Science of Synthesis: Asymmetric Organocatalysis Vol. 2 E-Book

• Herausgeber: Thieme
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Deutsch
• Veröffentlichungsjahr: 2014

Beschreibung

Asymmetric Organocatalysis 2 from the Science of Synthesis series gives an authoritative, broad overview of the field, compiled by 3 8 experts, as well as a critical presentation of the best organocatalytic and related methodologies available today for practical as ymmetric synthesis. It provides alternative, greener syntheses with simple and easily used catalysts helping avoid the use of expens ive and/or toxic metals. The reference work covers all the catalysts and reactions within the activation modes Brønsted base catalys is and Brønsted acid catalysis. Typical or general experimental procedures as well as mechanistic, technical and theoretical aspects are included, allowing the reader to clearly see how simple, clean and efficient this chemistry is. // The content of this e-book w as originally published in December 2011.

Leseprobe

Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

– Methods critically evaluated by leading scientists

– Background information and detailed experimental procedures

– Schemes and tables which illustrate the reaction scope

Preface

As the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. Organic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail.

The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance.

The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben–Weyl Methoden der Organischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface.

From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods.

Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in Organic Synthesis, and Asymmetric Organocatalysis, among others. With expertevaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules.

Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality.

The Editorial Board

July 2010

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. A. Molander (Philadelphia, USA)

P. J. Reider (Princeton, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Asymmetric Organocatalysis Volumes

Asymmetric Organocatalysis 1

Lewis Base and Acid CatalystsVolume Editor: B. List

Asymmetric Organocatalysis 2

Brønsted Base and Acid Catalysts, and Additional TopicsVolume Editor: K. Maruoka

Abstracts

2.1.1 Chiral Guanidine and Amidine Organocatalysts

K. Nagasawa and Y. Sohtome

Guanidines and amidines are relatively strong Brønsted bases owing to the stability of their conjugate acids. The corresponding guanidinium and amidinium salts are able to serve as double hydrogen bond donors and play key roles in controlling the three-dimensional geometries of transition states. This review describes the development of useful general strategies for catalytic asymmetric transformations using chiral guanidines and amidines or their salts. Special emphasis is given to the key requirements for the design of guanidine and amidine organocatalysts and to reaction protocols employed.

Keywords: guanidines • amidines • guanidinium salts • amidinium salts • 2-aminoaceto-nitriles • alcohols • amines • nitroalkanes • epoxy ketones • hydrazines • phosphonates • phosphine oxides • δ-lactones • pyrrolidines • α-keto esters • Strecker • nitroaldol • Henry • aldol • nitro-Mannich • Mannich • Michael • epoxidation

2.1.2 Cinchona Alkaloid Organocatalysts

R. P. Singh and L. Deng

Cinchona alkaloid derivatives have emerged as one of the most powerful classes of chiral catalysts in asymmetric synthesis. At a fundamental level, this development resulted from the key mechanistic discovery that modified cinchona alkaloids could serve as efficient and general base catalysts to promote highly enantioselective asymmetric reactions via the activation of a broad range of nucleophiles. Moreover, this mode of asymmetric catalysis has been successfully coupled with various modes of catalysis centered on the activation of electrophiles, such as acid and iminium catalysis, thereby leading to the development of highly efficient and general cooperative catalysis based on organic catalysts. Importantly, this powerful strategy, proven to be among the most generally applicable in asymmetric catalysis, has been extended to multifunctional catalysis, which promotes and controls multiple stereoselective steps involving distinct transition states. In this review, we highlight the practice of these newly emerged concepts as a widely applicable strategy for the development of an extremely broad range of stereoselective transformations.

Keywords: cinchona alkaloids • enantioselective catalysis • acid–base bifunctional catalysis • base–iminium catalysis • Friedel–Crafts alkylations • kinetic resolution • organocatalyst • cooperative catalysis • bifunctional catalysts • cycloadditions • conjugate addition

2.1.3 Bifunctional Cinchona Alkaloid Organocatalysts

H. B. Jang, J. S. Oh, and C. E. Song

This chapter presents the current state of the art in the development of cinchona alkaloid based bifunctional catalysts in organocatalysis. In the last few years, cinchona alkaloid based bifunctional catalysts have been shown to catalyze an outstanding array of enantioselective chemical reactions by a dual activation mechanism, often with remarkable stereoselectivity. Although the bifunctionality of the catalysts has enabled cooperative catalysis to be achieved, it has also been identified as a potential source of self-aggregation of the catalysts which will have to be addressed in the coming years.

