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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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journal contribution
posted on 29.06.2017, 14:35 by Kazuhiko Takatori, Shoya Ota, Kenta Tendo, Kazuma Matsunaga, Kokoro Nagasawa, Shinya Watanabe, Atsushi Kishida, Hiroshi Kogen, Hiroto Nagaoka
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 methylene­cyclobutane 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.

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