Jiang Zhong-Tao, Chen Zhengzhao, Zeng Yaxin, Shi Jiang-Ling, Xia Ying
West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, China.
Org Lett. 2022 Aug 26;24(33):6176-6181. doi: 10.1021/acs.orglett.2c02410. Epub 2022 Aug 11.
Herein, we report an effective method to offer chiral -difluorinated cyclopropanes containing an all-carbon quaternary stereocenter by rhodium-catalyzed stereoablative kinetic resolution. The activation of a sterically hindered all-carbon quaternary C-C bond through oxidative addition with a chiral rhodium complex is proposed as the enantiodetermining step. A wide range of -difluorinated cyclopropanes can be obtained with excellent ee values (ee = 87% to >99.9%), which are demonstrated to be useful chiral fluorine-containing building blocks by a series of postfunctionalizations.
在此，我们报道了一种通过铑催化的立体消融动力学拆分来提供含有全碳季碳立体中心的手性二氟环丙烷的有效方法。通过与手性铑配合物进行氧化加成来活化空间位阻较大的全碳季碳C-C键被认为是对映体决定步骤。可以获得一系列具有优异对映体过量值（ee = 87%至>99.9%）的二氟环丙烷，通过一系列后官能团化反应证明它们是有用的含氟手性砌块。
