Science of Synthesis: Asymmetric Organocatalysis Vol. 2 Bronsted Base and Acid Catalysts, and Additional Topics Bearbeitet von Takahiko Akiyama, Yukihiro Arakawa, Ying-Chun Chen, Hai-Lei Cui, Li Deng 1. Auflage 2012. Taschenbuch. 1010 S. Paperback ISBN 978 3 13 169371 6 Format (B x L): 17 x 25,5 cm Weitere Fachgebiete > Chemie, Biowissenschaften, Agrarwissenschaften > Analytische Chemie > Organische Chemie Zu Leseprobe schnell und portofrei erhältlich bei Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft. Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, eBooks, etc.) aller Verlage. Ergänzt wird das Programm durch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr als 8 Millionen Produkte.
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Science of Synthesis: Asymmetric Organocatalysis Vol. 2
Bronsted Base and Acid Catalysts, and Additional Topics
Bearbeitet vonTakahiko Akiyama, Yukihiro Arakawa, Ying-Chun Chen, Hai-Lei Cui, Li Deng
Die Online-Fachbuchhandlung beck-shop.de ist spezialisiert auf Fachbücher, insbesondere Recht, Steuern und Wirtschaft.Im Sortiment finden Sie alle Medien (Bücher, Zeitschriften, CDs, eBooks, etc.) aller Verlage. Ergänzt wird das Programmdurch Services wie Neuerscheinungsdienst oder Zusammenstellungen von Büchern zu Sonderpreisen. Der Shop führt mehr
Asymmetric Organocatalysis 2Lewis Base and Acid Catalysts
Date of publication: December 28, 2011
b Georg Thieme Verlag KGStuttgart · New York
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Science of Synthesis
Asymmetric Organocatalysis 2Lewis Base and Acid Catalysts
Volume Editor B. List
Authors T. D. BeesonM. BenohoudJ. W. BodeS. ChenM. ChristmannP.-C. ChiangD. A. DiRoccoY. C. FanT. FurutaP. Garc�a-Garc�aS. HatakeyamaY. HayashiJ. JiaT. KawabataN. J. KerriganO. KwonY. LiuD. W. C. MacMillan
N. MaseP. MelchiorreS. MukherjeeA. PiisolaP. M. PihkoT. A. RamirezT. RovisE. C. SaloY. ShiA. D. SmithK. SuzukiH. TakikawaX.-W. WangY. WangA. J. B. WatsonO. A. WongP. A. WoodsS. M. Yliniemel�-Sipari
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Science of Synthesis
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� 2012 Georg Thieme Verlag KGR�digerstrasse 14D-70469 Stuttgart
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Dr. M. Fiona Shortt de HernandezManaging EditorScience of Synthesis/Houben–WeylThieme Chemistry
2.1.2.1.5.1 Synthesis of tert-Butyl Cyclopropanecarboxylates
2.1.2.1.5.2 Reaction of Indole with Morita–Baylis–Hillman Adducts
2.1.2.1.5.3 Reaction of Furan-2-ones with Morita–Baylis–Hillman Adducts
2.1.2.1.6 Asymmetric Electrophilic Halogenation of Alkenes
2.1.2.1.6.1 Chlorolactonization of Pent-4-enoic Acid
2.1.2.2 Enantioselective Base Catalysis
2.1.2.2.1 Asymmetric Brønsted Base Catalysis
2.1.2.2.1.1 Asymmetric Protonation of Silyl Enol Ethers
2.1.2.2.1.2 Alcoholysis of Anhydrides in the Presence of a Cinchona-Derived Catalyst
2.1.2.2.1.3 Alcoholysis in the Presence of a Substoichiometric Amount ofCatalyst and a Stoichiometric Amount of an Achiral Base
Asymmetric Organocatalysis 2: Table of Contents 7
2.1.2.2.1.4 Enantioselective Alcoholysis of Monosubstituted SuccinicAnhydrides by Parallel Kinetic Resolution
2.1.2.2.1.5 Alcoholysis of Urethane-Protected Æ-Amino Acid N-Carboxyanhydridesby Kinetic Resolution
