Synthesis of Methylenebicyclo[3.2.1]octanol by a Sm(II)-Induced 1,2-Rearrangement Reaction with Ring Expansion of Methylenebicyclo[4.2.0]octanone
Synthesis of Methylenebicyclo[3.2.1]octanol by a Sm(II)-Induced 1,2-Rearrangement Reaction with Ring Expansion of Methylenebicyclo[4.2.0]octanone
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DOI：
10.1021/acs.orglett.7b01604
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发表时间：
2017-07-21
期刊：
影响因子：
5.2
通讯作者：
Nagaoka, Hiroto
中科院分区：
文献类型：
--
作者：
Takatori, Kazuhiko;Ota, Shoya;Nagaoka, Hiroto
亚甲基双环[4.2.0]辛酮通过Sm（II）诱导的亚甲基环丁烷扩环1，2-重排直接转化为亚甲基双环[3.2.1]辛醇。三个条件进行了优化，以允许这种方法的适应各种基板。重排机制，提出涉及生成的酮基自由基和环戊烷的酮基-烯烃环化，然后由自由基断裂和随后的质子化。
Direct conversion of methylenebicyclo[4.2.0]-octanone to methylenebicyclo[3.2.1]octanol by a Sm(II)-induced 1,2-rearrangement with ring expansion of the methylene-cyclobutane is described. Three conditions were optimized to allow the adaptation of this approach to various substrates. A rearrangement mechanism is proposed involving the generation of a ketyl radical and cyclopentanation by ketyl-olefin Cyclization, followed by radical fragmentation and subsequent protonation.