Kawaguchi Yasuaki, Yabushita Kenya, Mukai Chisato
Division of Pharmaceutical Sciences, Graduate School of Medical Sciences, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.
Angew Chem Int Ed Engl. 2018 Apr 16;57(17):4707-4711. doi: 10.1002/anie.201713096. Epub 2018 Feb 14.
Upon exposure to a catalytic amount of [RhCl(CO) ] in 1,4-dioxane, homopropargylallene-alkynes underwent a novel cycloisomerization accompanied by the migration of the alkyne moiety of the homopropargyl functional group to produce six/five/five tricyclic compounds in good yields. A plausible mechanism was proposed on the basis of an experiment with C-labeled substrate. The resulting tricyclic derivatives were further converted into the corresponding bicyclo[3.3.0] skeletons with vicinal cis dihydroxy groups.
在1,4 - 二氧六环中，当暴露于催化量的[RhCl(CO)₂]时，高炔丙基丙二烯 - 炔烃发生了一种新型的环异构化反应，同时高炔丙基官能团的炔基部分发生迁移，以良好的产率生成六元/五元/五元三环化合物。基于用¹³C标记底物的实验提出了一种合理的机理。所得的三环衍生物进一步转化为具有邻位顺式二羟基的相应双环[3.3.0]骨架。
