New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids

• Published in: Synlett 2015-07, Vol.26 (11), p.1427-1436
• Main Authors: Bour, Christophe, Gandon, Vincent
• Format: Article
• Language: English
• Subjects: account; Chemical Sciences
• ISSN: 0936-5214; 1437-2096
• DOI: 10.1055/s-0034-1380712

Abstract Cationic gold(I) complexes are soft Lewis acids that are able to trigger numerous types of nucleophilic attack onto alkenes, allenes, and alkynes (π-acid catalysis). In this account, we initially summarize the novel methods that we have developed to generate such catalysts by silver-free activation of ligated gold(I) chlorides. The advantages of this approach are the use of lower quantities of gold and the ability to scale-up transformations during which the standard gold/silver catalytic system is rapidly decomposed. In the second part, the synthesis and catalytic activity of original organogallium compounds is described. We have shown that (NHC)GaCl 2 + -type complexes display a high affinity for alkenes and alkynes, and trigger tandem C–C/C–C or C–C/C–H bond formation processes. Thus, they also behave as π-acids. Practical applications of these different gold- and gallium-based catalytic systems for the synthesis of cyclic compounds are presented. 1 Introduction 2 Silver-Free Two-Component Approaches in Gold Catalysis 2.1 The Gold/Copper Catalytic System 2.2 Other Applications with Gold/Lewis Acid Systems 3 Gallium Catalysis 3.1 Cationic Gallium Complexes Supported by N-Heterocyclic Car­bene Ligands 3.2 Catalytic Applications 4 Conclusions