Practical Catalytic Asymmetric Epoxidations David White Stoltz Group Literature Presentation December 13, 2006 8 p.m. 147 Noyes R 4 R 2 R 1 R 3 R 4 R 2 R 1 R 3 O O O O Me O H Me OH OH H H O (–)-laulimalide OH HO O active metabolite of benzo[a]pyrene O O O O O Me Me HO Me Me OH H Me H Me H H Me H Me H proposed structure of glabrescol
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Practical Catalytic Asymmetric Epoxidations · Practical Catalytic Asymmetric Epoxidations David White Stoltz Group Literature Presentation December 13, 2006 8 p.m. 147 Noyes R4 R2
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Practical Catalytic Asymmetric Epoxidations
David WhiteStoltz Group Literature PresentationDecember 13, 20068 p.m.147 Noyes
R4R2
R1
R3
R4R2
R1
R3O
O
O
O
Me
OH
Me OH
OH
H
HO
(–)-laulimalide
OHHO
O
active metabolite ofbenzo[a]pyrene
O O O O O
Me
MeHO
Me
MeOH
H Me H Me H H Me H Me Hproposed structure of glabrescol
Outline
I. Directed EpoxidationsA. SharplessB. Yamamoto Homoallylic Alcohol Example
II. Metal Oxo-Catalyzed EpoxidationsA. Porphyrin ExampleB. Jacobsen-Katsuki
III. Dioxirane-Catalyzed EpoxidationsA. YangB. DenmarkC. Shi
IV. Nucleophilic EpoxidationsA. JuliáB. Shibasaki
V. Miscellaneous Methods
General Section OutlineI. HistoryII. ScopeIII. MechanismIV. Synthetic Example
Xia, Q.-H.; Ge, H.-Q.; Ye, C.-P.; Liu, Z.-M.; Su, K.-X.; Su, K.-X. Chem. Rev. 2005, 105, 1603–1662.
Extensive Current General Review
Directed Epoxidations
1965-1967 Development of the Halcon Oxirane process for the production of propene oxide1967 Discovery of directing effects in metal-mediated epoxidations of allylic alcohols1980 Discovery by Sharpless of the asymmetric Ti tartrate epoxidation of allylic alcohols1981 First reports of practical synthetic applications of the Ti tartrate technology1981 Development by Sharpless of the Ti-catalyzed kinetic resolution of secondary allylic alcohols1986-1987 Discovery by Sharpless that addition of molecular sieves renders Ti tartrate epoxidations truly catalytic
Timeline
R2
R1
R3
OH
R4
R2
R1
R3
OH
R4
OL*M OOR
Sharpless Asymmetric Epoxidation (SAE)
Johnson, R. A.; Sharpless. K. B. Catalytic Asymmetric Epoxidation of Allylic Alcohols. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I. Ed. Wiley-CVH:New York, 2000; 231–280.
Katsuki, T. Epoxidation of Allylic Alcohols. In Comprehensive Asymmetric Catalysis, 1st ed.; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: NewYork, 1999; Vol. 2, 621–648.
Johnson, R. A.; Sharpless. K. B. Addition Reactions with Formation of Carbon–Oxygen Bonds: Asymmetric Methods of Epoxidation. In ComprehensiveOrganic Synthesis, 1st ed.; Trost, B. M., Fleming, I. Eds.; Pergamon Press: New York,1991; Vol. 7, 389–436.
Jacobsen, E. N. Transition Metal-catalyzed Oxidations: Asymmetric Epoxidation. In Comprehensive Organometallic Chemistry II, 1st ed.; Abel, E. W.; Stone,F. G. A.; Wilkinson, G. Eds.; Pergamon Press: New York,1995; Vol. 12, 1097–1135
RO2COH
CO2R
OH
molecular sievesCH2Cl2≤ 0 °C
Ti(Oi-Pr)4t-BuOOH
Reviews
R2
R1
R3
OH
R4
R2
R1
R3
OH
R4
O
SAE: Substrate Scope
R3
R4
R2
OH
R1
R3
R4
R2
OH
R1
O
3 or 4Å MSCH2Cl2
–40–0 °C
4.7–10 mol% Ti(Oi-Pr)45.9–14 mol% (+)-DET or (+)-DIPT
t-BuOOH (1.5–2.5 equiv)
OHO
Me
Me
MeOH
O
Ph
Bn
MeOH
OMe
Bn
OOH
91% ee95% yield
93% ee77% yield
91% ee90% yield
Conditions not provided.