2.1.2.2.1.6 Alcoholysis of 1,3-Dioxolane-2,4-diones by Dynamic Kinetic Resolution
2.1.2.2.2 Asymmetric Lewis Base Catalysis
2.1.2.2.2.1 Asymmetric Sulfinyl Transfer Reactions via Dynamic Kinetic Resolution ofSulfinyl Chlorides: Synthesis of Sulfinates in the Presence of a StoichiometricAmount of Catalyst
2.1.2.2.2.2 Synthesis of Sulfinates in the Presence of a Catalytic Amount ofCatalyst and a Stoichiometric Amount of Achiral Base
2.1.2.2.2.3 Fluorodesilylation of Allylsilanes: Synthesis of Chiral Alkyl Fluorides
2.1.2.2.2.4 Conjugate Addition of Thiols to Cyclic Enones
2.1.2.2.2.5 Conjugate Addition of 1,3-Dicarbonyl Compounds to Alkynones
2.1.2.2.2.6 Conjugate Addition of 1,3-Dicarbonyl Compounds to Enones
2.1.2.2.2.7 Conjugate Addition of Alkylidenemalononitriles
2.1.2.2.2.8 Asymmetric Mannich Reaction of Æ-Substituted Cyanoacetates
2.1.2.2.2.9 Asymmetric Aldol Reaction of Oxindoles with Trifluoropyruvate
2.1.2.3 Acid–Base Cooperative Catalysis
2.1.2.3.1 Asymmetric 1,2-Addition to Carbonyl Compounds
2.1.2.3.1.1 Aldol Reaction of Cyclic Ketones
2.1.2.3.1.2 Aldol Reaction of Acyclic Ketones
2.1.2.3.1.3 Intramolecular Aldol Reaction of Diketones
2.1.2.3.2 Asymmetric 1,2-Addition to Imines
2.1.2.3.2.1 Hydrophosphonylation Reaction of Imines with Phosphites
2.1.2.3.2.2 Reaction of �-Oxo Esters with Imines
2.1.2.3.3 Asymmetric Friedel–Crafts Reactions
2.1.2.3.3.1 Reaction of Indoles and Trifluoropyruvate
2.1.2.3.3.2 Reaction of Indoles with Aldehydes or Pyruvates
2.1.2.3.3.3 Reaction of Indoles and Imines
2.1.2.3.4 Asymmetric Fragmentation
2.1.2.3.4.1 Enantioselective Fragmentation of Cyclic meso-Peroxides
2.1.2.3.4.2 Desymmetrization of meso-Cyclopropane-FusedCyclopentanones and Epoxycyclopentanones
2.1.2.3.5 Desymmetrization of meso-Diols
2.1.2.3.5.1 Monobenzoylation of meso-Diols
2.1.2.3.6 Asymmetric Halolactonization
2.1.2.3.6.1 Asymmetric Bromolactonization of Pentenoic Acids
8 Science of Synthesis Alert
2.1.2.3.6.2 Asymmetric Bromolactonization of Z-Enynes
2.1.2.4 Base–Iminium Catalysis
2.1.2.4.1 Asymmetric Conjugate Additions
2.1.2.4.1.1 Vinylogous Michael Addition of Æ,Æ-Dicyanoalkenes to Enones
2.1.2.4.1.2 Conjugate Addition of Benzannulated Cyclic 1,3-Dicarbonyl Compounds to Enones
2.1.2.4.1.3 Conjugate Addition of Nitrogen Nucleophiles to Enones
2.3.9.4 Asymmetric Aldol Reactions, Mannich Reactions, and Michael Additions
2.3.9.4.1 Practical Asymmetric Synthesis of a Key Building Block for an HIV ProteaseInhibitor by the Proline-Catalyzed Direct Cross-Aldol Reaction
2.3.9.4.2 Asymmetric Synthesis of a Key Building Block for Maraviroc bya Proline-Catalyzed Mannich Reaction of Acetaldehyde
2.3.9.4.3 Asymmetric Synthesis of a Pharmaceutical Intermediate byMichael Addition of a Dialkyl Malonate
2.3.9.4.4 Efficient Synthesis of (–)-Oseltamivir by an OrganocatalyzedMichael Reaction of an Aldehyde and a Nitroalkene
2.3.9.5 Organocatalyzed Asymmetric Epoxidations
2.3.9.5.1 Practical Procedure for the Large-Scale Preparation of Methyl (2R,3S)-3-(4-Methoxyphenyl)oxirane-2-carboxylate, a Key Intermediate for Diltiazem
2.3.9.5.2 Approach to a Chiral Lactone: Application of the Shi Epoxidation
2.3.9.6 Diastereoselective and Enantioselective Aza-Henry Reaction
2.3.9.9 Asymmetric Hydrocyanation and Strecker Reactions
2.3.9.10 Future Prospects
