Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.
Org Lett. 2012 Oct 5;14(19):5094-7. doi: 10.1021/ol302358j. Epub 2012 Sep 24.
A general and efficient route for the synthesis of enantiomerically pure α-substituted ketones and the corresponding lactones has been developed. Ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR) with a subsequent Cu-catalyzed α-allylic substitution are the key steps of the route. The α-substituted ketones were obtained in high yields and with excellent enantiomeric excess. The methodology was applied to the synthesis of a naturally occurring caprolactone, (R)-10-methyl-6-undecanolide, via a subsequent Baeyer-Villiger oxidation.
已开发出一种通用且高效的合成对映纯α-取代酮和相应内酯的方法。该方法的关键步骤是钌和酶催化的动态动力学拆分（DKR），以及随后的 Cu 催化的α-烯丙基取代。α-取代酮以高产率和优异的对映体过量获得。该方法通过随后的 Baeyer-Villiger 氧化应用于天然存在的己内酯（R）-10-甲基-6-十一烷内酯的合成。
