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DOI: 10.1055/s-0034-1380712
New Procedures for Catalytic Carbophilic Activation by Gold and Gallium π-Acids
Publikationsverlauf
Received: 20. März 2015
Accepted after revision: 14. April 2015
Publikationsdatum:
08. Juni 2015 (online)
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Dedicated, with admiration, to K. Peter C. Vollhardt
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)GaCl2 +-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
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See inter alia:
The presence of silver in the reaction mixture can actually play a positive or a negative role see:
For silver-free activation of gold(I) complexes by Lewis acids that do not belong to the silver series see inter alia:
For a discussion about main group elements behaving as transition metals see:
For the relationship between gold (and other noble metals) and polarizable main group elements in π-acid catalysis see:
N-Heterocyclic carbenes (NHCs), cyclic alkyl amino carbenes (CAAC), NHC-olefins carbodiphosphoranes carbodicarbenes etc:
Copper complexes are sometimes potent carbophilic catalysts, see inter alia:
For recent reviews on enantioselective gold catalysis, see:
For the first substantial report on the use of AuCl3 as a cycloisomerization catalyst, see:
See inter alia:
See inter alia: