title: Kinetics and mechanism of the racemization of aryl allenes catalyzed by cationic gold(I) phosphine complexes.
abstract: 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.
authors.affiliation: Department of Chemistry, Duke University, French Family Science Center, Durham, NC, 27708 (USA).
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Harris
authors.forename: Kohki
authors.initials: K
authors.lastname: Nakafuku
authors.forename: Ross A
authors.initials: RA
authors.lastname: Widenhoefer
keywords: allenes; allylic compounds; gold; pi complexes; racemization