91% ee90% yield
120 mol% Ti(Oi-Pr)4150 mol% (–)-DET
n-Pr OHO
OHO
OHO
n-Pr
90% ee65% yield
(cumene hydroperoxide)
94% ee85% yield
95% ee88% yield
Sharpless, K. B.; Behrens, C. H.; Katsuki, T.; Lee, A. W. M.; Marin, S.; Takatani, M.; Viti, S. M.; Walker, F. J.; WoodardS. S. Pure & Appl. Chem. 1983, 55, 589–604.
Schweitzer, M. J.; Sharpless, K. B. Tetrahedron Lett. 1985 26, 2543–2546.
Gao, Y. Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765–5780.
Johnson, R. A.; Sharpless. K. B.; Catalytic Asymmetric Epoxidation of Allylic Alcohols. In Catalytic Asymmetric Synthesis, 2nd ed.;Ojima, I. Ed.; Wiley-VCH: New York, 2000; 231–280 and references therein.
Johnson, R. A.; Sharpless. K. B.; Catalytic Asymmetric Epoxidation of Allylic Alcohols. In Catalytic Asymmetric Synthesis, 2nd ed.;Ojima, I. Ed.; Wiley-VCH: New York, 2000; 231–280 and references therein.
Me OH
c-hex
OTi(Oi-Pr)4tartratet-BuOOHOH
c-hex
Me
i-PrO2COH
CO2i-Pr
OH
i-PrO2COH
CO2i-Pr
OH
EtO2COH
CO2Et
OH
MeO2COH
CO2Me
OH
104 74 28 15
–20 °C 0 °C
DIPT DIPT DET DMT
SAE: Substrate Scope
Johnson, R. A.; Sharpless. K. B.; Catalytic AsymmetricEpoxidation of Allylic Alcohols. In Catalytic AsymmetricSynthesis, 2nd ed.; Ojima, I. Ed.; Wiley-VCH: New York,2000; 231–280.
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth.Catal. 2001, 343, 5–26, supporting information andreferences therein.
R OR
OR
R R
RO OR
R R
OH(remote) R
O
H
R
O
NR2
N3R
R
O
OR
RO
RO
RR
O
R
CNR
NO2R
RR
R
R
R
RR
NR
RO
SiR3 SO
ORR
RSO
R
R
N
NH
NN
RR2N
O
NR2
R2N
O
OR
SO
ONHR
NH2
R
O
NH
NH2
R NR2
R
O
OH
SHR
ROH
(most)
(most)
R PR2
Compatible Functional Groups Incompatible Functional Groups
PO
ArRAr
SAE: Kinetic Resolution – Unorthodox Substrates
Keith, J. M.; Larrow, J. F.; Jacobsen, E. N. Adv. Synth. Catal. 2001, 343, 5–26, supporting information and references therein.
i-PrTMS
OH
i-PrTMS
OHO
40–48% yield99% ee
40–48% yield>99% ee
n-pentn-Bu3Sn
OH
n-pentn-Bu3Sn
OHO
47% yield*
(inferred from text)80% ee
38–42% yield99% ee
n-pentI
OH
n-pentI
OHO
yield not given99% ee
45% yield99% ee
46% yieldee not determined
43% yield94% ee
47% yieldee not determined
46% yield95% ee
43% yield>95% ee
39% yield>95% ee
n-BuOOH
O
On-Bu
OH
n-PrONHTs
NTs
On-Pr
OH
n-PrS
OH
MeNTs
OH
D-(–)-diethyl tartrate (unnatural)
L-(+)-diethyl tartrate (natural)
O
O
R1R2
R3 OH
SAE: Selectivity Mnemonics
Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974–5976.
Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237–6240.
Johnson, R. A.; Sharpless. K. B.; Catalytic Asymmetric Epoxidation of Allylic Alcohols. In Catalytic Asymmetric Synthesis, 2nd ed.;Ojima, I. Ed.; Wiley-VCH: New York, 2000; 231–280 and references therein.
Asymmetric Epoxidation Kinetic Resolution
R1R2
R3 OHR4
H
R1R2
R3 OHH
R4
O
D-(–)-diethyl tartrate (unnatural)
slow fast
€
rate = k [Ti(tartrate)(OR)2] [TBHP] [allylic alcohol][inhibitor alcohol]2
SAE: Proposed Catalytic Cycle
Woodard, S. S.; Finn, M. G.; Sharpless. K. B.J. Am. Chem. Soc. 1991, 113, 106–113.
Finn, M. G.; Sharpless. K. B. J. Am. Chem. Soc. 1991, 113, 113–126.
