Department of Chemistry, The University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom.
J Am Chem Soc. 2012 Feb 29;134(8):3635-8. doi: 10.1021/ja210804r. Epub 2012 Feb 15.
The rhodium-catalyzed ene-cycloisomerization of alkenylidenecyclopropanes provides an atom-economical approach to five-membered carbo- and heterocycles that contain two new stereogenic centers. A key and striking feature of this protocol is that the alkene geometry does not impact the efficiency and diastereocontrol, which provides excellent synthetic versatility. For instance, (E)- and (Z)-allylic alcohols furnish the corresponding aldehydes with similar efficiency and selectivity. This process facilitates the construction of a key intermediate in an eight-step total synthesis of (-)-α-kainic acid.
铑催化的烯丙基环丙烷的烯环异构化提供了一种原子经济性的方法，用于合成含有两个新手性中心的五元碳环和杂环化合物。该方法的一个关键和显著特点是，烯烃的几何形状不影响反应的效率和非对映选择性，这为合成提供了极好的通用性。例如，(E)-和(Z)-烯丙醇以相似的效率和选择性得到相应的醛。该过程有利于(-)-α- kainic 酸的全合成中一个八步反应关键中间体的构建。
