Asymmetric Baylis-Hillman Reaction: An Enchanting Expedition

Abstract

The development of new strategies for realizing the asymmetric Baylis-Hillman reaction remains at the forefront of research into this important organic reaction. This review gives a comprehensive account of the work that has emanated from our group on the asymmetric Baylis-Hillman reaction. Herein, the use of homochiral electrophiles, Michael acceptors, and bases and double asymmetric induction protocols as tools for the asymmetric Baylis-Hillman reaction is discussed. The account also covers the application of such 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 Chiral Catalyst

2.3.2 Other Chiral Catalysts

2.4 Double Asymmetric Induction

2.5 Applications

2.5.1 α-Methylene-β-hydroxylactones via an Intramolecular Baylis-Hillman Reaction

2.5.2 Synthesis of Syributins

2.5.3 Sequential Baylis-Hillman Reaction and Ring-Closing Metathesis as a Protocol for Sugar-Linked α,β-Unsaturated γ-Lactone Library Generation

2.5.4 Synthesis of Non-natural Higher-Carbon Sugars

3 Conclusion

Key words

Baylis-Hillman reaction - asymmetric synthesis - aldehydes - acrylates - natural products

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16

Radha Krishna, P.; Sachwani, R. unpublished results.

23

Radha Krishna, P.; Sachwani, R. unpublished results.

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Radha Krishna, P.; Sachwani, R. unpublished results.