Asymmetric Baylis-Hillman Reaction: An Enchanting Expedition

Abstract

The development of new strategies for realizing the asymmetricBaylis-Hillman reaction remains at the forefront of researchinto this important organic reaction. This review gives a comprehensiveaccount of the work that has emanated from our group on the asymmetricBaylis-Hillman reaction. Herein, the use of homochiralelectrophiles, Michael acceptors, and bases and double asymmetricinduction protocols as tools for the asymmetric Baylis-Hillmanreaction is discussed. The account also covers the application ofsuch protocols in natural product synthesis. 1 Introduction 2 Asymmetric Baylis-Hillman Reaction: A Personal Account 2.1 Homochiral Electrophiles 2.1.1 Sugar-Derived Aldehydes 2.1.2 Chiral 2,3-Epoxy Aldehydes 2.2 Homochiral Michael Acceptors 2.2.1 TADDOL Acrylates 2.2.2 Sugar-Derived Acrylates 2.2.3 A Sugar-Derived Lactone 2.3 Homochiral Catalysts 2.3.1 N-Methylprolinol as the ChiralCatalyst 2.3.2 Other Chiral Catalysts 2.4 Double Asymmetric Induction 2.5 Applications 2.5.1 α-Methylene-β-hydroxylactones via anIntramolecular Baylis-Hillman Reaction 2.5.2 Synthesis of Syributins 2.5.3 Sequential Baylis-Hillman Reaction and Ring-Closing Metathesisas a Protocol for Sugar-Linked α,β-Unsaturated γ-LactoneLibrary Generation 2.5.4 Synthesis of Non-natural Higher-Carbon Sugars 3 Conclusion