Palladium/Copper-Catalyzed Oxidative Arylation of Terminal Alkenes with Aroyl Hydrazides
Palladium/Copper-Catalyzed Oxidative Arylation of Terminal Alkenes with Aroyl Hydrazides
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钯/铜催化芳酰肼对末端烯烃的氧化芳基化
DOI：
10.1002/chem.201304696
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发表时间：
2014
期刊：
影响因子：
--
通讯作者：
Tian Shi-Kai
中科院分区：
文献类型：
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作者：
Zhang Yong-Gang;Liu Xiang-Lei;He Zeng-Yang;Li Xi-Ming;Kang Hong-Jian;Tian Shi-Kai
在有氧条件下，以简单芳酰肼为催化剂，通过末端烯烃的氧化芳基化反应，立体选择性地合成了1，2-二取代烯烃。一系列芳酰肼与末端烯烃在二甲基亚砜和乙腈的1：1混合物中进行钯/铜催化的氧化Mizoroki-Heck反应，以中等至优异的产率和优异的区域选择性和E选择性得到结构多样的1，2-二取代烯烃。该反应耐受各种各样的官能团，如烷氧基，羟基，氨基，氟，氯，溴，氰基，硝基，酯，酰胺，酰亚胺，氧化膦和砜基团，并且，此外，分子氧和二甲亚砜被证明是作为末端氧化剂。本研究为通过直接转化末端烯烃中的乙烯基C-OH键立体选择性合成1，2-二取代烯烃提供了一种有效的方法。
An unprecedented oxidative arylation reaction of terminal alkenes with simple aroyl hydrazides has been developed under aerobic conditions for the stereoselective synthesis of 1,2‐disubstituted alkenes. A range of aroyl hydrazides underwent palladium/copper‐catalyzed oxidative Mizoroki–Heck reaction with terminal alkenes open to air in a 1:1 mixture of dimethyl sulfoxide and acetonitrile to give structurally diverse 1,2‐disubstituted alkenes in moderate to excellent yields with excellent regio‐ andE‐selectivity. The reaction tolerated a wide variety of functional groups, such as alkoxy, hydroxy, amino, fluoro, chloro, bromo, cyano, nitro, ester, amide, imide, phosphine oxide, and sulfone groups, and, moreover, molecular oxygen and dimethyl sulfoxide were demonstrated to serve as terminal oxidants. This study provides a useful method for the stereoselective synthesis of 1,2‐disubstituted alkenes through direct transformation of the vinylic CH bonds in terminal alkenes.