Johnson, R. A.; Sharpless. K. B.; Catalytic Asymmetric Epoxidation of Allylic Alcohols. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I. Ed.;Wiley-VCH: New York, 2000; 231–280.
TiOO OR
ORORO HOR
OROO Ti O
OO
O
RO
OOR
R1R2
t-BuROO
R3
H
SAE: Synthetic Example
Paterson, I.; De Savi, C.; Tudge, M. Org. Lett 2001, 3, 3149–3152.
Also see: Blanc, A.; Toste, F. D. Angew. Chem. Int. Ed. 2006, 45, 2096–2099.
Ph
OH
Me Me
OH OH Me OH
i-Pr OH t-Bu OH Ph OH 1-napthyl OH
24% yield46% ee
67% yield36% ee
61% yield74% ee
58% yield84% ee
42% yield91% ee
70% yield89% ee
89% yield90% ee
77% yield90% ee
R3R2
R1 OH
2 mol% VO(Oi-Pr3)6 mol% ligand
cumene hydroperoxide (1.5 equiv) R3R2
R1 OHOtoluene, 0 °C
10h
N
O
O
N
O
t-Bu
t-Bu
OH
ligand
HH
Porphyrin/Salen-Based Epoxidations
1975 Report by Collman of the chemically robust class of “picket fence” porphyrins1979 Discovery by Groves that iron porphyrin complexes mimic the epoxidation activity of cytochrome P-4501983 First report of porphyrin-catalyzed asymmeric epoxidation. Proposal by Groves of the side-on approach
transition state model1983–1986 Detailed mechanistic studies by Kochi on epoxidation reactions catalyzed by achiral salen complexes1990–1993 Discovery and development by Jacobsen and Katsuki of enantioselective epoxidation of unfunctionalized
Katsuki, T. Asymmetric Epoxidation of Unfunctionalized Olefins and Related Reactions. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I. Ed. Wiley-CVH:New York, 2000; 287–325.
Jacobsen, E. N.; Wu, M. H. Epoxidation of Alkenes other than Allylic Alcohols. In Comprehensive Asymmetric Catalysis, 1st ed.; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: New York, 1999; Vol. 2, 649–677.
Jacobsen, E. N. Transition Metal-catalyzed Oxidations: Asymmetric Epoxidation. In Comprehensive Organometallic Chemistry II, 1st ed.; Abel, E. W.; Stone,F. G. A.; Wilkinson, G. Eds.; Pergamon Press: New York, 1995; Vol. 12, 1097–1135
Reviews
Yields based on consumed PhIO Rose, E.; Ren, Q.-Z.; Andrioletti, B. Chem. Eur. J. 2004, 10, 224–230.
Porphyrin-Based Epoxidations: An Example
O O O
OOO
FF
FF
F
F
Cl O2N
Cl
96% yield97% ee
80% yield96% ee
87% yield93% ee
90% yield88% ee
84% yield90% ee
75% yield84% ee
R
O
(10 equiv)
R
PhIO (1 equiv)1 mol% catalyst
CH2Cl2–5 °C
NN
NNFe
MeO OMe
HN O OHN
OMeMeO
HNO NH OCl
catalyst
Salen-Based Epoxidations
oxidant
McGarrige, E. M.; Gilheany, D. G. Chem. Rev. 2005, 105, 1563–1602.
Katsuki, T. Adv. Synth. Catal. 2002, 344, 131–147.
Katsuki, T. Asymmetric Epoxidation of Unfunctionalized Olefins and Related Reactions. In Catalytic Asymmetric Synthesis, 2nd ed.; Ojima, I. Ed. Wiley-CVH:New York, 2000; 287–325.
Jacobsen, E. N.; Wu, M. H. Epoxidation of Alkenes other than Allylic Alcohols. In Comprehensive Asymmetric Catalysis, 1st ed.; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: New York, 1999; Vol. 2, 649–677.
Katsuki, T. J. Mol. Catal. A: Chem. 1996, 113, 87–107.
Jacobsen, E. N. Transition Metal-catalyzed Oxidations: Asymmetric Epoxidation. In Comprehensive Organometallic Chemistry II, 1st ed.; Abel, E. W.; Stone,F. G. A.; Wilkinson, G. Eds.; Pergamon Press: New York,1995; Vol. 12, 1097–1135.
Katsuki, T. Coord. Chem. Rev. 1995, 140, 189–214.
