Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Chemistry. 2010 Jul 26;16(28):8427-32. doi: 10.1002/chem.201000930.
An unusual ring-contraction rearrangement to give spirocyclopropanes from fused cyclobutanols (see scheme) has been developed. It is found that the strain energy of the substrates derived from an additional fused ring and the stereoelectronic effect of the migrating sigma bond are important factors. It is noteworthy that the rearrangement proceeds in a stereospecific manner. Moreover, the method provides a spiro(cyclopropane-indane) framework from tricyclo[6.3.0.02,5]undecane, which corresponds to illudane and the protoilludane skeleton.
已经开发出一种将稠合环丁醇转化为螺环丙烷（见方案）的不寻常的环收缩重排反应。研究发现，来自额外稠合环的底物的应变能和迁移σ键的立体电子效应是重要因素。值得注意的是，重排以立体专一的方式进行。此外，该方法还提供了一种来自三环[6.3.0.02,5]十一烷的螺（环丙烷-茚烷）骨架，该骨架对应于伊利烷和原伊利烷骨架。
