . . . . . . . . . . . .
. 144
42.5.2 Product Subclass 2: Tetraalkyldiphosphines and
Polyalkylpolyphosphineswith a P—P Bond . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . 145
42.5.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
146
42.5.2.1.1 Method 1: Synthesis from Dialkylphosphides or
Dialkylphosphines andDialkylhalophosphines . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . 146
42.5.2.1.2 Method 2: Coupling of Dialkylphosphine Derivatives .
. . . . . . . . . . . . . . . . . . 14742.5.2.1.2.1 Variation 1:
Oxidative Coupling of Dialkylphosphines by Transition-Metal
Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 14742.5.2.1.2.2 Variation
2: Reductive Coupling of Dialkylhalophosphines by Alkali
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 14842.5.2.1.3 Method
3: Interconversion of Alkylpolyphosphines . . . . . . . . . . . . .
. . . . . . . . 14842.5.2.1.3.1 Variation 1: Alkylation of
Polyphosphide Anions . . . . . . . . . . . . . . . . . . . . . . .
. . 14842.5.2.1.3.2 Variation 2: Insertion into P—P Bonds . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
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42.6 Product Class 6: Cyclic PhosphinesD. Gudat
42.6 Product Class 6: Cyclic Phosphines . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 155
42.6.1 Product Subclass 1: Phosphiranes . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
42.6.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
156
42.6.1.1.1 Method 1: P-Alkylation of Primary Phosphines . . . .
. . . . . . . . . . . . . . . . . . . . . 15642.6.1.1.1.1 Variation
1: From Phosphines or Metal Phosphides and 1,2-Dihalides
or 1,2-Bis(toluenesulfonates) . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . 15742.6.1.1.1.2 Variation 2: From Metal
Phosphides and Oxiranes . . . . . . . . . . . . . . . . . . . . . .
. 15942.6.1.1.2 Method 2: P-Alkylation of Dichlorophosphines . . .
. . . . . . . . . . . . . . . . . . . . . . 16042.6.1.1.3 Method 3:
Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 16142.6.1.1.3.1 Variation 1: From
Electrophilic Phosphinidene Complexes and Alkenes . . .
16142.6.1.1.3.2 Variation 2: From Phosphaalkenes and Diazoalkanes .
. . . . . . . . . . . . . . . . . . . 16242.6.1.1.3.3 Variation 3:
From Phosphaalkenes or Phosphacumulenes and Carbenes
or Carbenoids . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 16442.6.1.1.4 Methods 4:
Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 166
42.6.2 Product Subclass 2: Phosphetanes . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 166
42.6.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
167
42.6.2.1.1 Method 1: P-Alkylation of Primary Phosphines . . . .
. . . . . . . . . . . . . . . . . . . . . 16742.6.2.1.1.1 Variation
1: From Phosphines and 1,3-Dihalides or Derivatives of 1,3-Diols
16742.6.2.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates .
. . . . . . . . . . . . . . . . . . . . . . . 16942.6.2.1.2 Method
2: P-Alkylation of Dichlorophosphines . . . . . . . . . . . . . . .
. . . . . . . . . . 17142.6.2.1.2.1 Variation 1: Lewis Acid Induced
Cyclization of Dichlorophosphines
with Alkenes and Subsequent Reduction . . . . . . . . . . . . .
. . . . . . . 17142.6.2.1.2.2 Variation 2: P-Alkylation of
Dichlorophosphines . . . . . . . . . . . . . . . . . . . . . . . .
. 17342.6.2.1.3 Method 3: Transformation of Phosphetanes . . . . .
. . . . . . . . . . . . . . . . . . . . . . 17342.6.2.1.3.1
Variation 1: P-Substitution of P-Halophosphetanes . . . . . . . . .
. . . . . . . . . . . . . 17442.6.2.1.3.2 Variation 2:
C-Substitution of Protected Phosphetanes and Subsequent
Deprotection . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 17442.6.2.1.4 Methods 4:
Miscellaneous Reactions . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 176
42.6.3 Product Subclass 3: 1,3-Diphosphetanes . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 176
42.6.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
177
42.6.3.1.1 Method 1: Cycloaddition Reactions . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . 17742.6.3.1.1.1
Variation 1: Cyclodimerization of Phosphaalkenes . . . . . . . . .
. . . . . . . . . . . . . . 17742.6.3.1.1.2 Variation 2:
Cyclooligomerization of Phosphaalkynes . . . . . . . . . . . . . .
. . . . . . 17842.6.3.1.1.3 Variation 3: Oxidative Coupling of
Polyphospholides . . . . . . . . . . . . . . . . . . . .
17942.6.3.1.2 Methods 2: Miscellaneous Reactions . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 180
42.6.4 Product Subclass 4: Five- and Six-Membered Rings:
Phospholanes,Phosphinanes, 2,5-Dihydrophospholes, and
1,2,5,6-Tetrahydro-phosphinines . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . 180
42.6.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
181
42.6.4.1.1 Method 1: P-Alkylation of Primary Phosphines . . . .
. . . . . . . . . . . . . . . . . . . . . 181
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42.6.4.1.1.1 Variation 1: From Phosphines and a,w-Dihalides or
Disulfonates ofa,w-Diols . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
42.6.4.1.1.2 Variation 2: From Phosphines and Cyclic Sulfates .
. . . . . . . . . . . . . . . . . . . . . . . 18342.6.4.1.2 Method
2: Alkylation of Dichlorophosphines or Phosphinic Acid
O,S-Diesters . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 18642.6.4.1.2.1 Variation
1: From Dichlorophosphines or Phosphinic Acid O,S-Diesters
and a,w-Di-Grignard or Dilithium Reagents . . . . . . . . . . .
. . . . . . 18642.6.4.1.2.2 Variation 2: From Dichlorophosphines,
Alkenes, and Organometallic
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 18742.6.4.1.3 Method 3:
Hydrophosphination of Double Bonds . . . . . . . . . . . . . . . .
. . . . . . 18842.6.4.1.3.1 Variation 1: Addition of Phosphines to
Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . .
18942.6.4.1.3.2 Variation 2: Addition of Phosphine and Primary
Phosphines to
1,4-Dien-3-ones . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . 19042.6.4.1.3.3 Variation 3:
Addition of Phosphines to Carbonyl Compounds . . . . . . . . . . .
. 19242.6.4.1.4 Method 4: Cycloaddition or Metathesis Reactions . .
. . . . . . . . . . . . . . . . . . . . 19242.6.4.1.4.1 Variation
1: 2,5-Dihydrophospholes from Dihalophosphines and Dienes
via [4 + 1] Cycloaddition and Reduction . . . . . . . . . . . .
. . . . . . . . . 19342.6.4.1.4.2 Variation 2:
1,2,5,6-Tetrahydrophosphinines from Phosphaalkenes and
1,3-Dienes via [4 + 2] Cycloaddition . . . . . . . . . . . . . .
. . . . . . . . . . . 19542.6.4.1.4.3 Variation 3:
7-Phosphanorbornenes from [4 + 2] Cycloaddition of
Phosphole Derivatives with Dienophiles . . . . . . . . . . . . .
. . . . . . . . 19642.6.4.1.4.4 Variation 4: 2,5-Dihydrophospholes
from Diallylphosphines via Alkene
Metathesis . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 19942.6.4.1.5 Method 5:
Transformation of Cyclic Phosphines . . . . . . . . . . . . . . . .