Reviews
R R
NN
R' R'O OM
R4R2
R1
R3
R4R2
R1
R3O
NN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst
Jacobsen-Katsuki Epoxidation
Jacobsen, E. N.; Zhang, W.; Muci, A. R.; Ecker,J. R.; Deng, L. J. Am. Chem. Soc. 1991, 113,7063–7064.
Lee, N. H.; Muci, A. R.; Jacobsen, E. N.Tetrahedron Lett. 1991, 32, 5055–5058.
2–4 mol% catalystNaOCl (2 equiv)
Na2HPO4→ pH 11.3 with NaOH
CH2Cl2/H2O0–4 °C
πR
πR
O
PhMe
O
Me
O
Cl
PhCO2Me
O O
O
O
84% yield92% ee
67% yield92% ee
65% yield by GC89% ee
(with 40 mol% additive)
63% yield94% ee
O
O
Me
MeO
O
Me
MeO
O
Me
Me
NCO OMe
87% yield98% ee
(ent-catalyst)
96% yield97% ee
(ent-catalyst)
75% yield98% ee
(ent-catalyst)
N
Ph
O
additive
Jacobsen-Katsuki Epoxidation
NN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst
Lee, N. H.; Jacobsen, E. N. Tetrahedron Lett. 1991, 32, 6533–6536. Chang, S.; Lee, N. H.; Jacobsen, E. N. J. Org. Chem. 1993, 58, 6939–6941.
O
65% yield1.6:1 trans:cis
90/43 trans/cis % ee
N
Ph
O
additive
Me
n-hex
O
65% yield5.2:1 trans:cis
98/64 trans/cis % ee(20 mol% additive)
Cy
TMS
O
34% yield1:1 trans:cis
35/35 trans/cis % ee
Ph
TMS
OMe
n-hex
50% yield1.1:1 trans:cis92% ee trans
(20 mol% additive;ent-catalyst)
OEtO2C
58% yield7.3:1 trans:cis83% ee trans
(20 mol% additive;ent-catalyst)
OTBDMSO
EtO2C
81% yield9:1 trans:cis
87% ee(20 mol% additive;
ent-catalyst)
n-pent
3–4 mol% catalystNaOCl (2 equiv)
Na2HPO4→ pH 11.3 with NaOH
CH2Cl2/H2O0 °C–rt
πR
πO
R
Jacobsen-Katsuki Epoxidation
Chang, S.; Galvin, J. M.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 6937–6938.
4 mol% catalyst25 mol% salt
NaOCl (4 equiv)chlorobenzene/H2O
4 °Cπ
Rπ
OR
NN
O OMn
t-Bu t-Bu
TIPSO OTIPSCl
catalyst
PhO
Me
yield not determined95:5 trans:cis81% ee trans
t-BuO
Me
yield not determined69:31 trans:cis84% ee trans
configuration not determined
PhO
Ph
80% yield>96:4 trans:cis90% ee trans
OMe
yield not determined89:11 trans:cis86% ee trans
MeO
NBnOH
N
OMe
Cl
salt
Jacobsen-Katsuki Epoxidation
3 mol% catalyst20 mol% additiveNaOCl (1.5 equiv)
Na2HPO4→ pH 11.3 with NaOH
CH2Cl2/H2O0 °C
R ROπ π
R R NN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst
N
Ph
O
additive
Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378–4380.
PhO
69% yield93% ee
Ph
MePh
O87% yield
88% ee
Ph
PhMe
O91% yield
95% ee
Ph
PhPh
O97% yield
92% ee
Jacobsen-Katsuki Epoxidation
N
Ph
O
additive
Adam, W.; Fell, R. T.; Stegmann, V. R.; Saha-Möller, C. R.J. Am. Chem. Soc. 1998, 120, 708–714.
7 mol% catalyst30 mol% additiveNaOCl (7.5 equiv)
Na2HPO4→ pH 11.3 with NaOH
CH2Cl2/H2O0 °C
ππ
R2 ROSiR3Me2
O
OH
NN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst
R = Me88% conv.
12% ee
R = t-Bu70% conv.
57% ee
PhPh
O
OH
PhOMe
O
OH
R = Me82% conv.
87% ee
R = t-Bu95% conv.
81% ee
PhEt
O
OH
MePh
O
OH
Jacobsen-Katsuki EpoxidationNN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst A
NN
O OMn
t-Bu t-Bu
TIPSO OTIPSCl
catalyst B
Ph Ph
NN
O OMn
t-Bu t-Bu
Me MeCl
catalyst C
3 mol% catalyst20 mol% additiveNaOCl (1.5 equiv)
Na2HPO4→ pH 11.3 with NaOH
CH2Cl2/H2O0 °C
R RO
R R
π π
R R
O
EtMe
MeMe
BrO
catalyst A: 87% eecatalyst C: 97% ee (81% yield)
Ph
MeO catalyst B: 90% ee (90% yield)
catalyst C: 78% ee
Me
MeO catalyst A: 15% ee
catalyst C: 25% eeconfiguration not determined
Brandes, B. D.; Jacobsen, E. N. Tetrahedron Lett. 1995, 36, 5123–5126.