Keywords: organocatalysis • asymmetric catalysis • cooperative catalysis • bifunctional chiral catalysts • cinchona alkaloids • enantioselectivity • self-association

2.2.1 Phosphoric Acid Catalyzed Reactions of Imines

T. Akiyama

Chiral phosphoric acids derived from 1,1′-bi-2-naphthols catalyze nucleophilic addition reactions, cycloaddition reactions, and transfer hydrogenation reactions to imines, giving rise to chiral nitrogen-containing compounds with excellent enantioselectivities.

Keywords: amines • asymmetric catalysis • asymmetric synthesis • Brønsted acids • chiral compounds • cycloaddition • Friedel–Crafts alkylation • hetero-Diels–Alder reaction • imines • indoles • Mannich reaction • nucleophilic addition • phosphoric acids • transfer hydrogenation • reduction

2.2.2 Phosphoric Acid Catalysis of Reactions Not Involving Imines

M. Terada and N. Momiyama

Chiral phosphoric acid derivatives, in particular phosphoric acids and phosphoramides derived from 3,3′-disubstituted 1,1′-bi-2-naphthols, are highly effective catalysts for a diverse range of enantioselective reactions, including cycloadditions, ene reactions, ring-opening reactions, Friedel–Crafts reactions, Michael additions, aldol reactions, epoxidations, and various rearrangements. This chapter presents the state of the art of the rapidly developing field of reactions involving catalysis by chiral phosphoric acid derivatives, with the exception of transformations using imines as electrophiles.

Keywords: asymmetric catalysis • Baeyer–Villiger oxidation • binaphthols • chiral phosphoric acids • chiral phosphoramides • conjugate addition • cycloaddition • ene reaction • epoxidation • Friedel–Crafts reaction • Michael addition • Nazarov cyclization

2.2.3 Brønsted Acid Catalysts Other than Phosphoric Acids

T. Hashimoto

The decade 2001–2010 has witnessed the remarkable development of chiral Brønsted acid or hydrogen-bond donor catalysis, both in terms of the emergence of structurally diverse catalysts and applications in various novel synthetic transformations. As for the source of the hydrogen bond donor, the research has mainly relied on the use of weak acids such as diols and (thio)ureas, and strong acids, typically phosphoric acids. This chapter summarizes asymmetric reactions promoted by other chiral Brønsted acids, the acidity of which ranges from moderate to strong.

Keywords: acid catalysts • alkenylation • alkynylation • allylation • amines • arylation • asymmetric catalysis • aziridination • boron compounds • Brønsted acids • carboxylic acids • conjugate addition • diazo compounds • hydrazones • imines • Mannich reaction • Mukaiyama reaction • nitroso compounds • sulfonamides

2.2.4 Hydrogen-Bonding Catalysts: (Thio)urea Catalysis

K. 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 classified according to reaction type, focusing on: Michael reactions including phospha-Michael and nitrocyclopropanations; Mannich reactions including acyl- and anti-Mannich, vinylogous Mannich, and nitro-Mannich (aza-Henry) reaction; Henry (nitro-aldol) and aldol/vinylogous aldol reactions, and vinylogous Mukaiyama–aldol reactions; (aza-)Morita–Baylis–Hillman reactions; Strecker reactions; cyanosilylations; hydrophosphonylations; Friedel–Crafts reactions; desymmetrization; kinetic resolutions; cycloadditions, including the Diels–Alder reaction and 1,3-dipolar cycloadditions; Pictet–Spengler reactions, including acyl- and protio- variants; Biginelli reactions; Petasis-type reactions; transfer hydrogenations; reduction of ketones; aminations; alkylations; chlorinations; cationic polycyclization; and additions to oxocarbenium ions.

Keywords: thiourea • kinetic resolution • cycloaddition • Petasis reaction • transfer hydrogenation • addition • Henry reaction • Mannich reaction • chlorination • Morita–Baylis–Hillman reaction • reduction • alkylation • amination • Friedel–Crafts reaction • Pictet–Spengler reaction • polycyclization • cyanocyclization • Michael reaction • Biginelli reaction • hydrophosphonylation • aldol • desymmetrization • Strecker reaction

2.2.5 Hydrogen-Bonding Catalysts Other than Ureas and Thioureas

D. Uraguchi and T. Ooi

Asymmetric catalyses of weakly acidic chiral molecules featuring hydrogen-bonding donor capabilities are summarized in this section. Besides the reactions catalyzed by chiral diols, as representative nonionic Brønsted acids, enantioselective transformations under the influence of chiral ionic Brønsted acids are mainly described.

