Merck Center for Catalysis at Princeton University, Princeton, New Jersey 08544, United States.
J Am Chem Soc. 2013 Jun 26;135(25):9358-61. doi: 10.1021/ja4047312. Epub 2013 Jun 12.
A highly selective method for the synthesis of asymmetrically substituted carbocycles and heterocycles from unactivated aldehyde-olefin precursors has been achieved via enantioselective SOMO-catalysis. Addition of a catalytically generated enamine radical cation across a pendent olefin serves to establish a general asymmetric strategy toward the production of a wide range of formyl-substituted rings with alkene transposition. Conceptually, this novel mechanism allows direct access to "homo-ene"-type products.
通过对映选择性 SOMO 催化，实现了一种从非活化醛-烯烃前体合成不对称取代碳环和杂环的高选择性方法。催化生成的烯胺自由基阳离子与侧链烯烃加成，为合成各种取代的醛基环烯烃提供了一种通用的不对称策略，同时实现了烯烃的反式迁移。从概念上讲，这种新的机制允许直接获得“同烯”型产物。