. . . . . . . . 20042.6.4.1.5.1 Variation 1: Transformation of
P-Substituents in Five- and Six-Membered
Heterocycles . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 20042.6.4.1.5.2 Variation
2: Lithiation and Electrophilic Substitution at a-C—H Bonds
in Cyclic Phosphine Oxides and Borane Complexes . . . . . . . .
. . 20142.6.4.1.6 Methods 6: Miscellaneous Reactions . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
42.6.5 Product Subclass 5: Cyclic Phosphines with Seven-Membered
andLarger Rings . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. 204
42.6.5.1 Synthesis of Product Subclass 5 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
205
42.6.5.1.1 Method 1: P-Alkylation of Phosphines . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . 20542.6.5.1.2
Method 2: P-Alkylation of Dihalophosphines . . . . . . . . . . . .
. . . . . . . . . . . . . . . 20642.6.5.1.3 Method 3: P-Alkylation
of Tertiary Phosphines or Diphosphines and
Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 20742.6.5.1.4 Method 4:
Hydrophosphination of Alkenes and Alkynes . . . . . . . . . . . . .
. . . 21042.6.5.1.5 Methods 5: Miscellaneous Reactions . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
42.7 Product Class 7: Dialkylphosphinous Acids and DerivativesK.
M. Pietrusiewicz and M. Stankevič
42.7 Product Class 7: Dialkylphosphinous Acids and Derivatives .
. . . . . . . . . . . . . 221
42.7.1 Product Subclass 1: Dialkylphosphinous Acid Halides . . .
. . . . . . . . . . . . . . . . . 221
42.7.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
221
42.7.1.1.1 Method 1: Synthesis from Phosphorous Halides by P—C
Bond Formation 221
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42.7.1.1.2 Method 2: Ligand Exchange in Dialkylphosphinous Acid
Derivatives . . . . . 222
42.7.1.2 Applications of Product Subclass 1 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 223
42.7.2 Product Subclass 2: Dialkylphosphinous Acids . . . . . .
. . . . . . . . . . . . . . . . . . . . . 224
42.7.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
224
42.7.2.1.1 Method 1: Synthesis from H-Phosphonates by
Substitution . . . . . . . . . . . . . 22442.7.2.1.2 Method 2:
Hydrolysis of Dialkylphosphinous Acid Derivatives . . . . . . . . .
. . 226
42.7.2.2 Applications of Product Subclass 2 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 226
42.7.3 Product Subclass 3: Dialkylphosphinous Acid Esters . . .
. . . . . . . . . . . . . . . . . . 227
42.7.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
227
42.7.3.1.1 Method 1: Alcoholysis of Dialkylphosphinous Acid
Derivatives . . . . . . . . . . 22742.7.3.1.2 Method 2: Synthesis
from Phosphorous Acid Monoester Dihalides by
P—C Bond Formation . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . 228
42.7.3.2 Applications of Product Subclass 3 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 229
42.7.4 Product Subclass 4: Dialkylthiophosphinous Acids . . . .
. . . . . . . . . . . . . . . . . . . 230
42.7.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
230
42.7.4.1.1 Method 1: Synthesis from Dialkylphosphinous Acid
Derivatives . . . . . . . . . 230
42.7.4.2 Applications of Product Subclass 4 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 230
42.7.5 Product Subclass 5: Dialkylthiophosphinous Acid Esters .
. . . . . . . . . . . . . . . . 231
42.7.5.1 Synthesis of Product Subclass 5 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
231
42.7.5.1.1 Method 1: Synthesis from Dialkylphosphinous Acid
Halides . . . . . . . . . . . . 231
42.7.6 Product Subclass 6: Dialkylselenophosphinous Acids . . .
. . . . . . . . . . . . . . . . . . 231
42.7.6.1 Synthesis of Product Subclass 6 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
232
42.7.6.1.1 Method 1: Synthesis from Dialkylphosphines . . . . .
. . . . . . . . . . . . . . . . . . . . . 232
42.7.7 Product Subclass 7: Dialkylselenophosphinous Acid Esters
. . . . . . . . . . . . . . . 232
42.7.7.1 Synthesis of Product Subclass 7 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
232
42.7.7.1.1 Method 1: Synthesis from Dialkylphosphinous Acid
Halides . . . . . . . . . . . . 232
42.7.8 Product Subclass 8: Dialkylphosphinous Acid Amides . . .
. . . . . . . . . . . . . . . . . 233
42.7.8.1 Synthesis of Product Subclass 8 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
233
42.7.8.1.1 Method 1: Aminolysis of Dialkylphosphinous Acid
Derivatives . . . . . . . . . . 23342.7.8.1.2 Method 2: Synthesis
from Phosphorous Acid Derivatives by P—C Bond
Formation . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 234
42.7.8.2 Applications of Product Subclass 8 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 234
42.8 Product Class 8: Alkylphosphonous Acids and DerivativesK.
M. Pietrusiewicz and M. Stankevič
42.8 Product Class 8: Alkylphosphonous Acids and Derivatives . .
. . . . . . . . . . . . . . 243
42.8.1 Product Subclass 1: Alkylphosphonous Acid Dihalides . . .
. . . . . . . . . . . . . . . . 243
42.8.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
244
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42.8.1.1.1 Method 1: Electrophilic Alkylation of Phosphorus
Trihalides . . . . . . . . . . . . 24442.8.1.1.2 Method 2:
Nucleophilic Alkylation of Phosphorus Trihalides by
Organometallic Reagents . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . 24442.8.1.1.3 Method 3: Ligand Exchange
Using Alkylphosphines as Substrates . . . . . . . 245
42.8.1.2 Applications of Product Subclass 1 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 246
42.8.2 Product Subclass 2: Alkylphosphonous Acid Monohalides . .
. . . . . . . . . . . . . . 247
42.8.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
247
42.8.2.1.1 Method 1: Partial Hydrolysis of
Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . 247
42.8.3 Product Subclass 3: Alkylphosphonous Acid Monoester
Monohalides . . . . 247
42.8.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
247
42.8.3.1.1 Method 1: Ligand Exchange in Alkyl(dihalo)phosphines
. . . . . . . . . . . . . . . . 247
42.8.4 Product Subclass 4: Alkylthiophosphonous Acid Monohalide
Monoesters 248
42.8.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
248
42.8.4.1.1 Method 1: Ligand Exchange of Alkyl(dihalo)phosphines
. . . . . . . . . . . . . . . . 248
42.8.5 Product Subclass 5: Alkylphosphonous Acid Monoamide
Monohalides . . . 249
42.8.5.1 Synthesis of Product Subclass 5 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
249
42.8.5.1.1 Method 1: Partial Aminolysis of
Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . 24942.8.5.1.2
Method 2: Ligand Exchange in Alkyl(amino)phosphine Derivatives . .
