New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes

Identifier:  imarina:9228610

Handle: https://hdl.handle.net/20.500.11797/imarina9228610

Authors:  Zuccarello, Giuseppe; Escofet, Imma; Caniparoli, Ulysse; Echavarren, Antonio M

Abstract:
Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, the triple bond of alkynes cannot be prochiral. In addition, the linear coordination displayed by gold(I) complexes places the chiral ligand far away from the substrate resulting in an inefficient transfer of chiral information. This poses a significant challenge for the achievement of high enantiocontrol in gold(I)-catalyzed reactions of alkynes. Although considerable progress on enantioselective gold(I)-catalyzed transformations has recently been achieved, the asymmetric activation of non-prochiral alkyne-containing small molecules still represents a great challenge. Herein we summarize recent advances in intra- and intermolecular enantioselective gold(I)-catalyzed reactions involving alkynes, discussing new chiral ligand designs that lie at the basis of these developments. We also focus on the mode of action of these catalysts, their possible limitations towards a next-generation of more efficient ligand designs. Finally, square planar chiral gold(III) complexes, which offer an alternative to chiral gold(I) complexes, are also discussed.