2.4 Future PerspectivesB. List and K. Maruoka
2.4 Future Perspectives
2.4.1 Future Perspectives for Lewis Base and Acid Catalysts
2.4.2 Future Perspectives for Brønsted Base and Acid Catalysts, and Additional Topics
Keyword Index
Author Index
Abbreviations
26 Science of Synthesis Alert
Abstracts
2.1.1 Chiral Guanidine and Amidine OrganocatalystsK. Nagasawa and Y. Sohtome
Guanidines and amidines are relatively strong Brønsted bases owing to the stability oftheir conjugate acids. The corresponding guanidinium and amidinium salts are able toserve as double hydrogen bond donors and play key roles in controlling the three-dimen-sional geometries of transition states. This review describes the development of usefulgeneral strategies for catalytic asymmetric transformations using chiral guanidines andamidines or their salts. Special emphasis is given to the key requirements for the designof guanidine and amidine organocatalysts and to reaction protocols employed.
aldol • nitro-Mannich • Mannich • Michael • epoxidation
2.1.2 Cinchona Alkaloid OrganocatalystsR. P. Singh and L. Deng
Cinchona alkaloid derivatives have emerged as one of the most powerful classes of chiralcatalysts in asymmetric synthesis. At a fundamental level, this development resultedfrom the key mechanistic discovery that modified cinchona alkaloids could serve as effi-cient and general base catalysts to promote highly enantioselective asymmetric reactions
Asymmetric Organocatalysis 2: Abstracts 27
via the activation of a broad range of nucleophiles. Moreover, this mode of asymmetriccatalysis has been successfully coupled with various modes of catalysis centered on theactivation of electrophiles, such as acid and iminium catalysis, thereby leading to the de-velopment of highly efficient and general cooperative catalysis based on organic cata-lysts. Importantly, this powerful strategy, proven to be among the most generally applica-ble in asymmetric catalysis, has been extended to multifunctional catalysis, which pro-motes and controls multiple stereoselective steps involving distinct transition states. Inthis review, we highlight the practice of these newly emerged concepts as a widely appli-cable strategy for the development of an extremely broad range of stereoselective trans-formations.
2.1.3 Bifunctional Cinchona Alkaloid OrganocatalystsH. B. Jang, J. S. Oh, and C. E. Song
This chapter presents the current state of the art in the development of cinchona alkaloidbased bifunctional catalysts in organocatalysis. In the last few years, cinchona alkaloidbased bifunctional catalysts have been shown to catalyze an outstanding array of enantio-selective chemical reactions by a dual activation mechanism, often with remarkable ste-reoselectivity. Although the bifunctionality of the catalysts has enabled cooperative catal-ysis to be achieved, it has also been identified as a potential source of self-aggregation ofthe catalysts which will have to be addressed in the coming years.
2.2.1 Phosphoric Acid Catalyzed Reactions of IminesT. Akiyama
Chiral phosphoric acids derived from 1,1¢-bi-2-naphthols catalyze nucleophilic additionreactions, cycloaddition reactions, and transfer hydrogenation reactions to imines, givingrise to chiral nitrogen-containing compounds with excellent enantioselectivities.