Jacobsen-Katsuki Epoxidation
Ph Ph
NN
O OMn
t-Bu t-Bu
TIPSO OTIPSCl
catalyst A
Ph Ph
NN
O OMn
t-Bu t-Bu
MeO OMeCl
catalyst B
5 mol% catalystNMO (5 equiv)
m-CPBA (2 equiv)CH2Cl2–78 °C
*π πO
Palucki, M.; McCormick, G. J.; Jacobsen, E. N. Tetrahedron Lett. 1995, 36, 5457–5460.
Palucki, M.; Pospisil, P. J.; Zhang, W.; Jacobsen, E. N. J. Am. Chem. Soc. 1994, 116, 9333–9334.
56–69% ee with NaOCl
Configurations not indicated
*O
catalyst A89% yield
86% ee
*O
catalyst A83% yield
85% ee
*O
catalyst B83% yield
80% ee
*O
catalyst A85% yield
82% ee
F
F3CMe
Jacobsen-Katsuki Epoxidation
Me
Ph
Me
Ph
O5 mol% catalyst
NMOm-CPBACH2Cl2–78 °C
catalyst A: 86% eecatalyst B: 83% ee
NN
O OMn
F FClcatalyst A
Ph Ph
NN
O OMn
t-Bu
BrCl
catalyst B
Jacobsen, E. N.; Wu, M. H. Epoxidation of Alkenes other than Allylic Alcohols. In Comprehensive Asymmetric Catalysis, 1st ed.; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: New York, 1999; Vol. 2, 649–677.
Nishikori, H.; Ohta, C.; Katsuki, T. Synlett 2000, 1557–1560.
NN
O OMn
PhPh
PF6
catalyst B
Jacobsen-Katsuki Epoxidation: Stereoselectivity Model
Based on: Fukuda, T.; Irie, R.; Katsuki, T. Synlett 1995, 197–198.
Modified based on data from: Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378–4380.
πR
RR
πRπ
side-on vs. skewed side-on approach
Katsuki Jacobsen Jacobsenand
Katsuki
O
Mn
O
Mn
O
Mn
πR
πR
RRR
π
R
Rπ
Rπ
π
ππ
π
ππ
NN
O OMn
R2 R2
R3 R3
R1R1
πR
π
O
Jacobsen-Katsuki Epoxidation: Stereoselectivity Model
Based on: Katsuki, T. Adv. Synth. Catal. 2002, 344, 131–147.
Modified based on data from: Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378–4380, and Fukuda, T.; Irie, R.; Katsuki, T. Synlett 1995,197–198.
πR
RR
πRπ
side-on vs. skewed side-on approach
Katsuki Jacobsen Jacobsenand
Katsuki
O
Mn
O
Mn
O
Mn
NNO
OMn
R2R2
R3
R3
R1R1 O
L
πR
πR
R
RR
π R
Rπ
Rπ
π
ππ
π
ππ
πR
π
Jacobsen-Katsuki Epoxidation: Mnemonic
Rotate left π-substituent forward toPredict trans-epoxide stereochemistry.
Adapted from: Brandes, B. D.; Jacobsen, E. N. J. Org. Chem. 1994, 59, 4378–4380.
Modified based on data from: Fukuda, T.; Irie, R.; Katsuki, T. Synlett 1995, 197–198.
Taken from E. N. Jacobsen lecture notes, Chemistry 153, Harvard University, Spring 2001.
*McGarrige, E. M.; Gilheany, D. G. Chem. Rev. 2005, 105, 1563–1602.*
Jacobsen, E. N.; Wu, M. H. Epoxidation of Alkenes other than Allylic Alcohols. In Comprehensive Asymmetric Catalysis, 1st ed.; Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: New York, 1999; Vol. 2, 649–677.
O
Mn
L
Rπ
O
Mn
L
πR
Rπ
O
Rπ
O
Rπ
O
R
Oπ
O
Mn
L
π R
Mn
L
Oπ
R
Mn O
π R
‡
or
favored by Jacobsen
favored by Katsuki
NN
O OMn
t-Bu t-Bu
t-Bu t-BuCl
catalyst
Jacobsen-Katsuki Epoxidation: Synthetic Example
Huang, X.; Harris, T. M. J. Chem. Soc., Chem. Commun. 1995, 1699–1700.
