Ding Lu, Song Hao, Zheng Chao, You Shu-Li
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Road, Shanghai 201210, China.
J Am Chem Soc. 2022 Mar 23;144(11):4770-4775. doi: 10.1021/jacs.2c01103. Epub 2022 Mar 10.
Medium-sized rings are important structural units, but their synthesis, especially in a highly enantioselective manner, has been a great challenge. Herein we report an enantioselective synthesis of medium-sized-ring lactones by an iridium-catalyzed -retentive asymmetric allylic substitution reaction. The reaction features mild conditions and a broad substrate scope. Various eight- to 11-membered-ring lactones can be afforded in moderate to excellent yields (up to 88%) and excellent enantioselectivity (up to 99% ee). The utilization of both -allyl precursors and an Ir catalyst is critical for the medium-sized-ring formation.
中等大小的环是重要的结构单元，但其合成，尤其是以高度对映选择性的方式进行合成，一直是一项巨大的挑战。在此，我们报道了通过铱催化的构型保持不对称烯丙基取代反应对中等大小的环内酯进行对映选择性合成。该反应条件温和，底物范围广泛。各种八元至十一元的环内酯能够以中等至优异的产率（高达88%）和优异的对映选择性（高达99% ee）得到。烯丙基前体和铱催化剂的共同使用对于中等大小环的形成至关重要。