2.2.2 Phosphoric Acid Catalysis of Reactions Not Involving IminesM. Terada and N. Momiyama
Chiral phosphoric acid derivatives, in particular phosphoric acids and phosphoramidesderived from 3,3¢-disubstituted 1,1¢-bi-2-naphthols, are highly effective catalysts for a di-verse range of enantioselective reactions, including cycloadditions, ene reactions, ring-opening reactions, Friedel–Crafts reactions, Michael additions, aldol reactions, epoxida-tions, and various rearrangements. This chapter presents the state of the art of the rapidlydeveloping field of reactions involving catalysis by chiral phosphoric acid derivatives,with the exception of transformations using imines as electrophiles.
Asymmetric Organocatalysis 2: Abstracts 29
X
X
X = Ph, 4-t-BuC6H4, 4-PhC6H4, 2,4,6-iPr3C6H2, 2,4-iPr2-4-t-BuC6H2, SiPh3, 9-anthryl, 9-phenanthryl, etc; Z = bulky aryl group, SiPh3
epoxidation • Friedel–Crafts reaction • Michael addition • Nazarov cyclization
2.2.3 Brønsted Acid Catalysts Other than Phosphoric AcidsT. Hashimoto
The decade 2001–2010 has witnessed the remarkable development of chiral Brønsted acidor hydrogen-bond donor catalysis, both in terms of the emergence of structurally diversecatalysts and applications in various novel synthetic transformations. As for the source ofthe hydrogen bond donor, the research has mainly relied on the use of weak acids such asdiols and (thio)ureas, and strong acids, typically phosphoric acids. This chapter summa-rizes asymmetric reactions promoted by other chiral Brønsted acids, the acidity of whichranges from moderate to strong.
2.2.4 Hydrogen-Bonding Catalysts: (Thio)urea CatalysisK. Hof, K. M. Lippert, and P. R. Schreiner
This chapter reviews the application of thiourea organocatalysts in asymmetric synthesis,and the development and current status quo of the field. The chapter is then classifiedaccording to reaction type, focusing on: Michael reactions including phospha-Michaeland nitrocyclopropanations; Mannich reactions including acyl- and anti-Mannich, vinyl-ogous Mannich, and nitro-Mannich (aza-Henry) reaction; Henry (nitro-aldol) and aldol/vi-nylogous aldol reactions, and vinylogous Mukaiyama–aldol reactions; (aza-)Morita–Bay-lis–Hillman reactions; Strecker reactions; cyanosilylations; hydrophosphonylations; Frie-del–Crafts reactions; desymmetrization; kinetic resolutions; cycloadditions, includingthe Diels–Alder reaction and 1,3-dipolar cycloadditions; Pictet–Spengler reactions, includ-ing acyl- and protio- variants; Biginelli reactions; Petasis-type reactions; transfer hydroge-nations; reduction of ketones; aminations; alkylations; chlorinations; cationic polycycli-zation; and additions to oxocarbenium ions.
2.2.5 Hydrogen-Bonding Catalysts Other than Ureas and ThioureasD. Uraguchi and T. Ooi
Asymmetric catalyses of weakly acidic chiral molecules featuring hydrogen-bonding do-nor capabilities are summarized in this section. Besides the reactions catalyzed by chiraldiols, as representative nonionic Brønsted acids, enantioselective transformations underthe influence of chiral ionic Brønsted acids are mainly described.
Asymmetric Organocatalysis 2: Abstracts 31
O
O
OH
OH
OTBDMS
NMe2O
R1 H+
1.