. . . . 250
42.8.6 Product Subclass 6: Alkylphosphonous Acids . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 251
42.8.6.1 Synthesis of Product Subclass 6 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
251
42.8.6.1.1 Method 1: Hydrolysis of Alkyl(halo)phosphines . . . .
. . . . . . . . . . . . . . . . . . . . 25142.8.6.1.2 Method 2:
Hydrophosphination of Alkenes . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 252
42.8.6.2 Applications of Product Subclass 6 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 252
42.8.7 Product Subclass 7: Alkylphosphonous Acid Monoesters . .
. . . . . . . . . . . . . . . 253
42.8.7.1 Synthesis of Product Subclass 7 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
253
42.8.7.1.1 Method 1: Alcoholysis of Alkylphosphines . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 25342.8.7.1.2 Method
2: Esterification of Monoalkylphosphinic Acids . . . . . . . . . .
. . . . . . . 25442.8.7.1.3 Method 3: Hydrolysis of Dialkyl
Phosphonites and Related Compounds . 25542.8.7.1.4 Method 4:
Hydrophosphination of Alkenes . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 255
42.8.7.2 Applications of Product Subclass 7 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 256
42.8.8 Product Subclass 8: Alkylphosphonous Acid Diesters . . .
. . . . . . . . . . . . . . . . . . 256
42.8.8.1 Synthesis of Product Subclass 8 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
256
42.8.8.1.1 Method 1: Alcoholysis of Alkylphosphonites . . . . .
. . . . . . . . . . . . . . . . . . . . . . 25642.8.8.1.2 Method 2:
Synthesis from Halophosphonites . . . . . . . . . . . . . . . . . .
. . . . . . . . 257
42.8.8.2 Applications of Product Subclass 8 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 258
42.8.9 Product Subclass 9: Alkylthiophosphonous Acid
S-Monoesters . . . . . . . . . . . 258
42.8.9.1 Synthesis of Product Subclass 9 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
258
42.8.9.1.1 Method 1: Hydrolysis of
Alkyl(alkylsulfanyl)(halo)phosphines . . . . . . . . . . . 258
42.8.10 Product Subclass 10: Alkylphosphonous Acid Monoamides .
. . . . . . . . . . . . . 259
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42.8.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
259
42.8.10.1.1 Method 1: Hydrolysis of Alkyl(diamino)phosphines . .
. . . . . . . . . . . . . . . . . . . 259
42.8.11 Product Subclass 11: Alkylthiophosphonous Acid
O-Monoesters . . . . . . . . . 259
42.8.11.1 Synthesis of Product Subclass 11 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
260
42.8.11.1.1 Method 1: Synthesis from
Alkyl(alkoxy)(halo)phosphines . . . . . . . . . . . . . . . 260
42.8.12 Product Subclass 12: Alkylthiophosphonous Acid Diesters
. . . . . . . . . . . . . . . 260
42.8.12.1 Synthesis of Product Subclass 12 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
260
42.8.12.1.1 Method 1: Alcoholysis of
Alkyl(alkylsulfanyl)(halo)phosphines . . . . . . . . . . 260
42.8.13 Product Subclass 13: Alkylphosphonous Acid Monoester
Monoamides . . . 261
42.8.13.1 Synthesis of Product Subclass 13 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
261
42.8.13.1.1 Method 1: Alcoholysis of Alkylphosphine Derivatives
. . . . . . . . . . . . . . . . . . . 26142.8.13.1.2 Method 2:
Aminolysis of Alkylphosphonous Acid Derivatives . . . . . . . . . .
. 262
42.8.13.2 Applications of Product Subclass 13 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 262
42.8.14 Product Subclass 14: Alkyldithiophosphonous Acid
Diesters . . . . . . . . . . . . . 263
42.8.14.1 Synthesis of Product Subclass 14 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
42.8.14.1.1 Method 1: Synthesis from Primary Alkylphosphines and
Disulfides . . . . . . 26342.8.14.1.2 Method 2: Thioalcoholysis of
Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . . . . 263
42.8.15 Product Subclass 15: Alkylthiophosphonous Acid Monoester
Monoamides 264
42.8.15.1 Synthesis of Product Subclass 15 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
264
42.8.15.1.1 Method 1: Thioalcoholysis of
Alkyl(diamino)phosphines . . . . . . . . . . . . . . . . 264
42.8.16 Product Subclass 16: Alkyldiselenophosphonous Acid
Diesters . . . . . . . . . . . 265
42.8.16.1 Synthesis of Product Subclass 16 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
265
42.8.16.1.1 Method 1: Selenoalcoholysis of
Alkyl(dihalo)phosphines . . . . . . . . . . . . . . . 265
42.8.17 Product Subclass 17: Alkylphosphonous Acid Diamides . .
. . . . . . . . . . . . . . . . 265
42.8.17.1 Synthesis of Product Subclass 17 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
265
42.8.17.1.1 Method 1: Aminolysis of Substituted Alkylphosphines
. . . . . . . . . . . . . . . . . . 26542.8.17.1.2 Method 2:
Synthesis from Diamino(halo)phosphines . . . . . . . . . . . . . .
. . . . . 266
42.8.17.2 Applications of Product Subclass 17 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 266
42.9 Product Class 9: Phosphorous Acid and DerivativesM.
Stankevič and K. M. Pietrusiewicz
42.9 Product Class 9: Phosphorous Acid and Derivatives . . . . .
. . . . . . . . . . . . . . . . . 275
42.9.1 Product Subclass 1: Phosphorous Acid Monoester Dihalides
. . . . . . . . . . . . . 275
42.9.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
275
42.9.1.1.1 Method 1: Alcoholysis of Phosphorus Trihalides . . .
. . . . . . . . . . . . . . . . . . . . . 27542.9.1.1.2 Method 2:
Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 276
42.9.1.2 Applications of Product Subclass 1 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 276
42.9.2 Product Subclass 2: Phosphorothious Acid S-Monoester
Dihalides . . . . . . . 276
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42.9.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
277
42.9.2.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides .
. . . . . . . . . . . . . . . . . . . 277
42.9.2.2 Applications of Product Subclass 2 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 277
42.9.3 Product Subclass 3: Phosphorous Acid Monoamide Dihalides
. . . . . . . . . . . . 277
42.9.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
277
42.9.3.1.1 Method 1: Aminolysis of Phosphorus Trihalides . . . .
. . . . . . . . . . . . . . . . . . . . 27742.9.3.1.2 Method 2:
Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 278
42.9.3.2 Applications of Product Subclass 3 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 279
42.9.4 Product Subclass 4: Phosphorous Acid Monoester
Monohalides . . . . . . . . . . 279
42.9.5 Product Subclass 5: Phosphorous Acid Diester Monohalides
. . . . . . . . . . . . . 279
42.9.5.1 Synthesis of Product Subclass 5 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
280
42.9.5.1.1 Method 1: Alcoholysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . 28042.9.5.1.2 Method 2:
Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 280
42.9.5.3 Applications of Product Subclass 5 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 281
42.9.6 Product Subclass 6: Phosphorothious Acid Diester
Monohalides . . . . . . . . . 282
42.9.6.1 Synthesis of Product Subclass 6 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
282
42.9.6.1.1 Method 1: Amine–Halogen Exchange in Phosphorothious
Acid DiesterMonoamides . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 282
42.9.7 Product Subclass 7: Phosphorous Acid Monoester Monoamide
Monoha-lides . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . 282
42.9.7.1 Synthesis of Product Subclass 7 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
283
42.9.7.1.1 Method 1: Alcoholysis of Phosphorous Acid Monoamide
Dihalides . . . . . . 28342.9.7.1.2 Method 2: Aminolysis of
Phosphorous Acid Monoester Dihalides . . . . . . . 28342.9.7.1.3
Method 3: Consecutive Alcoholysis and Aminolysis of Phosphorus
Trihalides . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 28342.9.7.1.4 Method
4: Ligand-Exchange Reactions of Phosphorous Acid Derivatives .
