Chiral Primary-Amine-Catalyzed Conjugate Addition to alpha-Substituted Vinyl Ketones/Aldehydes: Divergent Stereocontrol Modes on Enamine Protonation
文献类型：期刊论文
| 作者 | Fu, Niankai; Zhang, Long; Luo, Sanzhong; Cheng, Jin-Pei |
| 刊名 | CHEMISTRY-A EUROPEAN JOURNAL
 |
| 出版日期 | 2013-11-11 |
| 卷号 | 19期号:46页码:15669-15681 |
| 关键词 | Alkylation Amines Asymmetric Catalysis Ketones Protonation |
| ISSN号 | 0947-6539 |
| DOI | 10.1002/chem.201302056 |
| 英文摘要 | Enantioselective protonation with a catalytic enamine intermediate represents a challenging, yet fundamentally important process for the synthesis of -chiral carbonyls. We describe herein chiral primary-amine-catalyzed conjugate additions of indoles to both -substituted acroleins and vinyl ketones. These reactions feature enamine protonation as the stereogenic step. A simple primary-tertiary vicinal diamine 1 with trifluoromethanesulfonic acid (TfOH) was found to enable both of the reactions of acroleins and vinyl ketones with good activity and high enantioselectivity. Detailed mechanistic studies reveal that these reactions are rate-limiting in iminium formation and they all involve a uniform H2O/acid-bridged proton transfer in the stereogenic steps but divergent stereocontrol modes for the protonation stereoselectivity. For the reactions of -branched acroleins, facial selections on H2O-bridged protonation determine the enantioselectivity, which is enhanced by an OH interaction with indole as uncovered by DFT calculations. On the other hand, the stereoselectivity of the reactions with vinyl ketones is controlled according to the Curtin-Hammett principle in the CC bond-formation step, which precedes a highly stereospecific enamine protonation. |
| 语种 | 英语 |
| WOS记录号 | WOS:000326311400033 |
| 出版者 | WILEY-V C H VERLAG GMBH |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/54403]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Luo, Sanzhong |
| 作者单位 | Chinese Acad Sci, Inst Chem, CAS Key Lab Mol Recognit & Funct, BNLMS, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Fu, Niankai,Zhang, Long,Luo, Sanzhong,et al. Chiral Primary-Amine-Catalyzed Conjugate Addition to alpha-Substituted Vinyl Ketones/Aldehydes: Divergent Stereocontrol Modes on Enamine Protonation[J]. CHEMISTRY-A EUROPEAN JOURNAL,2013,19(46):15669-15681. |
| APA | Fu, Niankai,Zhang, Long,Luo, Sanzhong,&Cheng, Jin-Pei.(2013).Chiral Primary-Amine-Catalyzed Conjugate Addition to alpha-Substituted Vinyl Ketones/Aldehydes: Divergent Stereocontrol Modes on Enamine Protonation.CHEMISTRY-A EUROPEAN JOURNAL,19(46),15669-15681. |
| MLA | Fu, Niankai,et al."Chiral Primary-Amine-Catalyzed Conjugate Addition to alpha-Substituted Vinyl Ketones/Aldehydes: Divergent Stereocontrol Modes on Enamine Protonation".CHEMISTRY-A EUROPEAN JOURNAL 19.46(2013):15669-15681. |
入库方式： OAI收割
来源：化学研究所
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