Department of Chemistry, Washington University, Saint Louis, Missouri 63130, USA.
Chemistry. 2011 Sep 26;17(40):11296-304. doi: 10.1002/chem.201101028. Epub 2011 Aug 23.
A new method for catalytic nonenzymatic kinetic resolution of α-substituted alkanoic acids has been developed, which relies on their activation with DCC followed by enantioselective alcoholysis of the intermediate symm-anhydrides in the presence of the amidine-based catalyst homobenzotetramisole (HBTM). Moderate to excellent selectivity factors (s=5-96) have been obtained in the case of several classes of substrates, namely, α-aryl-, α-aryloxy/alkoxy-, α-halo-, α-azido-, and α-phthalimido-alkanoic acids. Under similar conditions, α-(arylthio/alkylthio)-alkanoic acids undergo dynamic kinetic resolution providing corresponding esters in up to 92% ee and up to 93% yield.
已开发出一种新的用于催化非酶动力学拆分α-取代烷酸的方法，该方法依赖于用 DCC 对其进行活化，然后在脒基苯并四唑（HBTM）催化剂存在下，对中间对称酸酐进行对映选择性醇解。在几种底物的情况下，已获得中等至优异的选择性因子（s=5-96），这些底物包括α-芳基、α-芳氧基/烷氧基、α-卤代、α-叠氮基和α-邻苯二甲酰亚氨基烷酸。在类似条件下，α-（芳基硫代/烷基硫代）烷酸进行动态动力学拆分，以高达 92%的对映体过量和高达 93%的收率得到相应的酯。