Keywords: diol • guanidinium salt • amidinium salt • aminophosphonium salt • pyridinium salt • Diels–Alder reaction • Mannich-type reaction • aldol reaction • Michael addition • Henry reaction • Claisen rearrangement

2.2.6 Bifunctional (Thio)urea and BINOL Catalysts

T. 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. These catalysts can activate both a nucleophile and an electrophile simultaneously and promote a wide range of 1,2- and 1,4-nucleophilic additions with ketones, imines, nitroalkenes, enones, and α,β-unsaturated carboxylic acid derivatives in a highly stereoselective manner.

Keywords: α-amino acids • β-amino acids • γ-amino acids • 1,2-diamines • pyrrolidines • piperidines • Michael addition • aza-Morita–Baylis–Hillman reaction • Mannich Reaction • aza-Henry reaction • cyanation • [3+2] cycloaddition

2.3.1 Phase-Transfer Catalysis: Natural-Product-Derived PTC

H.-g. Park

Natural-product-derived chiral quaternary ammonium salts generate ionic complexes with nucleophilic anions under phase-transfer catalytic conditions. Reaction of these complexes with electrophiles results in the stereoselective formation of chiral compounds.

Keywords: asymmetric phase-transfer catalytic reaction • enantioselective synthesis • chiral quaternary ammonium salts • cinchona alkaloid • tartrate

2.3.2 Phase Transfer Catalysis: Non-Natural-Product-Derived PTC

S. 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 their molecular designs and synthetic applications.

Keywords: phase-transfer catalysis • organocatalysis • asymmetric synthesis • asymmetric catalysis • alkylation • amino acids • Michael addition • aldol reaction • amination • epoxidation

2.3.3 Computational and Theoretical Studies

I. Pápai

Thorough computational investigations, employing reliable electronic structure methods and realistic molecular models, provide valuable insight into the origin of catalysis and stereoselectivity of organocatalytic transformations. This knowledge can be effectively utilized in new synthetic developments.

Keywords: reaction mechanism • density functional theory • transition states • mechanistic models • stereoselectivity • hydrogen bonding • activation modes • C—C bond formation

2.3.4 Mechanism in Organocatalysis

M. Klussmann

The dramatic rise of asymmetric organocatalysis in recent years is certainly due, to a large extent, to the increased awareness of its generality, based on an understanding of its reaction mechanisms. In the first part of this chapter, a short overview of methods that have 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, the beneficial interplay of different methods in bringing about a full mechanistic picture is demonstrated by discussing two selected types of well-investigated organocatalytic reactions: enamine and iminium catalysis. The emphasis of this chapter is to highlight the information that can be retrieved from the various experimental methods and to guide the experimentalist in choosing the right experiments that can provide answers to their mechanistic questions.

Keywords: asymmetric catalysis • enamine catalysis • iminium catalysis • kinetics • spectroscopy • reaction mechanism

2.3.5 Supported Organocatalysts

S. Itsuno and N. Haraguchi

Polymer-immobilized chiral organocatalysts have been prepared and successfully used in various asymmetric reactions. An ionically immobilized chiral quaternary ammonium sulfonate polymer catalyzes the asymmetric alkylation of glycine derivatives with high enantioselectivity.

Keywords: chiral organocatalyst • polymer-immobilized catalyst • enantioselective methanolysis • ketene dimerization • aldol reaction • Michael addition • alkylation • epoxidation • Diels–Alder reaction • allylation

2.3.6 Organocatalysis Combined with Metal Catalysis or Biocatalysis

Z.-Y. Han, C. Wang, and L.-Z. Gong

This review describes recent developments in reactions catalyzed by binary catalytic systems consisting of an organocatalyst and a metal complex. The two catalysts may drive the reaction in a cooperative manner or sequentially.

Keywords: alkaloids • alkynes • α-amino acids • asymmetric catalysis • Brønsted acids • hydrogenation • Lewis base catalysts • tandem reaction • transfer hydrogenation • transition metals

2.3.7 Peptide Catalysis

J. Duschmalé, 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 catalyzed by peptides and highlights special features of peptidic catalysts.

