Understanding regioselectivities of corey-chaykovsky reactions of dimethylsulfoxonium methylide (dmsom) and dimethylsulfonium methylide (dmsm) toward enones: a dft study
文献类型：期刊论文
| 作者 | Xiang, Yu; Fan, Xing; Cai, Pei-Jun; Yu, Zhi-Xiang |
| 刊名 | European journal of organic chemistry
 |
| 出版日期 | 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 |
| WOS记录号 | WOS:000459821300041 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| URI标识 | http://www.irgrid.ac.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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来源：大连化学物理研究所
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