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	Understanding regioselectivities of corey-chaykovsky reactions of dimethylsulfoxonium methylide (dmsom) and dimethylsulfonium methylide (dmsm) toward enones: a dft study
	Xiang, Yu; Fan, Xing; Cai, Pei-Jun; Yu, Zhi-Xiang
刊名	European journal of organic chemistry
	2019-01-23
期号	2-3页码:582-590
关键词	Corey-chaykovsky reaction Cyclopropanation Epoxidation Dft calculations Regioselectivity
ISSN号	1434-193X
DOI	10.1002/ejoc.201801216
通讯作者	Yu, zhi-xiang(yuzx@pku.edu.cn)
英文摘要	The corey-chaykovsky reaction, using either in situ generated dimethylsulfoxonium methylide (dmsom) or dimethylsulfonium methylide (dmsm) to react with ketones or aldehydes, is widely used in the synthesis of epoxides. however, when dmsom and dmsm react with enones (such as chalcone), the former reactions give cyclopropanation products whereas the latter reactions still generate epoxides. dft calculations have been carried out to understand these different regioselectivities. we found that the cyclopropanation pathways for both dmsom and dmsm toward chalcone (a model for enones) start with rate-determining and irreversible 1,4-addition reactions, followed by easier intramolecular substitution reactions to give cyclopropanes. the overall activation free energies for cyclopropanation are 17.5 and 15.5 kcal/mol for dmsom and dmsm, respectively. the epoxidation pathways for both dmsom and dmsm have reversible 1,2-addition reactions, followed by rate-determining intramolecular substitution reactions to give epoxides. the computed barriers for the epoxidation are 23.0 and 13.3 kcal/mol for dmsom and dmsm, respectively. therefore, the cyclopropanation pathway is favored for dmsom while epoxidation is preferred for dmsm. we attribute these different reaction scenarios to thermodynamic reasons that dmsom is more stable than dmsm. the reaction pathways for reactions of other derivatives of dmsm toward enones have also been discussed.
WOS关键词	CORRELATED MOLECULAR CALCULATIONS ; CATALYTIC ASYMMETRIC-SYNTHESIS ; YLIDE-MEDIATED EPOXIDATION ; GAUSSIAN-BASIS SETS ; DIFFUSE BASIS-SETS ; SULFUR YLIDES ; MECHANISM ; SCOPE ; CYCLOPROPANATION ; CHEMISTRY
WOS研究方向	Chemistry
WOS类目	Chemistry, Organic
语种	英语
出版者	WILEY-V C H VERLAG GMBH
WOS记录号	WOS:000459821300041
内容类型	期刊论文
URI标识	http://www.corc.org.cn/handle/1471x/2372714
专题	大连化学物理研究所
通讯作者	Yu, Zhi-Xiang
作者单位	Peking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
推荐引用方式 GB/T 7714	Xiang, Yu,Fan, Xing,Cai, Pei-Jun,et al. Understanding regioselectivities of corey-chaykovsky reactions of dimethylsulfoxonium methylide (dmsom) and dimethylsulfonium methylide (dmsm) toward enones: a dft study[J]. European journal of organic chemistry,2019(2-3):582-590.
APA	Xiang, Yu,Fan, Xing,Cai, Pei-Jun,&Yu, Zhi-Xiang.(2019).Understanding regioselectivities of corey-chaykovsky reactions of dimethylsulfoxonium methylide (dmsom) and dimethylsulfonium methylide (dmsm) toward enones: a dft study.European journal of organic chemistry(2-3),582-590.
MLA	Xiang, Yu,et al."Understanding regioselectivities of corey-chaykovsky reactions of dimethylsulfoxonium methylide (dmsom) and dimethylsulfonium methylide (dmsm) toward enones: a dft study".European journal of organic chemistry .2-3(2019):582-590.

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