O OHHO
catalysttetralinNaOCl
CH2Cl2/H2O0 °C
21% yield86% ee
O
active metabolite ofbenzo[a]pyrene
Dioxirane-Based Epoxidations
1899 Intermediacy of dioxiranes first postulated by Baeyer and Villiger in the oxidation of menthone1972 Isolation of dioxiranes from the oxidation of dilithioalkoxides reported in a patent by Talbott and Thompson1974 Montgomery speculates that dioxiranes are the active intermediates in the decomposition of Oxone and the
oxidation of halides and dyes1977 Observation of the parent dioxirane in the gas phase reported separately by Suenram and Martinez1979 Montgomeryʼs speculation substantiated by 18O labeling studies reported by Curci and Edwards1985 Preparation and isolation of dimethyldioxirane from acetone reported by Murray1996 Yang reports up to 87% ee in oxidation of olefins with catalytic chiral dioxiranes1996 Shi reports stochiometric epoxidations in >90% ee with a fructose-derived dioxirane1997 Shi reports that modification of reaction conditions allow epoxidation with catalytic amounts of his chiral ketone
Timeline
R4R2
R1
R3
R4R2
R1
R3OR R'
OO
Dioxirane-Based Epoxidations
R4R2
R1
R3
R4R2
R1
R3OR R'
OO
Yang, D. Acc. Chem. Res. 2004, 37, 497–505.
Shi, Y. Acc. Chem. Res. 2004, 37, 488–496.
Shi, Y. J. Synth. Org. Chem. Jpn. 2002, 60, 342–349.
Frohn, M.; Shi, Y. Synthesis 2000, 1979–2000.
Denmark, S. E.; Wu, Z. Synlett 1999, 847–859.
For extensive referencing of other ketone-based catalysts, see: Shing, T. K. M.; Leung, G. Y. C.; Luk T. J. Org. Chem. 2005, 70, 7279–7289 (not a review).
Shen, Y.-M.; Wang, B.; Shi, Y. Tetrahedron Lett. 2006, 47, 5455–5488.
Shi Epoxidation: Synthetic Example
Xiong, Z.; Corey, E. J. J. Am. Chem. Soc.2000, 122, 4831–4832.
Me
Me
OH
Me Me
Me Me
Me
Me
HO
Me
Me
OH
Me Me
Me Me
Me
Me
HO
O O
O O O
88.4% ee
O O O O O
Me
MeHO
Me
MeOH
H Me H Me H H Me H Me H
ketone (3 equiv)oxoneK2CO3
n-BuNHSO4Na2•EDTA/Na2B4O7•10H2O
CH3CN/DMM/H2O0 °C
CSAPhMe0 °C
31% over two steps
O OO
OO
O
MeMe
MeMe
ketone
proposed structure of glabrescol
Nucleophilic Epoxidations
1980 First highly enantioselective epoxidation reaction reported by Juliá, epoxidizing chalcone in >90% ee1997 Shibasaki reports that BINOL-derived catalysts provide high enantioselectivity in the epoxidation of
α,β-unsaturated ketones
Timeline
ROOH or NaOCl
R1 R2
O
R1 R2
OO
Shibasaki, M.; Kanai, M.; Matsunaga, S. Aldrichachim. Acta 2006, 39, 31–39.
Porter, M. J.; Skidmore, J. Chem. Commun. 2000, 1215–1225.
Reviews
Polyamino Acid-Catalyzed Epoxidations: Lead References
Ph PhO
catalytic poly[(S)-alanine]NaOH/H2O2
toluene/H2Ort
85% yield93% ee
Ph
O
Ph
O
First report: Juliá, S.; Masana, J.; Vega, J. C. Angew. Chem. Int. Ed. Engl. 1980, 19, 929–9310.
For current lead references, see: Lauret, C.; Roberts, S. M. Aldrichim. Acta 2002, 35, 47–51.
Kelly, D. R.; Roberts, S. M. Biopolymers 2006, 84, 74–89.
Shibasaki Epoxidation: Enones
R1 R1O
R2
O
R2
O
4Å MS (not dried)THF
rt
TBHP (1.2 equiv)
5 mol% (R)-BINOL5 mol% La(Oi-Pr)3
Ph3As O5 mol%
Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725–2732.
