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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
Corresponding AuthorYu, Zhi-Xiang(yuzx@pku.edu.cn)
KeywordCorey-Chaykovsky Reaction Cyclopropanation Epoxidation DFT calculations Regioselectivity
Source PublicationEUROPEAN JOURNAL OF ORGANIC CHEMISTRY
2019-01-23
ISSN1434-193X
DOI10.1002/ejoc.201801216
Issue2-3Pages:582-590
Funding ProjectNational Natural Science Foundation of China
Funding OrganizationNational Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China
WOS SubjectChemistry, Organic
WOS Research AreaChemistry
WOS KeywordCORRELATED MOLECULAR CALCULATIONS ; CATALYTIC ASYMMETRIC-SYNTHESIS ; YLIDE-MEDIATED EPOXIDATION ; GAUSSIAN-BASIS SETS ; DIFFUSE BASIS-SETS ; SULFUR YLIDES ; MECHANISM ; SCOPE ; CYCLOPROPANATION ; CHEMISTRY
AbstractThe 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.
Language英语
Funding OrganizationNational Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China ; National Natural Science Foundation of China
WOS IDWOS:000459821300041
PublisherWILEY-V C H VERLAG GMBH
Citation statistics
Cited Times:1[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://cas-ir.dicp.ac.cn/handle/321008/165891
Collection中国科学院大连化学物理研究所
Corresponding AuthorYu, Zhi-Xiang
AffiliationPeking Univ, BNLMS, Key Lab Bioorgan Chem & Mol Engn, Minist Educ,Coll Chem, Beijing 100871, Peoples R China
Recommended Citation
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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