The intermolecular hydroamination of allenes occurs readily with hydrazide nucleophiles, in the presence of 3-12% Ph3PAuNTf2. Mechanistic studies have been conducted to establish the resting state of the gold catalyst, the kinetic order of the reaction, the effect of ligand electronics on the overall rate, and the reversibility of the last steps in the catalytic cycle. We have found the overall reaction to be first order in gold and allene and zero order in nucleophile. Our studies suggest that the rate-limiting transition state for the reaction does not involve the nucleophile and that the active catalyst is monomeric in gold(I). Computational studies support an "outersphere" mechanism and predict that a two-step, no intermediate mechanism may be operative. In accord with this mechanistic proposal, the reaction can be accelerated with the use of more electron-deficient phosphine ligands on the gold(I) catalyst.
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Gandon, Vincent
论文数: 引用数:
h-index:
机构:
Lemiere, Gilles
Hours, Alexandra
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Hours, Alexandra
Fensterbank, Louis
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Fensterbank, Louis
Malacria, Max
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Gandon, Vincent
论文数: 引用数:
h-index:
机构:
Lemiere, Gilles
Hours, Alexandra
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Hours, Alexandra
Fensterbank, Louis
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France
Fensterbank, Louis
Malacria, Max
论文数: 0引用数: 0
h-index: 0
机构:
Univ Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, FranceUniv Paris 06, Chim Organ Lab, UMR 7611, Inst Chim Mol FR2769, F-75252 Paris, France