Aryl vinyl cyclopropane Cope rearrangements
Aryl vinyl cyclopropane Cope rearrangements
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DOI：
10.1016/j.tet.2019.04.061
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发表时间：
2019-06-14
期刊：
影响因子：
2.1
通讯作者：
Tunge, Jon
中科院分区：
文献类型：
--
作者：
Allegre, Kevin;Tunge, Jon
虽然二乙烯基环丙烷Cope重排是众所周知的，并且已广泛应用于合成中，但芳基乙烯基环丙烷Cope重排的例子不太常见，并且通常在范围或反应产率方面受到限制。芳基乙烯基环丙烷 Cope 重排可以得到苯并环庚烯支架，该支架存在于各种天然存在的和医学相关的产品中。在此，我们报告了一种通过芳基乙烯基环丙烷 Cope 重排获得两种区域异构苯并环庚烯产物中的一种的方法，具有添加剂控制的区域选择性。机理研究表明环丙烷立体异构体的动态平衡，然后是顺式非对映异构体的重排。 (C) 2019 年由爱思唯尔有限公司出版。
While the divinyl cyclopropane Cope rearrangement is well-known, and has been broadly applied in synthesis, examples of the aryl vinyl cyclopropane Cope rearrangement are less common and generally limited in scope or reaction yield. The aryl vinyl cyclopropane Cope rearrangement gives access to the benzocycloheptene scaffold, which is present in a variety of naturally occurring and medicinally relevant products. Herein we report a method to obtain either of two regioisomeric benzocycloheptene products via an aryl vinyl cyclopropane Cope rearrangement, featuring additive-controlled regioselectivity. Mechanistic studies indicate a dynamic equilibration of cyclopropane stereoisomers, followed by rear-rangement of the cis diastereomer. (C) 2019 Published by Elsevier Ltd.