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
收藏
页码：1672 / 1675
页数：4
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