Modern Methods in Stereoselective Aldol Reactions -- Contents -- Preface -- List of Contributors -- 1 Stereoselective Acetate Aldol Reactions -- 1.1 Introduction -- 1.2 Mukaiyama Aldol Reaction -- 1.2.1 Concept and Mechanism -- 1.2.2 Chiral Auxiliaries -- 1.2.3 Chiral Methyl Ketones -- 1.2.4 Chiral Aldehydes -- 1.2.4.1 1,2-Asymmetric Induction -- 1.2.4.2 1,3-Asymmetric Induction -- 1.2.4.3 Merged 1,2- and 1,3-Asymmetric Induction -- 1.2.5 Chiral Lewis Acids -- 1.2.6 Chiral Lewis Bases -- 1.3 Metal Enolates -- 1.3.1 Concept and Mechanism -- 1.3.2 Chiral Auxiliaries -- 1.3.3 Stoichiometric Lewis Acids -- 1.3.4 Catalytic Lewis Acids -- 1.3.5 Chiral Aldehydes -- 1.3.6 Chiral Methyl Ketones -- 1.3.6.1 a-Methyl Ketones -- 1.3.6.2 a-Hydroxy Ketones -- 1.3.6.3 b-Hydroxy Ketones -- 1.3.6.4 b-Hydroxy a-Methyl Ketones -- 1.3.6.5 a,b-Dihydroxy Ketones -- 1.3.6.6 Remote Stereocontrol -- 1.4 Conclusions -- References -- 2 The Vinylogous Mukaiyama Aldol Reaction in Natural Product Synthesis -- 2.1 Introduction -- 2.2 Aldehyde-Derived Silyl Dienol Ethers -- 2.2.1 Aldehyde-Derived Silyl Dienol Ethers - Diastereoselective Processes -- 2.2.2 Aldehyde-Derived Silyl Dienol Ethers - Enantioselective Processes -- 2.3 Ester-Derived Silyl Dienol Ethers -- 2.3.1 Ester-Derived Silyl Dienol Ethers - Diastereoselective Processes -- 2.3.2 Ester-Derived Silyl Dienol Ethers - Enantioselective Processes -- 2.3.3 Ester-Derived Silyl Dienol Ethers - Enantioselective and Substrate-Controlled Processes -- 2.4 Amide-Derived Silyl Dienol Ethers - Vinylketene Silyl N,O-Acetals -- 2.4.1 Model Systems - Kobayashi's Pioneering Studies -- 2.4.2 Total Syntheses -- 2.5 Acyclic Acetoacetate-Derived Silyl Dienolates - Chan's Diene -- 2.5.1 Chan's Diene in Diastereoselective Processes -- 2.5.2 Chan's Diene in Enantioselective Processes.

