一种用于自裂解氯四氟乙基亚磺酰基（-SOCFCFCl）导向的钯（II）催化C-H活化的机理研究
A Mechanism Study for Self-Cleaving Chlorotetrafluoroethylsulfinyl (-SOCFCFCl)-Directed Pd(II)-Catalyzed C-H Activation.
作者信息
Shao Nan-Qi, Wang Dong-Hui
机构信息
Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Rd., Shanghai 200032, China.
Department of Pharmacy, Nanjing University of Chinese Medicines, 138 Xianlin Ave., Nanjing 210023, China.
出版信息
J Org Chem. 2021 Dec 3;86(23):16511-16517. doi: 10.1021/acs.joc.1c01852. Epub 2021 Nov 16.
A mechanism study for Pd(II)-catalyzed C(sp)-H activation using a self-cleaving chlorotetrafluoroethylsulfinyl (-SOCFCFCl) auxiliary as a directing group is reported. Mechanistic studies reveal that (1) the auxiliary group is crucial for C(sp)-H activation, (2) the reaction undergoes a C(sp)-H olefination-Michael addition-removal of the auxiliary sequence, (3) the removal of the auxiliary (SOR) is most likely the alcoholic solvolysis of the -SOCFCFCl group on the -tri-substituted sulfonamides, and (4) the C(sp)-H cleavage is involved in the rate-determining step.
报道了一项关于使用自裂解氯四氟乙基亚磺酰基（-SOCFCFCl）助剂作为导向基团的钯（II）催化C（sp）-H活化的机理研究。机理研究表明：（1）助剂基团对C（sp）-H活化至关重要；（2）反应经历了C（sp）-H烯基化-迈克尔加成-助剂基团消除的过程；（3）助剂（SOR）的消除最有可能是三取代磺酰胺上的-SOCFCFCl基团的醇解；（4）C（sp）-H裂解参与了速率决定步骤。
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