Substrate-Controlled Aldol Reactions from Chiral α-Hydroxy Ketones

Dedicated to Professor Clayton H. Heathcock on the occasion of his 80^th birthday

Abstract

Chiral α-hydroxy ketones are valuable platforms from which highly stereoselective substrate-controlled aldol reactions may be performed. The suitable choice of the hydroxyl protecting group and the enolization conditions produce aldol adducts that can be easily manipulated to give a variety of enantiomerically pure compounds. Moreover, such aldol reactions often play a crucial role in the coupling of elaborate fragments in advanced steps of the synthesis of natural products. Together, these features confer to the α-hydroxy ketones a prominent position among the chiral substrates that are capable of providing highly asymmetric transformations.

1 Introduction

2 Pioneering Contributions

3 Boron-Mediated Aldol Reactions from α-Hydroxy Ethyl Ketones

4 Titanium-Mediated Aldol Reactions from α-Hydroxy Ethyl Ketones

5 Other Aldol Reactions from α-Hydroxy Ethyl Ketones

6 Aldol Reactions from α-Hydroxy Methyl Ketones

7 Conclusions

Key words

stereoselective synthesis - substrate-controlled reactions - aldol reactions - chiral α-hydroxy ketones - boron enolates - titanium enolates

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