关于在质子溶剂中使用烯丙基三甲氧基硅烷进行金属氟化物催化烯丙基化反应催化循环的机理研究。

Mechanistic studies on the catalytic cycle of metal fluoride-catalyzed allylation using allyltrimethoxysilane in protic solvents.

作者信息

Aoyama Naohiro, Hamada Tomoaki, Manabe Kei, Kobayashi Shū

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

J Org Chem. 2003 Sep 19;68(19):7329-33. doi: 10.1021/jo0346196.

DOI:10.1021/jo0346196

PMID:12968883

Abstract

The catalytic cycles of CdF(2).1-catalyzed and AgF.BINAP-catalyzed allylation using allyltrimethoxysilane in protic solvents were investigated. The experimental and (19)F NMR studies strongly supported that metal fluorides were regenerated from silyl fluoride species, and that these reactions were truly fluoride-catalyzed reactions. It was revealed that these catalytic cycles were much different from that of TBAF-catalyzed allylation using allyltrimethylsilane in THF.

摘要

研究了在质子溶剂中使用烯丙基三甲氧基硅烷进行CdF₂·1催化和AgF·BINAP催化的烯丙基化反应的催化循环。实验和¹⁹F NMR研究有力地支持了金属氟化物是由甲硅烷基氟化物物种再生的，并且这些反应是真正的氟化物催化反应。结果表明，这些催化循环与在四氢呋喃中使用烯丙基三甲基硅烷进行的TBAF催化的烯丙基化反应的催化循环有很大不同。