3,3′-Bithiophene-Based Chiral Bisphosphine Oxides as Organocatalysts in Silicon-Derived Lewis Acid Mediated Reactions

Published as part of the ISySyCat2019 Special Issue

Abstract

This account summarizes the development of new biheteroaromatic chiral bisphosphine oxides. 3,3′-Bithiophene-based phosphine oxides (BITIOPOs) have been successfully used as organocatalysts to promote Lewis base catalyzed, Lewis acid mediated stereoselective transformations. These highly electron-rich compounds, in combination with trichorosilyl derivatives (allyltrichlorosilane and silicon tetrachloride), generate hypervalent silicon species that act as chiral Lewis acids in highly diastereo- and enantioselective organic reactions. Several relevant examples related to these applications are discussed in detail.

1 Introduction

2 The BITIOPO Family

3 Enantioselective Opening of Epoxides

4 Enantioselective Allylation of Aldehydes

5 Stereoselective Direct (Double) Aldol-Type Reaction with Ketones

6 Stereoselective Direct Aldol-Type Reaction with Ester Derivatives

7 Conclusions

Key words

silicon hypercoordination - organocatalysis - Lewis bases - aldol reactions - stereoselective reactions - chiral phosphine oxides

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