Laboratory of Molecular Recognition and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou, 310027, Zhejiang, PR China.
Org Biomol Chem. 2009 Aug 21;7(16):3258-63. doi: 10.1039/b903769a. Epub 2009 Jun 18.
A highly regio- and stereoselective CuCl-mediated carbometallation reaction of 3-aryl-substituted secondary propargylic alcohols with alkyl, aryl, vinyl or allyl Grignard reagents for the synthesis of fully-substituted allylic alcohols was developed. The R(2) group from the Grignard reagent was successfully introduced to the 2-position of the propargylic alcohols due to the chelation of metal atom with the hydroxyl oxygen atom forming 5-membered metallacyclic intermediates, which smoothly react with various electrophiles to afford stereodefined polysubstituted allylic alcohols. By this method, optically active allylic alcohols can be prepared from readily available optically active propargylic alcohols without obvious racemization. Five-membered lactones can also be synthesized by Pd-catalyzed carbonylation with iodoallylic alcohols.
发展了一种高区域和立体选择性的 CuCl 介导的 3-芳基取代的二级炔丙醇与烷基、芳基、乙烯基或烯丙基格氏试剂的碳金属化反应，用于合成全取代的烯丙醇。由于金属原子与羟基氧原子的螯合形成 5 元金属环中间体，因此来自格氏试剂的 R(2)基团成功地引入到炔丙醇的 2-位，该中间体可与各种亲电试剂顺利反应，得到立体定义的多取代烯丙醇。通过该方法，可以从易得的光学活性炔丙醇制备光学活性的烯丙醇，而没有明显的外消旋化。碘代烯丙醇的钯催化羰基化反应也可以合成五元内酯。
