Synthesis of Medium-Sized Carbocycles by Gallium-Catalyzed Tandem Carbonyl-Olefin Metathesis/Transfer Hydrogenation
Synthesis of Medium-Sized Carbocycles by Gallium-Catalyzed Tandem Carbonyl-Olefin Metathesis/Transfer Hydrogenation
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DOI：
10.1021/acs.orglett.9b03240
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发表时间：
2019-10-04
期刊：
影响因子：
5.2
通讯作者：
Bour, Christophe
中科院分区：
文献类型：
--
作者：
Djuroyic, Alexandre;Vayer, Marie;Bour, Christophe
描述了涉及闭环羰基-烯烃复分解和转移氢化的催化串联方法的第一实施例。1，4-环己二烯已被用作H-2替代物以减少复分解步骤后形成的环烯烃。相同的阳离子镓（III）络合物[IPr中心点GaCl 2][SbF 6]以官能团耐受性执行两个步骤。这种立体选择性反应导致1，2-顺式-二取代的环戊烷和各种环己烷。DFT计算支持一个意想不到的机制，涉及超亲电镓（III）二聚体的1，4-环己二烯的活化。
The first examples of a catalytic tandem process involving a ring-closing carbonyl-olefin metathesis and a transfer hydrogenation are described. 1,4-Cyclo-hexadiene has been used as an H-2 surrogate to reduce the cyclic alkenes formed after the metathesis step. The same cationic gallium(III) complex, [IPr center dot GaCl2][SbF6], performs the two steps with functional group tolerance. This stereo selective reaction leads to 1,2-cis-disubstituted cyclopentanes and various cyclohexanes. DFT computations support an unexpected mechanism involving activation of 1,4-cyclo-hexadiene by superelectrophilic gallium(III) dimers.