Mechanistic Study of Gold(I)-Catalyzed Intermolecular Hydroamination of Allenes

被引:145
作者
Wang, Z. Jane [1 ]
Benitez, Diego [2 ]
Tkatchouk, Ekaterina [2 ]
Goddard, William A., III [2 ]
Toste, F. Dean [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] CALTECH, Mat & Proc Stimulat Ctr, Pasadena, CA 91125 USA
关键词
GOLD CATALYSIS; INTRAMOLECULAR HYDROAMINATION; HIGHLY EFFICIENT; ALLYLIC ETHERS; COMPLEXES; CYCLOISOMERIZATION; HYDROARYLATION; HYDROALKOXYLATION; AUROPHILICITY; CYCLIZATION;
D O I
10.1021/ja105530q
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
引用
收藏
页码:13064 / 13071
页数:8
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