Dual gold catalysis: stepwise catalyst transfer via dinuclear clusters

TY - JOUR

T1 - Dual gold catalysis

T2 - stepwise catalyst transfer via dinuclear clusters

AU - Larsen, Mie Højer

AU - Houk, K. N.

AU - Hashmi, A. Stephen K.

PY - 2015/8/10

Y1 - 2015/8/10

N2 - The interest in and use of dual gold catalysts is forever increasing, but little is known of the mechanism for the catalyst transfer and its effect on the continued high turnover frequency. Herein, we present a computational investigation of the mechanism for the final intermolecular catalyst transfer in the synthesis of dibenzopentalene from 1-ethynyl-2-(phenylethynyl)benzene. Three different scenarios have been explored: a single catalyst transfer from the monoaurated product complex, the analogous water mediated single transfer, and a dual catalyst transfer from the diaurated product complex. Transition structures have been found for each step of the three possible pathways, and a stepwise dual catalyst transfer has proven to be the lowest energy pathway. We here describe a three-step transfer of two gold moieties from one dibenzopentalene to one diyne. This process directly gives the σ,π-gold coordinated diyne for the further intramolecular cyclization reaction.

AB - The interest in and use of dual gold catalysts is forever increasing, but little is known of the mechanism for the catalyst transfer and its effect on the continued high turnover frequency. Herein, we present a computational investigation of the mechanism for the final intermolecular catalyst transfer in the synthesis of dibenzopentalene from 1-ethynyl-2-(phenylethynyl)benzene. Three different scenarios have been explored: a single catalyst transfer from the monoaurated product complex, the analogous water mediated single transfer, and a dual catalyst transfer from the diaurated product complex. Transition structures have been found for each step of the three possible pathways, and a stepwise dual catalyst transfer has proven to be the lowest energy pathway. We here describe a three-step transfer of two gold moieties from one dibenzopentalene to one diyne. This process directly gives the σ,π-gold coordinated diyne for the further intramolecular cyclization reaction.

U2 - 10.1021/jacs.5b05773

DO - 10.1021/jacs.5b05773

M3 - Journal article

C2 - 26258807

SN - 0002-7863

VL - 137

SP - 10668

EP - 10676

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 33

ER -