20 mol%
toluene
2. AcCl, toluene, CH2Cl2 O
OR1
Keywords: diol • guanidinium salt • amidinium salt • aminophosphonium salt • pyridin-ium salt • Diels–Alder reaction • Mannich-type reaction • aldol reaction • Michael addition •
Henry reaction • Claisen rearrangement
2.2.6 Bifunctional (Thio)urea and BINOL CatalystsT. Inokuma and Y. Takemoto
Chiral bifunctional (thio)ureas and 1,1¢-bi-2-naphthol derivatives (BINOLS) bearing amine,alcohol, phosphine, sulfinamide, or pyridine substituents have been developed. Thesecatalysts can activate both a nucleophile and an electrophile simultaneously and promotea wide range of 1,2- and 1,4-nucleophilic additions with ketones, imines, nitroalkenes, en-ones, and Æ,�-unsaturated carboxylic acid derivatives in a highly stereoselective manner.
2.3.2 Phase Transfer Catalysis: Non-Natural-Product-Derived PTCS. Shirakawa and K. Maruoka
This chapter focuses on the progress of asymmetric reactions with various types of non-natural-product-derived chiral phase-transfer catalysts, showcasing the variations of theirmolecular designs and synthetic applications.
2.3.3 Computational and Theoretical StudiesI. P�pai
Thorough computational investigations, employing reliable electronic structure methodsand realistic molecular models, provide valuable insight into the origin of catalysis andstereoselectivity of organocatalytic transformations. This knowledge can be effectivelyutilized in new synthetic developments.
Asymmetric Organocatalysis 2: Abstracts 33
N
OO
O
O
H
‡
Keywords: reaction mechanism • density functional theory • transition states • mecha-nistic models • stereoselectivity • hydrogen bonding • activation modes • C-C bond forma-tion
2.3.4 Mechanism in OrganocatalysisM. Klussmann
The dramatic rise of asymmetric organocatalysis in recent years is certainly due, to a largeextent, to the increased awareness of its generality, based on an understanding of its re-action mechanisms. In the first part of this chapter, a short overview of methods thathave been used for the investigation of reaction mechanisms in organocatalysis is given,illustrated by selected examples of their application. In the second part of the chapter, thebeneficial interplay of different methods in bringing about a full mechanistic picture isdemonstrated by discussing two selected types of well-investigated organocatalytic reac-tions: enamine and iminium catalysis. The emphasis of this chapter is to highlight the in-formation that can be retrieved from the various experimental methods and to guide theexperimentalist in choosing the right experiments that can provide answers to theirmechanistic questions.
2.3.5 Supported OrganocatalystsS. Itsuno and N. Haraguchi
Polymer-immobilized chiral organocatalysts have been prepared and successfully used invarious asymmetric reactions. An ionically immobilized chiral quaternary ammoniumsulfonate polymer catalyzes the asymmetric alkylation of glycine derivatives with highenantioselectivity.
2.3.6 Organocatalysis Combined with Metal Catalysis or BiocatalysisZ.-Y. Han, C. Wang, and L.-Z. Gong
This review describes recent developments in reactions catalyzed by binary catalytic sys-tems consisting of an organocatalyst and a metal complex. The two catalysts may drivethe reaction in a cooperative manner or sequentially.
hydrogenation • Lewis base catalysts • tandem reaction • transfer hydrogenation • transi-tion metals
2.3.7 Peptide CatalysisJ. Duschmal�, Y. Arakawa, and H. Wennemers
Peptides have been developed as excellent asymmetric catalysts for numerous reactions.This manuscript summarizes the range of different reactions that are effectively cata-lyzed by peptides and highlights special features of peptidic catalysts.
2.3.8 Organocatalytic Cascade ReactionsY.-C. Chen and H.-L. Cui
This section focuses on organocatalytic cascade reactions, which enable the enantioselec-tive assembly of complex molecules and efficient formation of multiple bonds in onestep. The well-known activation modes of organocatalysis, such as enamine activation,iminium activation, SOMO activation, Brønsted acid catalysis, hydrogen-bonding activa-tion, and homoenolate activation, or combinations of these, may be implemented to com-plete various cascade transformations.
2.3.9 Industrial ApplicationsK. Izawa, T. Torii, T. Nishikawa, and H. Imai
This review describes recent progress in asymmetric organocatalyzed reactions particu-larly focusing on industrial applications, although some of the reactions cited here havenot yet been performed on an industrial scale.