284
42.9.7.2 Applications of Product Subclass 7 in Organic Synthesis
. . . . . . . . . . . . . . . . . . . . . 284
42.9.8 Product Subclass 8: Phosphorodithious Acid Diester
Monohalides . . . . . . . 285
42.9.8.1 Synthesis of Product Subclass 8 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
285
42.9.8.1.1 Method 1: Thioalcoholysis of Phosphorus Trihalides .
. . . . . . . . . . . . . . . . . . . 28542.9.8.1.2 Method 2:
Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 285
42.9.9 Product Subclass 9: Phosphorothious Acid Monoester
MonoamideMonohalides . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . 286
42.9.9.1 Synthesis of Product Subclass 9 . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
286
42.9.9.1.1 Method 1: Amine–Halogen Exchange in Phosphorothious
Acid DiesterMonoamides . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 286
42.9.10 Product Subclass 10: Phosphorous Acid Diamide
Monohalides . . . . . . . . . . . 287
42.9.10.1 Synthesis of Product Subclass 10 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
287
42.9.10.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 28742.9.10.1.2 Method 2:
Ligand-Exchange Reactions of Phosphorous Acid Derivatives . 288
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42.9.10.2 Applications of Product Subclass 10 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 288
42.9.11 Product Subclass 11: Phosphorous Acid Monoesters . . . .
. . . . . . . . . . . . . . . . . 288
42.9.11.1 Synthesis of Product Subclass 11 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
289
42.9.11.1.1 Method 1: Hydrolysis of Phosphorous Acid Esters . .
. . . . . . . . . . . . . . . . . . . . 28942.9.11.1.2 Method 2:
Synthesis from Other Phosphorous Acid Derivatives . . . . . . . . .
28942.9.11.1.3 Method 3: Esterification of Phosphorous Acid . . . .
. . . . . . . . . . . . . . . . . . . . . . 290
42.9.11.2 Applications of Product Subclass 11 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 291
42.9.12 Product Subclass 12: Phosphorous Acid Diesters
(Secondary Phosphites) 291
42.9.12.1 Synthesis of Product Subclass 12 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
291
42.9.12.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 29142.9.12.1.2 Method 2:
Alcoholysis of Phosphorous Acid Derivatives . . . . . . . . . . . .
. . . . 29242.9.12.1.3 Method 3: Other Syntheses from Phosphorous
Acid Derivatives . . . . . . . . 29342.9.12.1.4 Method 4:
Esterification of Phosphorous Acid Derivatives . . . . . . . . . .
. . . . 293
42.9.12.2 Applications of Product Subclass 12 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 294
42.9.13 Product Subclass 13: Phosphorous Acid Triesters
(Tertiary Phosphites) . . . 295
42.9.13.1 Synthesis of Product Subclass 13 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
295
42.9.13.1.1 Method 1: Alcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . . . . . 29542.9.13.1.2 Method
2: Transesterification of Phosphorous Acid Triesters . . . . . . .
. . . . . 297
42.9.13.2 Applications of Product Subclass 13 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 297
42.9.14 Product Subclass 14: Phosphorothious Acid O-Monoesters .
. . . . . . . . . . . . . . 298
42.9.14.1 Synthesis of Product Subclass 14 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
298
42.9.14.1.1 Method 1: Sulfanylation of Phosphorous Acid Diesters
. . . . . . . . . . . . . . . . . 298
42.9.15 Product Subclass 15: Phosphorothious Acid O,O-Diesters .
. . . . . . . . . . . . . . . 299
42.9.15.1 Synthesis of Product Subclass 15 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
299
42.9.15.1.1 Method 1: Sulfanylation of Phosphorous Acid
Derivatives . . . . . . . . . . . . . . 299
42.9.15.2 Applications of Product Subclass 15 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 300
42.9.16 Product Subclass 16: Phosphorothious Acid Triesters . .
. . . . . . . . . . . . . . . . . . 300
42.9.16.1 Synthesis of Product Subclass 16 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
300
42.9.16.1.1 Method 1: Alcoholysis of Phosphorothious Acid
Derivatives . . . . . . . . . . . . 30042.9.16.1.2 Method 2:
Thioalcoholysis of Phosphorous Acid Derivatives . . . . . . . . . .
. . 301
42.9.17 Product Subclass 17: Phosphorodithious Acid S,S-Diesters
. . . . . . . . . . . . . . . 301
42.9.18 Product Subclass 18: Phosphorodithious Acid O-Monoesters
. . . . . . . . . . . . . 301
42.9.19 Product Subclass 19: Phosphorodithious Acid Triesters .
. . . . . . . . . . . . . . . . . 302
42.9.19.1 Synthesis of Product Subclass 19 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
302
42.9.19.1.1 Method 1: Thioalcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . 302
42.9.20 Product Subclass 20: Phosphoroselenous Acid O,O-Diesters
. . . . . . . . . . . . . . 303
42.9.20.1 Synthesis of Product Subclass 20 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
303
42.9.20.1.1 Method 1: Selanylation of Phosphorous Acid Diester
Monohalides . . . . . . 303
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42.9.21 Product Subclass 21: Phosphorous Acid Monoester
Monoamides . . . . . . . . 303
42.9.21.1 Synthesis of Product Subclass 21 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
303
42.9.21.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 303
42.9.22 Product Subclass 22: Phosphorous Acid Diester Monoamides
. . . . . . . . . . . . 304
42.9.22.1 Synthesis of Product Subclass 22 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
304
42.9.22.1.1 Method 1: Alcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . . . . . 30442.9.22.1.2 Method
2: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . .
. . . . . . 306
42.9.22.2 Applications of Product Subclass 22 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 306
42.9.23 Product Subclass 23: Phosphorothious Acid Diester
Monoamides . . . . . . . . 307
42.9.23.1 Synthesis of Product Subclass 23 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
307
42.9.23.1.1 Method 1: Thioalcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . 307
42.9.24 Product Subclass 24: Phosphorous Acid Diamides . . . . .
. . . . . . . . . . . . . . . . . . . 308
42.9.24.1 Synthesis of Product Subclass 24 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
308
42.9.24.1.1 Method 1: Hydrolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 308
42.9.25 Product Subclass 25: Phosphorous Acid Monoester Diamides
. . . . . . . . . . . . 309
42.9.25.1 Synthesis of Product Subclass 25 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
309
42.9.25.1.1 Method 1: Alcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . . . . . 30942.9.25.1.2 Method
2: Aminolysis of Phosphorous Acid Derivatives . . . . . . . . . . .
