Gold carbenes, gold-stabilized carbocations, and cationic intermediates relevant to gold-catalysed enyne cycloaddition. (5th May 2016)

• Record Type: Journal Article
• Authors: Harris, R. J.; Widenhoefer, R. A.
• Is Part Of: Chemical Society reviews. Volume 45:Number 16(2016:Aug.)
• Page Start: 4533
• Page End: 4551
• Publication Date: 2016-05-05
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c6cs00171h
• Languages: English
• ISSNs: 0306-0012

Abstract

Abstract : This review highlights recent advances made in the synthesis of cationic gold carbene complexes and in the direct detection of cationic intermediates generated via gold-catalysed enyne cycloaddition. Abstract : Cationic gold complexes in which gold is bound to a formally divalent carbon atom, typically formulated as gold carbenes or α-metallocarbenium ions, have been widely invoked in a range of gold-catalyzed transformations, most notably in the gold-catalyzed cycloisomerization of 1, n -enynes. Although the existence of gold carbene complexes as intermediates in gold-catalyzed transformations is supported by a wealth of indirect experimental data and by computation, until recently no examples of cationic gold carbenes/α-metallocarbenium ions had been synthesized nor had any cationic intermediates generated via gold-catalyzed enyne cycloaddition been directly observed. Largely for this reason, there has been considerable debate regarding the electronic structure of these cationic complexes, in particular the relative contributions of the carbene (LAu + CR2 ) and α-metallocarbenium (LAu–CR2 + ) forms, which is intimately related to the extent of d → p backbonding from gold to the C1 carbon atom. However, over the past ∼ seven years, a number of cationic gold carbene complexes have been synthesized in solution and generated in the gas phase and cationic intermediates have been directly observed in the gold-catalyzed cycloaddition of enynes. Together, these advances provide insight into the nature and electronic structure of gold carbene/α-metallocarbenium complexes and the cationic intermediates generated via gold-catalyzed enyne cycloaddition. Herein we review recent advances in this area.