Benzyne Cascade Reactions via Benzoxetenonium Ions and Their Rearrangements to o-Quinone Methides

被引：10

作者：

Shen, Hang ^{[1
,2
]}

Xiao, Xiao ^{[1
]}

Hoye, Thomas R. ^{[1
]}

机构：

[1] Univ Minnesota, Dept Chem, 207 Pleast St SE, Minneapolis, MN 55455 USA

[2] Univ Wisconsin, Dept Chem, 1101 Univ Ave, Madison, WI 53706 USA

来源：

ORGANIC LETTERS | 2019年 / 21卷 / 06期

基金：

美国国家科学基金会;

关键词：

THERMAL REARRANGEMENT; COUPLING REACTION; ARYNES; CYCLOAROMATIZATION; STEREOCHEMISTRY; MECHANISMS; INSERTION; BOND; FORM;

D O I：

10.1021/acs.orglett.9b00215

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new thermal isomerization of polyynes is described. Benzyne intermediates substituted by a C(RR')OR '' substituent adjacent to one of the benzyne sp-hybridized carbons give rise to products in which the OR' moiety has migrated to the proximal benzyne carbon. This process likely proceeds via sequential formation of multiple reactive intermediates: an initial thermally generated benzyne, a strained benzoxetenonium ion, and an o-quinone methide. As some examples demonstrate, the overall transformation can be quite efficient. The mechanism of this novel reaction is further supported by experiments and DFT calculations.

引用

页码：1672 / 1675

页数：4

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