Kinetics and mechanism of the racemization of aryl allenes catalyzed by cationic gold(I) phosphine complexes.

Journal Article (Journal Article)

The kinetics of the racemization of aromatic 1,3-disubstituted allenes catalyzed by gold phosphine complexes has been investigated. The rate of gold-catalyzed allene racemization displayed first-order dependence on allene, and catalyst concentration and kinetic analysis of gold-catalyzed allene racemization as a function of allene and phosphine electron-donor ability established the accumulation of electron density on the phosphine atom and the depletion of electron density on the terminal allenyl carbon atoms in the rate-limiting transition state for racemization. These and other observations were in accord with a mechanism for allene racemization involving rapid and reversible inter- and intramolecular allene exchange followed by turnover-limiting, unimolecular conversion of a chiral gold η(2)-allene complex to an achiral η(1)-allylic cation intermediate through a bent and twisted η(1)-allene transition state. With respect to proper ligand selection, these studies reveal that both electron-poor phosphine ligands and polar solvents facilitate racemization.

Full Text

Duke Authors

Cited Authors

  • Harris, RJ; Nakafuku, K; Widenhoefer, RA

Published Date

  • September 2014

Published In

Volume / Issue

  • 20 / 38

Start / End Page

  • 12245 - 12254

PubMed ID

  • 25111202

Pubmed Central ID

  • 25111202

Electronic International Standard Serial Number (EISSN)

  • 1521-3765

International Standard Serial Number (ISSN)

  • 0947-6539

Digital Object Identifier (DOI)

  • 10.1002/chem.201402729


  • eng