. . . . . . 310
42.9.25.2 Applications of Product Subclass 25 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 311
42.9.26 Product Subclass 26: Phosphorotrithious Acid Triesters .
. . . . . . . . . . . . . . . . . 311
42.9.26.1 Synthesis of Product Subclass 26 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
311
42.9.26.1.1 Method 1: Thioalcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . 311
42.9.27 Product Subclass 27: Phosphorodithious Acid Diester
Monoamides . . . . . . 312
42.9.27.1 Synthesis of Product Subclass 27 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
312
42.9.27.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 312
42.9.28 Product Subclass 28: Phosphorothious Acid Monoester
Diamides . . . . . . . . 312
42.9.28.1 Synthesis of Product Subclass 28 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
313
42.9.28.1.1 Method 1: Thioalcoholysis of Phosphorous Acid
Derivatives . . . . . . . . . . . . 313
42.9.29 Product Subclass 29: Phosphorotriselenous Acid Triesters
. . . . . . . . . . . . . . . 313
42.9.29.1 Synthesis of Product Subclass 29 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
313
42.9.29.1.1 Method 1: Reaction of a Diselenide with Elemental
Phosphorus . . . . . . . . . 313
42.9.30 Product Subclass 30: Phosphorous Acid Triamides . . . .
. . . . . . . . . . . . . . . . . . . 313
42.9.30.1 Synthesis of Product Subclass 30 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
314
42.9.30.1.1 Method 1: Aminolysis of Phosphorous Acid Derivatives
. . . . . . . . . . . . . . . . . 314
42.9.30.2 Applications of Product Subclass 30 in Organic
Synthesis . . . . . . . . . . . . . . . . . . . . 315
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42.10 Applications of Tricoordinated Phosphorus Compoundsin
Homogeneous Catalysis
42.10.1 General Catalytic MethodsM. Toffano
42.10.1 General Catalytic Methods . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
347
42.10.1.1 Formation of C—C Bonds . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
347
42.10.1.1.1 Method 1: Palladium-Promoted Cross-Coupling
Reactions . . . . . . . . . . . . . . 34742.10.1.1.2 Method 2:
Catalysis with Phosphonium Salts as Ligand Precursors . . . . . .
352
42.10.1.2 Formation of C—N Bonds . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
353
42.10.1.2.1 Method 1: Amination of Aryl and Hetaryl Halides
orTrifluoromethanesulfonates . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 353
42.10.1.2.2 Method 2: Amination of Alk-1-enyl Halides
orTrifluoromethanesulfonates . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 360
42.10.1.2.3 Method 3: Intramolecular Amination Reactions . . . .
. . . . . . . . . . . . . . . . . . . . 360
42.10.1.3 Formation of C—O Bonds . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
361
42.10.1.3.1 Method 1: Alkyl Aryl Ether Synthesis . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . 36142.10.1.3.2
Method 2: Diaryl Ether Synthesis . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 362
42.10.1.4 Formation of C—P Bonds . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
363
42.10.1.4.1 Method 1: Formation of Alkylphosphorus Compounds . .
. . . . . . . . . . . . . . . 36342.10.1.4.2 Method 2: Formation of
Alkenylphosphorus Compounds . . . . . . . . . . . . . . .
36442.10.1.4.2.1 Variation 1: Hydrophosphination of Alkynes . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 36442.10.1.4.2.2
Variation 2: Coupling Reactions . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 36642.10.1.4.3 Method
3: Formation of Alkynylphosphorus Compounds . . . . . . . . . . . .
. . . 36842.10.1.4.4 Method 4: Formation of Arylphosphorus
Compounds . . . . . . . . . . . . . . . . . . 368
42.10.1.5 Formation of C—S Bonds . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
369
42.10.1.5.1 Method 1: Formation of an Aryl—Sulfur Bond . . . . .
. . . . . . . . . . . . . . . . . . . . . 37042.10.1.5.2 Method 2:
Formation of an Alkenyl—Sulfur Bond . . . . . . . . . . . . . . . .
. . . . . . . 37042.10.1.5.3 Method 3: Formation of an
Alkynyl—Sulfur Bond . . . . . . . . . . . . . . . . . . . . . . .
371
42.10.1.6 Formation of C—Sn Bonds . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
372
42.10.1.7 Synthesis with Catalyst Recycling . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
373
42.10.1.7.1 Method 1: Catalysis with Fluorinated Phosphines . .
. . . . . . . . . . . . . . . . . . . . 37342.10.1.7.2 Method 2:
Catalysis with Water-Soluble Phosphines . . . . . . . . . . . . . .
. . . . . . 37442.10.1.7.2.1 Variation 1: Catalysis with Sulfonated
and Carboxylated Phosphines . . . . . 37542.10.1.7.2.2 Variation 2:
Catalysis with Phosphines Bearing Ammonium Groups . . . . . .
37642.10.1.7.2.3 Variation 3: Catalysis with Carbohydrate-Derived
Phosphines . . . . . . . . . . . . 37742.10.1.7.2.4 Variation 4:
Catalysis with Polyether Phosphines . . . . . . . . . . . . . . . .
. . . . . . . . 37742.10.1.7.3 Method 3: Catalysis with
Polymer-Supported Phosphines . . . . . . . . . . . . . .
37842.10.1.7.3.1 Variation 1: Metal-Promoted Catalysis with
Polymer-Supported
Phosphines . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 37842.10.1.7.3.2
Variation 2: Catalysis with Polymer-Supported Phosphine Reagents .
. . . . . 380
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42.10.2 Enantioselective Catalytic MethodsJ.-C. Fiaud and A.
Marinetti
42.10.2 Enantioselective Catalytic Methods . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . 391
42.10.2.1 Approaches to Enantioselective Catalysts . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
42.10.2.1.1 Method 1: Approaches to Chiral Cyclic Phosphines . .
. . . . . . . . . . . . . . . . . . . 39742.10.2.1.1.1 Variation 1:
Phospholane-Based Chiral Ligands . . . . . . . . . . . . . . . . .
. . . . . . . . . 39742.10.2.1.1.2 Variation 2: Phosphetane-Based
Chiral Ligands . . . . . . . . . . . . . . . . . . . . . . . . . .
39842.10.2.1.1.3 Variation 3: Phosphepin-Based Chiral Ligands . . .
. . . . . . . . . . . . . . . . . . . . . . . . 39942.10.2.1.2
Method 2: Approaches to Atropisomeric Biaryl Bisphosphines . . . .
. . . . . . 39942.10.2.1.3 Method 3: Approaches to
Ferrocenylphosphines with Planar Chirality . . . 40242.10.2.1.4
Method 4: Approaches to Hybrid Phosphorus–Nitrogen Ligands . . . .
. . . . 40542.10.2.1.4.1 Variation 1: Phosphino-4,5-dihydrooxazole
Ligands . . . . . . . . . . . . . . . . . . . . . 40542.10.2.1.4.2
Variation 2: Phosphinite–4,5-Dihydrooxazole Ligands . . . . . . . .
. . . . . . . . . . . 40842.10.2.1.4.3 Variation 3:
Phosphino-4,5-dihydro-1H-imidazole Ligands . . . . . . . . . . . .
. . . 40842.10.2.1.4.4 Variation 4: Phosphinopyridine and
Phosphinoquinoline Ligands . . . . . . . . . 40842.10.2.1.4.5
Variation 5: Pyridylphosphinite and Quinolylphosphinite Ligands . .
. . . . . . . 40942.10.2.1.4.6 Variation 6: Trost Ligands . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . 40942.10.2.1.5 Method 5: Approaches to Ligands
Bearing P—O and P—N Bonds . . . . . . . . 41042.10.2.1.5.1
Variation 1: Phosphinite [P(C,C,O)] Ligands . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 41042.10.2.1.5.2 Variation 2:
Phosphonite [P(C,O,O)] Ligands . . . . . . . . . . . . . . . . . .