Keywords: peptides • asymmetric catalysis • epoxidation • oxidation • acylation • phosphorylation • sulfonylation • kinetic resolution • C—C bond forming reaction • aldol reaction • hydrocyanation • conjugate addition reaction • Stetter reaction • Morita–Baylis–Hillman reaction • acylanion equivalents • bromination • protonation

2.3.8 Organocatalytic Cascade Reactions

Y.-C. Chen and H.-L. Cui

This section focuses on organocatalytic cascade reactions, which enable the enantioselective assembly of complex molecules and efficient formation of multiple bonds in one step. The well-known activation modes of organocatalysis, such as enamine activation, iminium activation, SOMO activation, Brønsted acid catalysis, hydrogen-bonding activation, and homoenolate activation, or combinations of these, may be implemented to complete various cascade transformations.

Keywords: organocatalysts • cascade reactions • enamine activation • iminium activation • SOMO activation • Brønsted acid catalysis • hydrogen-bonding activation • homoenolate activation

2.3.9 Industrial Applications

K. Izawa, T. Torii, T. Nishikawa, and H. Imai

This review describes recent progress in asymmetric organocatalyzed reactions particularly focusing on industrial applications, although some of the reactions cited here have not yet been performed on an industrial scale.

Keywords: kinetic resolution • desymmetrization • bifunctional thiourea-type organocatalyst • alkylation • α-alkylated amino acids • cross-aldol reactions • Mannich reaction • maraviroc • Michael reaction • (−)-oseltamivir • Shi epoxidation • aza-Henry reaction • β-amino acid • enantioselective Friedel–Crafts reaction • hydrocyanation • Strecker reaction

Asymmetric Organocatalysis 2: Brønsted Base and Acid Catalysts, and Additional Topics

