Kinetics and Mechanism of Allene Racemization Catalyzed by a Gold N-Heterocyclic Carbene Complex

Published

Journal Article

© 2016 American Chemical Society. The kinetics of the racemization of 1,3-disubstituted allenes catalyzed by (IPr)AuOTf (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) has been investigated. The rate of gold-catalyzed allene racemization obeyed the following second-order rate law: rate = krac[allene][Au]. An analysis of the rate of the gold-catalyzed racemization of 1-aryl-1,2-butadienes as a function of allene electron donor ability established moderate depletion of electron density on the C1 allenyl carbon atom in the rate-limiting transition state for racemization. Analysis of the temperature dependence of the rate of racemization of 1-(p-tolyl)-1,2-butadiene established the activation parameters ΔH∞ = 8.3 ± 1 kcal mol-1 and ΔS∞ = -28 ± 4 eu. These observations were in accord with a mechanism for allene racemization involving turnover-limiting, intermolecular allene exchange followed by rapid allene stereomutation.

Full Text

Duke Authors

Cited Authors

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

Published Date

  • July 11, 2016

Published In

Volume / Issue

  • 35 / 13

Start / End Page

  • 2242 - 2248

Electronic International Standard Serial Number (EISSN)

  • 1520-6041

International Standard Serial Number (ISSN)

  • 0276-7333

Digital Object Identifier (DOI)

  • 10.1021/acs.organomet.6b00307

Citation Source

  • Scopus