title: Gold(I)-catalyzed intermolecular hydroalkoxylation of allenes: a DFT study.
abstract: The mechanistic and regiochemical aspects in the Au(I)-catalyzed intermolecular hydroalkoxylation of allenes have been studied computationally. The most favorable pathway is nucleophilic attack of an Au(I)-coordinated allene, which occurs irreversibly. An Au(I)-catalyzed mechanism is proposed that allows the facile interconversion of regioisomeric allylic ether products. The regioisomers are connected via a stabilized diether intermediate with a C-Au sigma-bond, which successfully explains the observed regioselectivity for the thermodynamic product.
authors.affiliation: Unilever Centre for Molecular Science Informatics, Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, United Kingdom. rsp25@cam.ac.uk
authors.forename: Robert S
authors.initials: RS
authors.lastname: Paton
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras