Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Huaxi District, Guiyang 550025, China.
Division of Chemistry & Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Org Lett. 2020 May 1;22(9):3335-3338. doi: 10.1021/acs.orglett.0c00748. Epub 2020 Apr 14.
Optically active α-aryloxycarboxylic acids and their derivatives are important functional molecules. Disclosed here is a carbene-catalyzed dynamic kinetic resolution and transesterification reaction for access to this class of molecules with up to 99% yields and 99:1 er values. Addition of a chiral carbene catalyst to the ester substrate leads to two diastereomeric azolium ester intermediates that can quickly epimerize to each other and thus allows for effective dynamic kinetic resolution to be realized. The optically enriched ester products from our reaction can be quickly transformed to chiral herbicides and other bioactive molecules.
手性α-芳氧基羧酸及其衍生物是一类重要的功能分子。本文报道了一种通过卡宾催化的动态动力学拆分和酯交换反应来合成这类分子的方法，产率高达 99%，对映选择性高达 99:1。将手性卡宾催化剂添加到酯底物中，生成两种非对映异构的唑鎓酯中间体，它们可以快速互变异构，从而实现有效的动态动力学拆分。我们反应得到的光学富集酯产物可以快速转化为手性除草剂和其他生物活性分子。