PhO
Ph
O
i-PrO
Ph
O
PhO
i-Pr
O
n-pentO
Me
OO
Ph
O
n-Pr Me
On-pent
99% yield96% ee
95% yield94% ee
72% yield95% ee
95% yield96% ee
89% yield95% ee
61% yield<10% trans-epoxide
59% ee(10 mol% catalyst)
O
Shibasaki Epoxidation: Amides
R RO
N
O
OMe
O
4Å MSTHF
rt
TBHP (2.4 equiv)
10 mol% (S)-BINOL10 mol% La(Oi-Pr)3
Ph3As O10 mol%
N
Ph
MeOH
PhO
OMe
OO
OOt-Bu
O
OOMe
OO
OMe
O
Ph Me
O
86% yield92% ee
58% yield91% ee
(using CMHP)
92% yield*79% ee
81% yield*81% ee
Me
* MeOH not added. could be converted to corresponding ester in similar yield by MeOH addition.
Nemoto, T.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 9474–9475.
Ohshima, T.; Nemoto, T.; Tosakai, S.-Y.; Kakei, H.; Gnanadesikan, V.; Shibasaki, M. Tetrahedron Lett. 2003, 59, 10485–10497.
Shibasaki Epoxidation: Amides
R1 R1O
N
O
N
O
4Å MS (dried or wet)THF
rt
TBHP (1.2 equiv)
10 mol% (S)-BINOL10 mol% Sm(Oi-Pr)3
Ph3As O10 mol%R2
R3
R2
R3
ONHCH3
O
Ph99% yield>99% ee
ONH
O
Ph95% yield
98% ee
n-PrO
NHBn
O
94% yield94% ee
PhO
NMe2
O
96% yield>99% ee
Ohshima, T.; Nemoto, T.; Tosakai, S.-Y.; Kakei, H.; Gnanadesikan, V.; Shibasaki, M. Tetrahedron Lett. 2003, 59, 10485–10497.
Shibasaki Epoxidation: Amides
R RO
N
O
N
O
4Å MSTHF/toluene
rt
CMHP (1.5 equiv)
5 mol% (R)-H8-BINOL5 mol% Sm(Oi-Pr)3
Ph3P O100 mol%
PhO
N
O ON
O
CyO
N
OO
N
O
8
R
98% yield>99.5% ee
95% yield99% ee
90% yield>99.5% ee
R = OMe91% yield
99% ee
R = Cl97% yield>99.5% ee
Matsunaga, S.; Qin, H.; Sugita, M.; Okada, S.; Kinoshita, T.; Yamagiwa, N.; Shibasaki, M. Tetrahedron 2006, 62, 6630–6639.
OHOH
H8-BINOL
Nemoto, T.; Ohshima, T.; Yamaguchi, K.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 2725–2732.
Shibasaki Epoxidation: Mechanism
La-BINOLoligomer
(less active)
La(Oi-Pr)3(less active)
BINOL Ph3As O
La Oi-PrO
OO
AsPh3
LaO
OO
AsPh3
OO
H
LaOO
OOHO
O OPh3As AsPh3
Ph3As
La OO
OO
AsPh3
Ot-BuLa Ot-BuO
OO
AsPh3
La OO
OO
AsPh3
Ot-BuO
R R
LaO
OO
AsPh3
O
R R
OOt-Bu
TBHP
t-BuOHO
R RO O
R R
La(Oi-Pr)3
(O AsPh3)n Ph3As Oadditional
2
La(Oi-Pr)3
Shibasaki Epoxidation: Stereoselectivity Model
O
OLnO
AsO
t-BuO
RO
R
O
OLnO
AsOOt-Bu
RO
R
favored
Tosakai, S.-Y.; Horiuchi, Y.; Nemoto, T.; Ohshima, T.; Shibasaki, M. Chem. Eur. J. 2004, 10, 1527–1544.
Shibasaki Epoxidation: Esters
OO
OOHOH
ligand
OOEt
OO
OEt
O
OOEt
OO
OEt
O
R
81% yield93% ee
R = OAc89% yield
89% ee
R = OMe74% yield
99% ee
O
PMBO81% yield
96% ee
Ph
78% yield92% ee
OOEt
O
OOEt
O
Me
O
93% yield98% ee
78% yield92% ee
N
Kakei, H.; Tsuji, R.; Ohshima, T.; Shibasaki, M. J. Am. Chem. Soc. 2005, 127, 8962–8963.
