Conjugate Alkynylation of Electrophilic Double Bonds. From Regioselectivity to Enantioselectivity

Dedicated to the memory of Professor Aede de Groot

Abstract

This review surveys the historical efforts addressed toward the development of the conjugate alkynylation reaction. The regio- and enantioselective conjugate alkynylation of electron-deficient double bonds, most commonly unsaturated carbonyl compounds, has been an elusive reaction for a long time. Intensive research during the last decades has resulted in the identification of a number of effective reagents and catalysts to perform this reaction. Non-stereoselective conjugate alkynylation of unsaturated carbonyl compounds was first achieved by using preformed alkynyl organometallics and later with terminal alkynes under catalytic conditions. These methods paved the way for the development of enantioselective procedures. After initial methods requiring stoichiometric amounts of chiral material, the findings by Corey on Ni-catalyzed addition of alkynylalanes and, particularly, by Carreira on Cu-catalyzed addition of terminal alkynes boosted the research on the development other asymmetric procedures catalyzed by Cu, Zn, Rh, Co, Ru and Pd complexes. The alkynylation of electrophilic alkenes conjugated with groups other than carbonyl and the alkynylation of extended conjugated systems are also discussed in the last part of this review.

1 Introduction

2 Non-Stereoselective Conjugate Alkynylation of α,β-Unsaturated Carbonyl Compounds

3 Enantioselective Conjugate Alkynylation of α,β-Unsaturated Carbonyl Compounds

4 Non-Stereoselective and Enantioselective Alkynylation of Other Electrophilic Alkenes

5 γ-Alkynylation of α,β-Unsaturated Amides and δ-Alkynylation of Electrophilic Dienes

6 Alternative Enantioselective Procedures

7 Conclusion and Outlook

Key words

conjugate addition - alkynes - enones - C–C bond formation - asymmetric catalysis - regioselectivity - electrophilic alkenes

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