Rhodium-catalyzed enantioselective C-H alkynylation of sulfoxides in diverse patterns: desymmetrization, kinetic resolution, and parallel kinetic resolution

被引:8
|
作者
Kong, Lingheng [1 ]
Zou, Yun [1 ]
Li, Xiao-Xi [2 ]
Zhang, Xue-Peng [1 ]
Li, Xingwei [1 ,2 ]
机构
[1] Shaanxi Normal Univ, Sch Chem & Chem Engn, Xian 710062, Peoples R China
[2] Shandong Univ, Inst Mol Sci & Engn, Inst Frontier & Interdisciplinary Sci, Qingdao 266237, Peoples R China
基金
中国博士后科学基金;
关键词
BASIS-SETS; ACTIVATION; LIGANDS; C(SP(2))-H; RH(III); FUNCTIONALIZATION; ANNULATION; COMPLEXES; EXCHANGE; ACCESS;
D O I
10.1039/d2sc05310a
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Rhodium-catalyzed enantioselective C-H alkynylation of achiral and racemic sulfoxides is disclosed with alkynyl bromide as the alkynylating reagent. A wide range of chiral sulfoxides have been constructed in good yield and excellent enantioselectivity (up to 99% ee, s-factor up to > 500) via desymmetrization, kinetic resolution, and parallel kinetic resolution under mild reaction conditions. The high enantioselectivity was rendered by the chiral cyclopentadienyl rhodium(iii) catalyst paired with a chiral carboxamide additive. The interactions between the chiral catalyst, the sulfoxide, and the chiral carboxylic amide during the C-H bond cleavage offer the asymmetric induction, which is validated by DFT calculations. The chiral carboxamide functions as a base to promote C-H activation and offers an additional chiral environment during the C-H cleavage.
引用
收藏
页码:317 / 322
页数:6
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