Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory

doi:10.1021/ja103253d

CORC > 北京大学 > 化学与分子工程学院

	Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory
	Liu, Peng ; Sirois, Lauren E. ; Cheong, Paul Ha-Yeon ; Yu, Zhi-Xiang ; Hartung, Ingo V. ; Rieck, Heiko ; Wender, Paul A. ; Houk, K.N.
刊名	journal of the american chemical society
	2010
DOI	10.1021/ja103253d
英文摘要	The first studies on the regioselectivity of Rh(I)-catalyzed (5 + 2) cycloadditions between vinylcyclopropanes (VCPs) and alkynes have been conducted experimentally and analyzed using density functional theory (DFT). The previously unexplored regiochemical consequences for this catalytic, intermolecular cycloaddition were determined by studying the reactions of several substituted VCPs with a range of unsymmetrical alkynes. Experimental trends were identified, and a predictive model was established. VCPs with terminal substitution on the alkene reacted with high regioselectivity (>20:1), as predicted by a theoretical model in which bulkier alkyne substituents prefer to be distal to the forming C-C bond to avoid steric repulsions. VCPs with substitution at the internal position of the alkene reacted with variable regioselectivity (ranging from >20:1 to a reversed 1:2.3), suggesting a refined model in which electron-withdrawing substituents on the alkyne decrease or reverse sterically controlled selectivity by stabilizing the transition state in which the substituent is proximal to the forming C-C bond. ? 2010 American Chemical Society.; EI; 0; 29; 10127-10135; 132
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/412815]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Liu, Peng,Sirois, Lauren E.,Cheong, Paul Ha-Yeon,et al. Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory[J]. journal of the american chemical society,2010.
APA	Liu, Peng.,Sirois, Lauren E..,Cheong, Paul Ha-Yeon.,Yu, Zhi-Xiang.,Hartung, Ingo V..,...&Houk, K.N..(2010).Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory.journal of the american chemical society.
MLA	Liu, Peng,et al."Electronic and steric control of regioselectivities in Rh(I)-catalyzed (5 + 2) cycloadditions: Experiment and theory".journal of the american chemical society (2010).