R RO
OEt
O
OEt
O
4Å MS (dried)THF
rt
TBHP (1.2 equiv)
2–10 mol% ligand2–10 mol% Y(Oi-Pr)3
Ph3As O2–10 mol%
R2R1 R2
R1
R3
R2
R1
π ππ
R4R2
R1
R3
πR
R
ππ'
R1R2
General
Context Dependent
Few Examples
Phase-Transfer Epoxidations: Lead References
R RO
catalystNaOCl
aqueous biphasicR
O
R
O
Zhang, F.-Y.; Corey, E. J. Org. Lett. 1999, 1, 1287–4832.1290.
Lygo, B.; To, D. C. M. Tetrahedron Lett. 2001,, 42, 1343–1346.
Oxaziridine-Catalyzed Epoxidations: Lead References
5–10 mol% catalystOxone or TPPP
Na2CO3, CH3CN/H2O0 °Cor
CHCl3–40 °C
R1 R2
R1 R2O
R3 R3
OPh
catalyst A66% yield
95% ee
MePh
OPh
catalyst A58% yield
49% ee
Ph
OPh
catalyst B59% yield
97% ee
OMe
Me
NCO
catalyst A58% yield
20% ee
Ph4B NO
O Me
MePh
catalyst A
O
ON
MeMe
MeO2S
Ph4B
catalyst B
Page, P. C. B.; Buckley, B. R.; Blacker, A. J.Org. Lett. 2004, 6, 1543–1546.
Page, P. C. B.; Buckley, B. R.; Heaney, H.; Blacker, A. J.Org. Lett. 2005, 7, 375–377.
Imminium-Catalyzed Epoxidations: Lead References
R RO
catalystH2O2 or NsNIPh
CH2Cl2/H2Ortor
CH2Cl2/AcOH–30 °C
H
O
H
O
RO
H
O
catalyst BR = alkyl or Ar72–95% yield
≥7:1 dr85–97% ee
RO
H
O
catalyst AR = alkyl or Ar or CO2R
63–90% yield≥9:1 dr
94–98% ee
NH
catalyst A
OTMS
F3CCF3
F3C
CF3
Marigo, M.; Franzén, J.; Poulsen, T. B.; Zhung, W.;Jørgensen, K. A. J. Am. Chem. Soc. 2005, 127,
6964–6965.
Lee, S.; MacMillan, D. W. C.Tetrahedron 2006, 62, 11413–11424.
N
NH
t-Bu Bn
Me O
catalyst B
•HClO4
Sulfur Ylide-Catalyzed Epoxidations: Lead References
1 mol% Rh2(OAc)45–20 mol% sulfide
5–10 mol% BnEt3NClCH3CN40 °C
Ph N PhR
ON
Ts
NaH R
O
R = alkyl, olefin, Ar21–100% yield3:1 to ≥98:2 dr
87–94% ee
1 mol% Rh2(OAc)45–20 mol% sulfide
0–20 mol% BnEt3NClvarious solvents
40 °CR N Ph
RO
NTs
NaH Ph
O
R = olefin, Ar10–95% yield
1:1 to ≥98:2 dr20–94% ee
S
O
Ph
sulfide
Aggarwal, V. K. et al. J. Am. Chem. Soc. 2003, 125, 10926–10940.
Aggarwal, V. K. Acc. Chem. Res. 2004, 37, 611–620.
Also see: Winn, C. L.; Bellanie, B.; Goodman, J. M.; Tetrahedron Lett. 2002, 43,, 5427–5430.
Davoust, M.; Brière, J.-F.; Jaffrès, P.-A.; Metzner, P. J. Org. Chem. 2005, 70, 4166–4169.
Schaus, S. E; Brandes, B. D.; Larrow, J. F.; Tokunaga, M.; Hansen, K. B.; Gould, A. E.; Furrow, M. E.; Jacobsen, E. N.J. Am. Chem. Soc. 2002, 124, 1307–1315.
For an improved monomer catalyst, see: Nielsen, L. P. C.; Stevenson, C. P.; Blackmond, D. G.; Jacobsen, E. N.J. Am. Chem. Soc. 2004, 126, 1360–1362.
For a highly active oligomeric catalyst, see: White, D. E.; Jacobsen, E. N. Tetrahedron: Asymmetry 2003, 14, 3633–3638.
NN
O OCo
t-Bu t-Bu
t-Bu t-BuX
catalyst
0.05–2 mol% catalystH2O (0.55–0.7 equiv)
various solvents or neatrt
R RO
36–48% yield>99% ee
R
OHOH
Highly general for R = alkyl, aryl, olefin, alkynyl
Highly functional group tolerant
Hydrolytic Kinetic Resolution of Terminal Epoxides