High-yielding palladium-catalyzed intramolecular alkane arylation: Reaction development and mechanistic studies

被引：331

作者：

Lafrance, Marc ^{[1
]}

Gorelsky, Serge I. ^{[1
]}

Fagnou, Keith ^{[1
]}

机构：

[1] Univ Ottawa, Ctr Catalys Res & Innovat, Dept Chem, Ottawa, ON K1N 6N5, Canada

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2007年 / 129卷 / 47期

关键词：

D O I：

10.1021/ja076588s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Palladium-catalyzed alkane arylation reactions with aryl halides are described for the preparation of 2,2-dialkyl-dihydrobenzofuran substrates. These reactions occur in excellent yield and very high selectivity for the formation of one sole product arising from a reaction at nearby methyl groups. Mechanistic and computational studies point to the involvement of a concerted, inner-sphere palladation-deprotonation pathway that is enabled by the presence of three-center agostic interactions at the transition state. This mechanism accurately predicts the experimentally observed kinetic isotope effect as well as the site selectivity and should be useful in the design of new reactions and catalysts.

引用

页码：14570 / +

页数：3

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