Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian, 350002 (P. R. of, China.
University of Chinese Academy of Sciences, Beijing, 100049 (P. R. of, China.
Angew Chem Int Ed Engl. 2022 Jul 11;61(28):e202202077. doi: 10.1002/anie.202202077. Epub 2022 May 19.
Chiral lactones are found in many natural products. The reaction of simple alkenes with iodoacetic acid is a powerful method to build lactones, but the enantioselective version of this reaction has not been implemented to date. Herein, we report the efficient catalytic radical enantioselective carbo-esterification of styrenes enabled by a newly developed Cu -perfluoroalkylated PyBox system. Simple styrenes have been converted to useful chiral lactones, whose synthetic applications are showcased. Mechanistic studies reveal that this reaction is a rare example of an efficient ligand-decelerated system, in which the ligand decelerates the reaction, but the reaction is still efficient with reduced amounts of ligand. This uncommon catalytic system may inspire further consideration of the effect of ligands in asymmetric catalysis.
手性内酯广泛存在于天然产物中。简单烯烃与碘乙酸的反应是构建内酯的一种有效方法，但目前尚未实现该反应的对映选择性版本。在此，我们报告了一种新开发的 Cu-全氟烷基化 PyBox 体系，可有效催化自由基对映选择性碳酯化反应。简单的苯乙烯已被转化为有用的手性内酯，展示了它们的合成应用。机理研究表明，该反应是高效配体减速体系的一个罕见实例，其中配体减缓了反应，但在减少配体用量的情况下，反应仍然高效。这种不常见的催化体系可能会激发人们进一步考虑配体在不对称催化中的作用。
