由 PVP 稳定的纳米金催化的烯烃的分子内羟烷化反加成反应机理。

Anti-addition mechanism in the intramolecular hydroalkoxylation of alkenes catalyzed by PVP-stabilized nanogold.

机构信息

Research Center for Molecular Scale Nanoscience, Institute for Molecular Science, Myodaiji, Okazaki 444-8787, Japan.

出版信息

Molecules. 2012 Mar 2;17(3):2579-86. doi: 10.3390/molecules17032579.

DOI:10.3390/molecules17032579

PMID:22388968

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6268499/

Abstract

(1R*,4S*,4aR*,9aS*,10S*)-10-Hydroxy-10-phenyl-1,4a,9a,10-tetrahydro-1,4-methanoanthracen-9(4H)-one (1c) was prepared for the elucidation of the reaction mechanism of intramolecular hydroalkoxylation of alkenes catalyzed by gold nanoclusters stabilized by a hydrophilic polymer, poly(N-vinyl-2-pyrrolidone) (Au:PVP). It was found that the reaction proceeded via anti-addition of alcohol to the alkene assisted by p-activation of the gold clusters, which is the same mechanism as the hydroamination by toluenesulfonamides.

摘要

(1R*,4S*,4aR*,9aS*,10S*)-10-羟基-10-苯基-1,4a,9a,10-四氢-1,4-甲撑蒽-9(4H)-酮（1c）被制备用于阐明由亲水聚合物稳定的金纳米簇催化的烯烃的分子内氢烷氧基化反应机理，该亲水聚合物为聚（N-乙烯基-2-吡咯烷酮）（Au：PVP）。研究发现，该反应通过醇的反加成进行，金簇的 p-活化辅助了该反应，这与甲苯磺酰胺的氢胺化反应机制相同。