Rh-Catalyzed Cycloisomerization of 1,7-Ene-Dienes to Synthesize trans-Divinylpiperidines: A Formal Intramolecular Addition Reaction of Allylic C-H Bond into Dienes
Rh-Catalyzed Cycloisomerization of 1,7-Ene-Dienes to Synthesize trans-Divinylpiperidines: A Formal Intramolecular Addition Reaction of Allylic C-H Bond into Dienes
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Rh 催化 1,7-烯-二烯环异构化合成反式二乙烯基哌啶：烯丙基 C-H 键形成二烯的正式分子内加成反应
DOI：
10.1021/acs.orglett.9b02319
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发表时间：
2019
期刊：
影响因子：
5.2
通讯作者：
Yu Zhi Xiang
中科院分区：
文献类型：
--
作者：
Cui Qi;Liao Wei;Tian Zi You;Li Qian;Yu Zhi Xiang
原来设计的铑催化氮栓1，7-烯-二烯的[4 + 2]环加成反应是一个环异构化反应，该反应涉及烯丙基C-H活化/烯烃插入Rh-H键/还原消除过程。氘标记实验支持所提出的机制。这种意想不到的环异构化反应提供了一种从容易获得的直链1，7-烯-二烯合成反式-二乙烯基哌啶的有效方法。
An originally designed Rh-catalyzed [4 + 2] cycloaddition reaction of nitrogen-tethered 1,7-ene-dienes turned out to be a cycloisomerization reaction, which involves allylic C–H activation/alkene insertion into Rh–H bond/reductive elimination processes. Deuterium labeling experiments gave support to the proposed mechanism. This unexpected cycloisomerization reaction provides an efficient way to synthesizetrans-divinylpiperidines from easily accessed linear 1,7-ene-dienes.