. . . . . . . . . . 41042.10.2.1.5.3 Variation 3: Phosphite
[P(O,O,O)] Ligands . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . 41042.10.2.1.5.4 Variation 4: Phosphoramidite
[P(O,O,N)] Ligands . . . . . . . . . . . . . . . . . . . . . . .
410
42.10.2.2 Enantioselective C—C Bond-Forming Reactions . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 411
42.10.2.2.1 Method 1: Metal-Catalyzed Allylic Alkylation
(Tsuji–Trost Reaction) . . . . . 41142.10.2.2.1.1 Variation 1:
Using 1,3-Symmetrically Substituted Allylic Ligands . . . . . . . .
. 41142.10.2.2.1.2 Variation 2: Using Monosubstituted Allylic
Ligands . . . . . . . . . . . . . . . . . . . . . .
41342.10.2.2.1.3 Variation 3: Using 1,3-Dissymmetrically
Disubstituted Allylic Substrates . . 41542.10.2.2.2 Method 2:
Palladium-Catalyzed Arylation of Alkenes (Heck Reaction) . . .
41842.10.2.2.2.1 Variation 1: Selection of Enantiotopic C=C Bonds
of an Achiral Substrate . 41942.10.2.2.2.2 Variation 2: Selection
of Enantiotopic Faces of an Achiral Alkenic Substrate
42042.10.2.2.2.3 Variation 3: Selection of Enantiotopic Sites of an
Achiral Alkenic Substrate 42342.10.2.2.3 Method 3: Metal-Catalyzed
Coupling Reactions . . . . . . . . . . . . . . . . . . . . . . . .
42442.10.2.2.4 Method 4: Conjugate Addition Reactions . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 42742.10.2.2.4.1
Variation 1: Metal-Catalyzed 1,4-Addition of Organometallic
Reagents to
Activated Alkenes . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 42742.10.2.2.4.2 Variation 2:
Copper-Catalyzed Asymmetric 1,4-Addition of Organozinc
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 42742.10.2.2.4.3
Variation 3: Conjugate Addition to Cyclohexa-2,5-dienones . . . . .
. . . . . . . . . 42842.10.2.2.4.4 Variation 4: Copper-Catalyzed
Asymmetric 1,4-Addition of Grignard
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 42942.10.2.2.4.5
Variation 5: Rhodium-Catalyzed Asymmetric 1,4-Addition of
Organoboron
Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 42942.10.2.2.5 Methods
5: Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . 43142.10.2.2.5.1 Variation 1:
Metal-Catalyzed Addition of Organometallic Reagents to
Unactivated Alkenes . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 431
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42.10.2.2.5.2 Variation 2: Metal-Catalyzed Addition of
Organometallic Reagentsto Carbonyl Compounds . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 432
42.10.2.3 Enantioselective C—H Bond-Forming Reactions . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 433
42.10.2.3.1 Method 1: Rhodium-Promoted Hydrogenation of Alkenes
. . . . . . . . . . . . . . 43342.10.2.3.2 Method 2:
Iridium-Promoted Hydrogenation of Nonfunctionalized
Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 43842.10.2.3.3 Method
3: Iridium-Promoted Hydrogenation of Imines . . . . . . . . . . . .
. . . . . 44142.10.2.3.4 Method 4: Ruthenium-Promoted Hydrogenation
of Ketones . . . . . . . . . . . . 44442.10.2.3.5 Method 5:
Rhodium-Promoted Hydroformylation of Alkenes . . . . . . . . . . .
45142.10.2.3.6 Method 6: Rhodium-Promoted Hydroboration of Alkenes
. . . . . . . . . . . . . . 454
42.11 Applications of Tricoordinated Phosphorus Compounds
inOrganocatalysisJ. L. Methot and W. R. Roush
42.11 Applications of Tricoordinated Phosphorus Compounds
inOrganocatalysis . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
469
42.11.1 Method 1: Morita–Baylis–Hillman Reactions . . . . . . .
. . . . . . . . . . . . . . . . . . . . 46942.11.1.1 Variation 1:
Tandem Phosphorylsilylation/Ireland–Claisen Rearrangement
47242.11.1.2 Variation 2: Intramolecular Morita–Baylis–Hillman
Allylic Alkylation . . . . . . 47342.11.1.3 Variation 3:
a-Arylation of Enones with Hypervalent Bismuth Reagents . .
47442.11.1.4 Variation 4: Phosphine-Mediated Reductive Condensation
of
Acyloxybutynoates . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 47442.11.1.5 Variation 5:
Regioselective Allylic Displacement . . . . . . . . . . . . . . . .
. . . . . . . . . 47542.11.1.6 Variation 6: The
Morita–Baylis–Hillman Reaction Using Air-Stable
Phosphine Reagents . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . 47642.11.1.7 Variation 7:
Asymmetric Morita–Baylis–Hillman Reactions . . . . . . . . . . . .
. . . 47642.11.1.8 Variation 8: The Aza-Morita–Baylis–Hillman
Reaction . . . . . . . . . . . . . . . . . . . . 47742.11.2 Method
2: Michael Addition Reactions . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . 47942.11.3 Method 3: Nucleophilic
Addition Reactions at Nonactivated Positions . . . 48142.11.3.1
Variation 1: Chiral Nucleophilic Addition Reactions . . . . . . . .
. . . . . . . . . . . . . . 48442.11.3.2 Variation 2: Nucleophilic
Interception at the a-Position . . . . . . . . . . . . . . . . .
48542.11.3.3 Variation 3: Tandem a- or g-Addition and Michael
Addition Reactions . . . . 48642.11.4 Method 4: [3 +
2]-Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . 48742.11.5 Method 5: [4 + 2]-Cycloaddition
Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
49242.11.6 Method 6: Acylation and Kinetic Resolution of Alcohols .
. . . . . . . . . . . . . . . 49542.11.7 Method 7: Isomerization of
Activated Alkynes to Dienes . . . . . . . . . . . . . . . 497
42.12 Product Class 12: Alkylphosphonium SaltsD. Virieux, J.-N.
Volle, and J.-L. Pirat
42.12 Product Class 12: Alkylphosphonium Salts . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 503
42.12.1 Product Subclass 1:
Non-Heteroatom-SubstitutedAlkylphosphonium Salts . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . 503
42.12.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
503
42.12.1.1.1 Method 1: Alkylation of Phosphines . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . .
50342.12.1.1.1.1 Variation 1: Alkylation of Tertiary Phosphines . .
. . . . . . . . . . . . . . . . . . . . . . . . . 503
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42.12.1.1.1.2 Variation 2: Alkylation of Tertiary Phosphines
Using Alcohols or Derivatives 50442.12.1.1.1.3 Variation 3:
Successive Alkylation of Phosphines, Phosphides, or
Polyphosphines . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 50542.12.1.1.1.4 Variation 4:
Nucleophilic Addition of Phosphines or Derivatives
to Alkenes or Alkynes . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . 50542.12.1.1.2 Method 2:
Modification of Phosphonium Salts . . . . . . . . . . . . . . . . .
