Synthesis 2012; 44(22): 3401-3420
DOI: 10.1055/s-0032-1316788
review
© Georg Thieme Verlag Stuttgart · New York

π-Acid Mediated Insertion of Alkynes into Carbon–Heteroatom σ-Bonds


Holly V. Adcock, Paul W. Davies*
  • School of Chemistry, University of Birmingham, B15 2TT, UK   Fax: +44(121)4144403   Email: p.w.davies@bham.ac.uk
Further Information

Publication History

Received: 10 August 2012

Accepted: 10 September 2012

Publication Date:
02 October 2012 (eFirst)

Abstract

The rapidly expanding field of gold and platinum π-acid catalysis has led to the discovery of diverse transformations that are initiated with nucleophilic attack onto a metal-activated alkyne. This review brings together those reactions which employ a heteroatom nucleophile bearing a functional group that can subsequently migrate to effect a formal insertion of the alkyne into a carbon–heteroatom­ σ-bond. This reactivity profile is encountered in a range of efficient and powerful cycloisomerisations for the preparation of carbo- and heterocycles.

1 Introduction

2 1,2-Addition of Carbon–Heteroatom Bonds across Alkynes

2.1 Heteroatom-to-Carbon Allyl Migrations

2.2 Accessing Sigmatropic Rearrangements

2.3 Related Palladium-Catalysed 1,2-Carboalkoxylations and Carboaminations

2.4 Beyond Allyl Migration in the 1,2-Carbofunctionalisation of Alkynes

2.5 Oxonium Ion Migration

2.6 Migrating Centres at Higher Oxidation Levels

2.7 Migration of Heteroatoms

3 1,5 Heteroatom-to-Carbon Migrations

3.1 Alkynyl Benzoates as Alkylating Agents

4 Internal versus External Migrations

4.1 Internal Migrations of Oxonium Species

5 1,1-Carbofunctionalisations

6 Application in Natural Products

7 Summary and Conclusions