2.5.3 Chan's Diene in Enantioselective and Substrate-Controlled Processes -- 2.6 Cyclic Acetoacetate-Derived Dienolates -- 2.6.1 Cyclic Acetoacetate-Derived Dienolates - Diastereoselective Processes -- 2.6.2 Cyclic Acetoacetate-Derived Dienolates - Enantioselective Processes -- 2.6.3 Cyclic Acetoacetate-Derived Dienolates - Enantioselective and Substrate-Controlled Processes -- 2.7 Furan-Derived Silyloxy Dienes -- 2.7.1 Furan-Derived Silyloxy Dienes - Diastereoselective Processes -- 2.7.2 Furan-Derived Silyloxy Dienes - Enantioselective Processes -- 2.7.3 Furan-Derived Silyloxy Dienes - Enantioselective and Substrate-Controlled Processes -- 2.8 Pyrrole-Based 2-Silyloxy Dienes -- 2.9 Comparison with Other Methods -- References -- 3 Organocatalyzed Aldol Reactions -- 3.1 Introduction -- 3.2 Proline as Organocatalyst -- 3.2.1 Intramolecular Reactions -- 3.2.1.1 Intramolecular Proposed Mechanism -- 3.2.1.2 Application to Natural Product Synthesis -- 3.2.2 Intermolecular Reactions -- 3.2.2.1 Ketones as Source of Nucleophile -- 3.2.2.2 Aldehydes as Source of Nucleophile -- 3.2.2.3 Intermolecular Reaction Mechanism -- 3.2.2.4 Application to Natural Product Synthesis -- 3.3 Proline Derivatives as Organocatalysts -- 3.3.1 Prolinamide Derivatives -- 3.3.1.1 Ketones as Source of Nucleophile -- 3.3.1.2 Aldehydes as Source of Nucleophile -- 3.3.1.3 Application to Natural Product Synthesis -- 3.3.2 Proline Peptide Derivatives -- 3.3.2.1 Ketones as Source of Nucleophile -- 3.3.3 Hydroxyproline Derivatives -- 3.3.3.1 Intramolecular Reactions -- 3.3.3.2 Intermolecular Reactions -- 3.3.4 Sulfonimide Proline Derivatives -- 3.3.4.1 Ketones as Source of Nucleophile -- 3.3.4.2 Application to Natural Product Synthesis -- 3.3.5 Other Proline Derivatives -- 3.3.5.1 Intramolecular Reactions -- 3.3.5.2 Intermolecular Reactions.

3.3.5.3 Application to Natural Product Synthesis -- 3.3.6 Other Organocatalysts -- 3.3.6.1 Intramolecular Reactions -- 3.3.6.2 Intermolecular Reactions -- 3.3.7 Phase-Transfer Catalysis -- 3.4 Conclusions and Outlook -- References -- 4 Supersilyl Protective Groups in Aldol Reactions -- 4.1 Introduction -- 4.2 Aldol Addition with Acetaldehyde-Derived Super Silyl Enol Ether (1) -- 4.3 a-Substituted Silyl Enol Ethers Derived from Aldehydes -- 4.4 Aldol Addition to Chiral Aldehydes -- 4.5 One-Pot Sequential Aldol Reactions -- 4.6 Sequential Aldol-Aldol Reactions of Acetaldehyde -- 4.6.1 Acetaldehyde Double Aldol Reactions -- 4.6.2 Acetaldehyde Triple Aldol Reactions -- 4.6.3 Mixed Sequential Aldol-Aldol Reactions -- 4.7 Double Aldol Reactions with a-Substituted Silyl Enol Ethers -- 4.7.1 Sequential Aldol-Aldol Reactions with Mixed SEEs -- 4.7.2 Propionaldehyde Aldol-Aldol Cascade Reactions -- 4.7.3 Haloacetaldehyde Aldol-Aldol Cascades -- 4.8 Stereochemical Considerations -- 4.9 Aldol Reactions of b-Supersiloxy Methyl Ketones -- 4.10 Total Synthesis of Natural Products Using Supersilyl Aldol Reactions -- 4.11 Conclusion and Outlook -- References -- 5 Asymmetric Induction in Aldol Additions -- 5.1 Introduction -- 5.2 Asymmetric Induction Using Chiral Ketones -- 5.2.1 1,4-Asymmetric Induction Using a-Alkyl Ketones -- 5.2.2 1,4-Asymmetric Induction Using a-Methyl-b-Branched Ketones -- 5.2.3 1,4-Asymmetric Induction Using a-Alkoxy Ketones -- 5.2.4 1,5-Asymmetric Induction Using b-Alkoxy Methyl Ketones -- 5.2.5 1,6-Asymmetric Induction Using Chiral Methyl Ketones -- 5.3 Asymmetric Induction Using Chiral Aldehydes -- 5.3.1 1,2-Asymmetric Induction Using Chiral Aldehydes -- 5.3.2 1,3-Asymmetric Induction Using Chiral Aldehydes -- 5.3.3 Asymmetric Induction Using a-Methyl-b-Alkoxy Aldehydes -- 5.3.4 Asymmetric Induction Using a,b-Bisalkoxy Aldehydes.

