Multiselective Catalytic Asymmetric Reactions Using α-Keto Esters as Pronucleophiles

In memory of Professor Dieter Enders

Published as part of the ISySyCat2019 Special Issue

Abstract

In the reactions of simple starting materials, precise catalytic control of the stereochemical outcome (enantio- and diastereoselectivity), as well as chemoselectivity and regioselectivity is an efficient approach to increase molecular complexity with minimal use of protecting groups. Here, we introduce our ongoing studies on asymmetric catalytic reactions using α-keto esters as pronucleophiles or formal 1,3-dipolarophiles. Capitalizing on the high tunability of our late transition-metal complexes with a suitable basic counteranion, we have established a range of multiselective catalytic protocols starting from α-keto esters to provide a wide variety of stereochemically complex molecules incorporating adjacent stereocenters.

1 Introduction

2 Catalytic Asymmetric Monofluorination with NSFI

3 Catalytic Asymmetric Michael Reaction with Nitroolefins

4 Catalytic Asymmetric [3+2] Cycloaddition with (E)-Nitrones

5 Catalytic Asymmetric [3+2] Cycloaddition with Nitrile Oxides

6 Summary

Key words

α-keto esters - enolates - chemoselectivity - stereoselectivity - regioselectivity - transition metals - asymmetric catalysis - nucleophilic addition

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