. . . . . . . . 50742.12.1.1.2.1 Variation 1: Diels–Alder Reaction
of Triphenyl(vinyl)phosphonium Salts
with 1,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . 50742.12.1.1.2.2 Variation 2:
Modification of Phosphonium Salts by Reaction of Ylides . . . .
50742.12.1.1.3 Method 3: Reaction of Phosphaalkenes . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 508
42.12.2 Product Subclass 2: Hydroxyphosphonium Salts . . . . . .
. . . . . . . . . . . . . . . . . . . 509
42.12.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
509
42.12.2.1.1 Method 1: Synthesis of a-Hydroxyphosphonium Salts
and Derivatives . . 50942.12.2.1.1.1 Variation 1: Addition of
Phosphines to Aldehydes or Ketones . . . . . . . . . . . .
50942.12.2.1.1.2 Variation 2: Alkylation of
(a-Hydroxyalkyl)phosphines or Derivatives . . . . .
51142.12.2.1.1.3 Variation 3: Reaction of Phosphines with Acetals,
Ketals, or Hemiacetals . 51342.12.2.1.1.4 Variation 4: Reaction of
Phosphines with Enol Ethers . . . . . . . . . . . . . . . . . . . .
51342.12.2.1.2 Method 2: Synthesis of b-Hydroxyphosphonium Salts
and Derivatives . . . 51442.12.2.1.2.1 Variation 1: Alkylation of
Phosphines with b-Hydroxyalkyl Halides or
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 51442.12.2.1.2.2
Variation 2: Alkylation of (b-Hydroxyalkyl)phosphines or
Derivatives . . . . . 51742.12.2.1.2.3 Variation 3: Reaction of
Phosphines with Epoxides . . . . . . . . . . . . . . . . . . . . .
. 52042.12.2.1.2.4 Variation 4: Reaction of Ylides with Ketones or
Aldehydes . . . . . . . . . . . . . . . 52242.12.2.1.2.5 Variation
5: Transformation of b-Functionalized Phosphonium Salts . . . . . .
52442.12.2.1.3 Method 3: Synthesis of g-Hydroxyphosphonium Salts
and Derivatives . . . 52642.12.2.1.3.1 Variation 1: Alkylation of
Phosphines with g-Hydroxyalkyl Halides or
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 52642.12.2.1.3.2
Variation 2: Alkylation of g-Hydroxyphosphines and Derivatives
with
Alkyl Halides . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 52842.12.2.1.3.3
Variation 3: Reaction of Ylides with Epoxides and 3-Oxaalkyl
Halides . . . . . 52942.12.2.1.3.4 Variation 4: Transformation of
g-Functionalized Phosphonium Salts . . . . . . 530
42.12.3 Product Subclass 3: Sulfanyl- and Selanylphosphonium
Saltsand Derivatives . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. 531
42.12.3.1 Synthesis of Product Subclass 3 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
531
42.12.3.1.1 Method 1: Synthesis of a-Sulfanyl and
a-Selanylphosphonium Salts andDerivatives . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. 531
42.12.3.1.1.1 Variation 1: Alkylation of Phosphines with Sulfur-
or Selenium-SubstitutedAlkyl Halides . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
531
42.12.3.1.1.2 Variation 2: Alkylation of Phosphines with
Bis(sulfanyl)- or Bis(selanyl)Alkyl Halides, or Cationic
Derivatives . . . . . . . . . . . . . . . . . . . . . . . 533
42.12.3.1.1.3 Variation 3: Transformation of Phosphonium Salts
with Anionic SulfurNucleophiles . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 535
42.12.3.1.1.4 Variation 4: Reaction of Ylides with Sulfur- or
Selenium-ContainingElectrophiles . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 536
42.12.3.1.2 Method 2: Synthesis of b-Sulfanyl- and
b-Selanylphosphonium Saltsand Derivatives . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
537
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42.12.3.1.2.1 Variation 1: Alkylation of Phosphines with Sulfur-
or Selenium-ContainingAlkyl Halides or Sulfonates . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 538
42.12.3.1.2.2 Variation 2: Reaction of Phosphines with
1,1,2-Trimethyldisulfaniumor 1-Methyl-1,2-diphenyldisulfanium Salts
. . . . . . . . . . . . . . . . . . 539
42.12.3.1.2.3 Variation 3: Reaction of Vinylphosphonium Salts
with Sulfur Dioxide,Thiols, or Associated Anions . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 540
42.12.3.1.2.4 Variation 4: Reaction of Ylides with Miscellaneous
Electrophiles . . . . . . . . . . 54242.12.3.1.3 Method 3:
Synthesis of g-Sulfanyl- and g-Selanylphosphonium Salts
and Derivatives . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 54342.12.3.1.3.1 Variation
1: Alkylation of Phosphines with Sulfur- or
Selenium-Substituted
Alkyl Halides or Related Compounds . . . . . . . . . . . . . . .
. . . . . . . . . 54342.12.3.1.3.2 Variation 2: Transformation of
Phosphonium Salts . . . . . . . . . . . . . . . . . . . . . .
544
42.12.4 Product Subclass 4: Carbonylphosphonium Salts and
Derivatives . . . . . . . . 545
42.12.4.1 Synthesis of Product Subclass 4 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
545
42.12.4.1.1 Method 1: Synthesis of P-Carbonylphosphonium Salts
and Derivatives . . 54542.12.4.1.1.1 Variation 1: Reaction of
Phosphines with Various Carbonyl Electrophiles . . 54642.12.4.1.1.2
Variation 2: Alkylation of P-Carbonylphosphines with Alkyl Halides
or
Sulfonates . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . 54842.12.4.1.2 Method 2:
Synthesis of a-Carbonylphosphonium Salts and Derivatives . .
55042.12.4.1.2.1 Variation 1: Alkylation of Phosphines with
a-(Halomethyl)carbonyl Species 55042.12.4.1.2.2 Variation 2:
Reaction of Ylides with Carbonylated Electrophiles . . . . . . . .
. . 55342.12.4.1.2.3 Variation 3: Reaction of Stabilized Ylides
with Other Electrophiles . . . . . . . . 55642.12.4.1.2.4
Variations 4: Miscellaneous Reactions . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . 55742.12.4.1.3 Method 3:
Synthesis of b-Carbonyl-Substituted Phosphonium Salts and
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 55842.12.4.1.3.1
Variation 1: Alkylation of Phosphines with b-Carbonyl-Substituted
Alkyl
Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 55942.12.4.1.3.2
Variation 2: Reaction of Phosphines with a,b-Unsaturated
Carbonyl
Species . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 56142.12.4.1.3.3
Variation 3: Alkylation of b-Carbonylphosphines with Alkyl Halides
. . . . . . . 565
42.12.5 Product Subclass 5: Polyphosphonium Salts . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 565
42.12.5.1 Synthesis of Product Subclass 5 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
565
42.12.5.1.1 Method 1: Synthesis of Multiphosphonium Salts . . .
. . . . . . . . . . . . . . . . . . . . 56642.12.5.1.1.1 Variation
1: Reaction with Multihalides . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . 56642.12.5.1.1.2 Variation 2: Reaction
of Unsaturated Precursors . . . . . . . . . . . . . . . . . . . . .