5.4 Asymmetric Induction in the Aldol Addition of Chiral Enolates to Chiral Aldehydes -- References -- 6 Polypropionate Synthesis via Substrate-Controlled Stereoselective Aldol Couplings of Chiral Fragments -- 6.1 Introduction -- 6.2 Principles of Stereoselective Aldol Reactions -- 6.2.1 Relative Topicity -- 6.2.2 Chiral Reactants -- 6.2.2.1 Diastereoface Selectivity of Chiral Ethyl Ketones -- 6.2.2.2 Diastereoface Selectivity of Chiral Aldehydes -- 6.2.2.3 Multiplicativity Rule -- 6.3 Stereoselective Aldol Coupling of Chiral Reactants -- 6.3.1 2-Alkoxy-1-Methylethyl Ethyl Ketones: Paterson's Dipropionate Equivalent -- 6.3.1.1 Reactions with Achiral Aldehydes -- 6.3.1.2 Reactions with Chiral Aldehydes -- 6.3.2 1-Methylalkyl Ethyl Ketones: 3-Deoxy Polypropionate Equivalents -- 6.4 2-Alkoxyalkyl Ethyl Ketones: 2-Desmethyl Polypropionate Equivalents -- 6.4.1 2-Alkoxy-1-Methylalkyl Ethyl Ketones: Polypropionate Equivalents -- 6.4.1.1 (E) Boron Enolates -- 6.4.1.2 (Z) Boron Enolates -- 6.4.1.3 Silyl Enolates -- 6.4.1.4 Lithium Enolates -- 6.4.1.5 Titanium Enolates -- 6.4.1.6 Tin Enolates -- 6.5 Conclusions -- References -- 7 Application of Oxazolidinethiones and Thiazolidinethiones in Aldol Additions -- 7.1 Introduction -- 7.2 Preparation of Oxazolidinethione and Thiazolidinethione Chiral Auxiliaries -- 7.3 Acylation of Oxazolidinethione and Thiazolidinethione Chiral Auxiliaries -- 7.4 Propionate Aldol Additions -- 7.5 Acetate Aldol Additions -- 7.6 Glycolate Aldol Additions -- 7.6.1 Synthetic Applications of Aldol Additions of N-Propionyl Oxazolidinethiones and Thiazolidinethiones and Their Substituted Variants -- 7.6.2 Synthetic Applications of Aldol Additions of N-Acetyloxazolidinethiones and Thiazolidinethiones -- 7.6.3 Synthetic Applications of anti-Aldol Additions of N-Glycolyloxazolidinethiones -- References.

8 Enzyme-Catalyzed Aldol Additions -- 8.1 Introduction -- 8.2 Pyruvate Aldolases -- 8.3 N-Acetylneuraminic Acid Aldolase (NeuA) -- 8.3.1 Novel NeuA Biocatalyst by Protein Engineering -- 8.3.2 Large-Scale Process -- 8.3.3 Related Pyruvate Aldolases/2-Oxobutyrate Aldolases -- 8.4 Dihydroxyacetone Phosphate (DHAP) Aldolases -- 8.4.1 Structure and Mechanism -- 8.4.2 L-Rhamnulose-1-Phosphate Aldolase as a DHA-Dependent Aldolase -- 8.5 D-Fructose-6-Phosphate Aldolase and Transaldolase B Phe178Tyr: FSA-Like Aldolases -- 8.6 2-Deoxy-D-Ribose-5-Phosphate Aldolase (RibA or DERA -- EC 4.1.2.4) -- 8.7 Glycine/Alanine Aldolases -- 8.8 Aldol Reactions Catalyzed by Non aldolases -- 8.9 Conclusions and Perspectives -- 8.9.1 Substrate Tolerance/Stereoselectivity -- 8.9.2 Future Perspectives -- References -- Index.