Preface

Abstracts

Table of Contents

2.1 Brønsted Bases

2.1.1 Chiral Guanidine and Amidine Organocatalysts

K. Nagasawa and Y. Sohtome

2.1.2 Cinchona Alkaloid Organocatalysts

R. P. Singh and L. Deng

2.1.3 Bifunctional Cinchona Alkaloid Organocatalysts

H. B. Jang, J. S. Oh, and C.E. Song

2.2 Brønsted Acids

2.2.1 Phosphoric Acid Catalyzed Reactions of Imines

T. Akiyama

2.2.2 Phosphoric Acid Catalysis of Reactions Not Involving Imines

M. Terada and N. Momiyama

2.2.3 Brønsted Acid Catalysts Other than Phosphoric Acids

T. Hashimoto

2.2.4 Hydrogen-Bonding Catalysts: (Thio)urea Catalysis

K. Hof, K. M. Lippert, and P. R. Schreiner

2.2.5 Hydrogen-Bonding Catalysts Other than Ureas and Thioureas

D. Uraguchi and T. Ooi

2.2.6 Bifunctional (Thio)urea and BINOL Catalysts

T. Inokuma and Y. Takemoto

2.3 Additional Topics

2.3.1 Phase-Transfer Catalysis: Natural-Product-Derived PTC

H.-g.Park

2.3.2 Phase-Transfer Catalysis: Non-Natural-Product-Derived PTC

S. Shirakawa and K. Maruoka

2.3.3 Computational and Theoretical Studies

I. Pápai

2.3.4 Mechanism in Organocatalysis

M. Klussmann

2.3.5 Supported Organocatalysts

S. Itsuno and N. Haraguchi

2.3.6 Organocatalysis Combined with Metal Catalysis or Biocatalysis

Z.-Y. Han, C. Wang, and L.-Z. Gong

2.3.7 Peptide Catalysis

J. Duschmalé, Y. Arakawa, and H. Wennemers

2.3.8 Organocatalytic Cascade Reactions

Y.-C. Chen and H.-L. Cui

2.3.9 Industrial Applications

K. Izawa, T. Torii, T. Nishikawa, and H. Imai

2.4 Future Perspectives

B. List and K. Maruoka

Keyword Index

Author Index

Abbreviations

Table of Contents

2.1 Brønsted Bases

2.1.1 Chiral Guanidine and Amidine Organocatalysts

K. Nagasawa and Y. Sohtome

2.1.1 Chiral Guanidine and Amidine Organocatalysts

2.1.1.1 Synthesis of 2-Aminoacetonitriles

2.1.1.1.1 Catalytic Asymmetric Strecker Reactions

2.1.1.2 Synthesis of Chiral Alcohols

2.1.1.2.1 Catalytic Nitroaldol (Henry) Reactions

2.1.1.2.1.1 Nitroaldol Reactions with α-Chiral Aldehydes

2.1.1.2.1.2 Nitroaldol Reactions with α-Keto Esters

2.1.1.2.2 Catalytic Asymmetric Aldol Reactions

2.1.1.2.2.1 Aldol Reactions with Dihalofuran-2(5H)-ones

2.1.1.3 Synthesis of Chiral Amines

2.1.1.3.1 Catalytic Asymmetric Nitro-Mannich-Type Reactions

2.1.1.3.1.1 Nitro-Mannich-Type Reactions with Nitroacetates

2.1.1.3.1.2 Nitro-Mannich-Type Reactions with α-Substituted Nitroacetates

2.1.1.3.2 Catalytic Asymmetric Mannich-Type Reactions

2.1.1.4 Synthesis of Chiral Nitroalkanes

2.1.1.4.1 Catalytic Asymmetric Michael Reactions

2.1.1.4.1.1 Michael Reactions with β-Keto Esters

2.1.1.4.1.2 Michael Reactions with Phenols

2.1.1.4.1.3 Michael Reactions with Nitroalkanes

2.1.1.4.1.4 Michael Reactions with 4,7-Dihydroindoles

2.1.1.5 Synthesis of Chiral Epoxy Ketones

2.1.1.5.1 Catalytic Asymmetric Nucleophilic Epoxidation Reactions

2.1.1.6 Synthesis of Chiral Hydrazines

2.1.1.6.1 Catalytic Asymmetric Amination Reactions

2.1.1.7 Synthesis of Chiral Phosphonates and Phosphine Oxides

2.1.1.7.1 Catalytic Asymmetric 1,4-Addition Reactions

2.1.1.7.1.1 1,4-Addition Reactions with Phosphites

2.1.1.7.1.2 1,4-Addition Reactions with Phosphine Oxides

2.1.1.8 Synthesis of Chiral δ-Lactones

2.1.1.8.1 Catalytic Asymmetric Inverse-Electron-Demand Hetero-Diels–Alder Reactions

2.1.1.9 Synthesis of Chiral Pyrrolidines

2.1.1.9.1 Catalytic Asymmetric [3+2]-Cycloaddition Reactions

2.1.1.10 Synthesis of Chiral α-Keto Esters

2.1.1.10.1 Catalytic Asymmetric Claisen Rearrangement Reactions

2.1.2 Cinchona Alkaloid Organocatalysts

R. P. Singh and L. Deng

2.1.2 Cinchona Alkaloid Organocatalysts

2.1.2.1 Nucleophilic Catalysis

2.1.2.1.1 Asymmetric Reactions with Ketenes

2.1.2.1.1.1 Synthesis of β-Lactones

2.1.2.1.1.2 Intramolecular Synthesis of β-Lactones

2.1.2.1.1.3 Synthesis of β-Lactams

2.1.2.1.1.4 Synthesis of β-Oxo Amides

2.1.2.1.1.5 Asymmetric Synthesis of α-Halogenated Esters

2.1.2.1.1.6 Cycloaddition of Ketenes and N-Thioacylimines

2.1.2.1.2 Asymmetric Morita–Baylis–Hillman Reactions

2.1.2.1.2.1 Synthesis of Hydroxy Acrylates

2.1.2.1.2.2 Synthesis of Sulfonamido Enones

2.1.2.1.3 Enantioselective Protonation

2.1.2.1.3.1 Thiol Addition to Alkyl(silyl)ketenes

2.1.2.1.4 Asymmetric Cyanation of Simple Ketones

2.1.2.1.4.1 Synthesis of Cyanohydrin Carbonates

2.1.2.1.5 Asymmetric Conjugate Additions

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 of Catalyst and a Stoichiometric Amount of an Achiral Base

2.1.2.2.1.4 Enantioselective Alcoholysis of Monosubstituted Succinic Anhydrides by Parallel Kinetic Resolution

2.1.2.2.1.5 Alcoholysis of Urethane-Protected α-Amino Acid N-Carboxyanhydrides by 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 of Sulfinyl Chlorides: Synthesis of Sulfinates in the Presence of a Stoichiometric Amount of Catalyst

2.1.2.2.2.2 Synthesis of Sulfinates in the Presence of a Catalytic Amount of Catalyst 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 α-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 β-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