Highly enantioselective S-H bond insertion cooperatively catalyzed by   dirhodium complexes and chiral spiro phosphoric acids

doi:10.1039/c3sc52807c

CORC > 北京大学 > 化学与分子工程学院

	Highly enantioselective S-H bond insertion cooperatively catalyzed by dirhodium complexes and chiral spiro phosphoric acids
	Xu, Bin ; Zhu, Shou-Fei ; Zhang, Zhi-Chao ; Yu, Zhi-Xiang ; Ma, Yi ; Zhou, Qi-Lin
刊名	chemical science
	2014
关键词	3+2 CYCLOADDITION REACTIONS DIAZO-COMPOUNDS DONOR/ACCEPTOR CARBENOIDS ASYMMETRIC-SYNTHESIS KINETIC RESOLUTION AROMATIC-ALDEHYDES EFFICIENT APPROACH RELAY CATALYSIS BINARY-SYSTEM TANDEM YLIDE
DOI	10.1039/c3sc52807c
英文摘要	The first highly enantioselective S-H bond insertion reaction was developed by cooperative catalysis of dirhodium(II) carboxylates and chiral spiro phosphoric acids (SPAs) under mild and neutral reaction conditions with fast reaction rates, high yields (77-97% yields), and excellent enantioselectivities (up to 98% ee). The catalytic S-H bond insertion reaction provides a highly efficient method for the synthesis of chiral sulfur-containing compounds and advances the synthesis of a chiral sulfur-containing drug (S)-Eflucimibe. A systematic P-31 NMR study revealed that no ligand exchange between dirhodium(II) carboxylates and SPAs occurred in the reaction. The distinct behaviors of cooperative catalysts Rh-2(TPA)(4)/(R)-1a and the prepared complex Rh-2(R-1a)(4) observed by in situ FT-IR spectroscopy excluded the feasibility of Rh-2(R-SPA)(4) being the real catalyst. DFT calculations showed that the activation barrier in the proton shift step became remarkably low as promoted by SPAs. Based on the experimental results and the calculations, the SPA was proposed as a chiral proton shuttle for the proton shift in reaction. Additionally, the single crystal structures of several SPAs were measured and used to rationalize the configurations of the S-H insertion products obtained in the reactions. The rigid and crowded environment around the SPAs ensures the high enantioselectivity in the S-H bond insertion reaction.; Chemistry, Multidisciplinary; SCI(E); 17; ARTICLE; sfzhu@nankai.edu.cn; yuzx@pku.edu.cn; qlzhou@nankai.edu.cn; 4; 1442-1448; 5
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/217686]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Xu, Bin,Zhu, Shou-Fei,Zhang, Zhi-Chao,et al. Highly enantioselective S-H bond insertion cooperatively catalyzed by dirhodium complexes and chiral spiro phosphoric acids[J]. chemical science,2014.
APA	Xu, Bin,Zhu, Shou-Fei,Zhang, Zhi-Chao,Yu, Zhi-Xiang,Ma, Yi,&Zhou, Qi-Lin.(2014).Highly enantioselective S-H bond insertion cooperatively catalyzed by dirhodium complexes and chiral spiro phosphoric acids.chemical science.
MLA	Xu, Bin,et al."Highly enantioselective S-H bond insertion cooperatively catalyzed by dirhodium complexes and chiral spiro phosphoric acids".chemical science (2014).