. . . 56642.12.5.1.1.3 Variation 3: Recursive Synthesis from a
Phosphine . . . . . . . . . . . . . . . . . . . . . .
56742.12.5.1.2 Method 2: Synthesis of Polymeric Phosphonium Salts .
. . . . . . . . . . . . . . . . . 56742.12.5.1.2.1 Variation 1:
Reaction of Phosphonium Monomers . . . . . . . . . . . . . . . . .
. . . . . . 56742.12.5.1.2.2 Variation 2: Functionalization of
Polymeric Backbones . . . . . . . . . . . . . . . . . . . 569
42.12.6 Product Subclass 6: Cyclic Phosphonium Salts . . . . . .
. . . . . . . . . . . . . . . . . . . . . 570
42.12.6.1 Synthesis of Product Subclass 6 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
570
42.12.6.1.1 Method 1: Cyclization onto Phosphorus . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 57042.12.6.1.1.1
Variation 1: Reaction of Secondary Phosphines or Derivatives
with
1,n-Dielectrophiles . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 57042.12.6.1.1.2 Variation 2:
Intramolecular Cyclization of Tertiary Phosphines . . . . . . . . .
. . 571
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42.12.6.1.1.3 Variation 3: Intermolecular Cyclization of
Tertiary Phosphines . . . . . . . . . . . 57242.12.6.1.1.4
Variation 4: Reaction of Halophosphines . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . 57442.12.6.1.1.5 Variation 5:
Reaction of Methylenephosphonium Ions . . . . . . . . . . . . . . .
. . . . 57542.12.6.1.2 Method 2: Cyclization between Two Phosphorus
Substituents . . . . . . . . . . 576
42.12.7 Product Subclass 7: Heterophosphonium Salts . . . . . .
. . . . . . . . . . . . . . . . . . . . . 577
42.12.7.1 Synthesis of Product Subclass 7 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
577
42.12.7.1.1 Method 1: Synthesis from Tricoordinate Phosphorus
Compounds . . . . . . . 57742.12.7.1.1.1 Variation 1: Alkylation of
Tricoordinate Reagents . . . . . . . . . . . . . . . . . . . . . .
. . 57742.12.7.1.1.2 Variation 2: Reaction of Phosphines with
Heteroatomic Electrophiles . . . . 58042.12.7.1.2 Method 2:
Synthesis from Tetracoordinate Phosphorus Compounds . . . .
58142.12.7.1.2.1 Variation 1: Modification of Heterophosphonium
Salts . . . . . . . . . . . . . . . . . . 58142.12.7.1.2.2
Variation 2: Reaction of Electrophiles with Tetracoordinate
Phosphorus
Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 58242.12.7.1.2.3
Variation 3: Reaction of Secondary Phosphine–Borane Complexes . . .
. . . . 582
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides,
Selenides, Tellurides,and ImidesN. L. Kilah and S. B. Wild
42.13 Product Class 13: Trialkylphosphine Oxides, Sulfides,
Selenides, Tellurides,and Imides . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . 595
42.13.1 Product Subclass 1: Trialkylphosphine Oxides . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 595
42.13.1.1 Synthesis of Product Subclass 1 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
595
42.13.1.1.1 Method 1: Oxidation of Trialkylphosphines . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 59542.13.1.1.1.1
Variation 1: Oxidation with Hydrogen Peroxide . . . . . . . . . . .
. . . . . . . . . . . . . . 59542.13.1.1.1.2 Variation 2: Oxidation
with Sulfur(VI) Oxides . . . . . . . . . . . . . . . . . . . . . .
. . . . . . 59642.13.1.1.1.3 Variation 3: Oxidation by Nitrous
Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. 59742.13.1.1.1.4 Variation 4: Oxidation with an Iodosylaryl
Sulfone . . . . . . . . . . . . . . . . . . . . . . .
59742.13.1.1.2 Method 2: Oxidation of Phosphonium Salts . . . . . .
. . . . . . . . . . . . . . . . . . . . . . 59842.13.1.1.3 Method
3: Addition of Dialkylphosphine Oxides to Alkenes . . . . . . . . .
. . . . 59942.13.1.1.4 Method 4: Addition of Dialkylphosphine
Oxides to Ketones or Aldehydes 60042.13.1.1.5 Method 5: Reactions
of Dialkylphosphine Oxides with Alkyl Halides . . . . .
60242.13.1.1.5.1 Variation 1: Base-Induced Ionization . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
60242.13.1.1.5.2 Variation 2: Lewis Acid Catalysis . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
60342.13.1.1.5.3 Variation 3: Reduction with Sodium
Bis(2-methoxyethoxy)aluminum
Hydride . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 60442.13.1.1.6 Method
6: Additions of Dialkyl(chloro)phosphines to Enones . . . . . . . .
. . . 60542.13.1.1.7 Method 7: Reactions of Chlorophosphine Oxides
with Grignard Reagents 60642.13.1.1.8 Method 8: Reactions of
Dialkylphosphinites with Alkyl Halides . . . . . . . . . .
60742.13.1.1.9 Method 9: Isomerization of Dialkylphosphinites . . .
. . . . . . . . . . . . . . . . . . . . . 60942.13.1.1.10 Method
10: Cycloaddition of Alkyl(dichloro)phosphines with Dienes . . . .
. 61042.13.1.1.11 Method 11: Addition of Dialkylphosphine Oxides to
Imines . . . . . . . . . . . . . . 61242.13.1.1.12 Method 12:
Hydrogenation of Tertiary Arylphosphine Oxides . . . . . . . . . .
. . 61242.13.1.1.13 Method 13: Conversion of Trialkylphosphine
Ylides into Trialkylphosphine
Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . 61442.13.1.1.14
Method 14: Oxygenation of Trialkylphosphine Imides . . . . . . . .
. . . . . . . . . . . 615
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42.13.1.1.14.1 Variation 1: By Reaction with a Ketone . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
61542.13.1.1.14.2 Variation 2: By Reaction with Methanol . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . .
61542.13.1.1.14.3 Variation 3: By Treatment with an Oxidizing Agent
. . . . . . . . . . . . . . . . . . . . . . 61642.13.1.1.15 Method
15: Oxygenation of Trialkylphosphine Sulfides . . . . . . . . . . .
. . . . . . . 61642.13.1.1.15.1 Variation 1: Treatment with
Phosgene . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . 61642.13.1.1.15.2 Variation 2: Treatment with
Dimethyldioxirane . . . . . . . . . . . . . . . . . . . . . . . . .
. 61742.13.1.1.15.3 Variation 3: Treatment with Trifluoroacetic
Anhydride . . . . . . . . . . . . . . . . . . . 61742.13.1.1.15.4
Variation 4: Treatment with 7-Oxabicyclo[4.1.0]heptane and
Trifluoroacetic
Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . 61742.13.1.1.16
Method 16: Oxygenation of a Trialkylphosphine Selenide . . . . . .
. . . . . . . . . . 617
42.13.2 Product Subclass 2: Trialkylphosphine Sulfides . . . . .
. . . . . . . . . . . . . . . . . . . . . . 618
42.13.2.1 Synthesis of Product Subclass 2 . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
618
42.13.2.1.1 Method 1: Addition of Dialkylphosphine Sulfides to
Alkenes . . . . . . . . . . . . 61842.13.2.1.1.1 Variation 1:
Base-Promote