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题名: Theoretical Study of N-Heterocyclic Carbenes-Catalyzed Cascade Annulation of Benzodienones and Enals
作者: Sun, Hui1;  Fang, Xinqiang2;  Chi, Yonggui Robin2;  Li, Guohui1
关键词: N-heterocyclic carbenes ;  homoenolate intermediates ;  annulation reaction
刊名: CHIRALITY
发表日期: 2013-09-01
DOI: 10.1002/chir.22157
卷: 25, 期:9, 页:521-528
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Life Sciences & Biomedicine ;  Physical Sciences
类目[WOS]: Chemistry, Medicinal ;  Chemistry, Analytical ;  Chemistry, Organic ;  Pharmacology & Pharmacy
研究领域[WOS]: Pharmacology & Pharmacy ;  Chemistry
英文摘要: Growing attention in developing new N-heterocyclic carbene (NHC)-mediated reactions involving homoenolate intermediates has prompted our interest in exploring the mechanistic details of the related reactions. In this work, we carried out a detailed theoretical study for the NHC-catalyzed annulation reaction of cinnamaldehyde (A) and benzodi(enone) (B) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). By performing density functional theory calculations, we show clearly the detailed reaction mechanism and rationalize the experimental observation. The reaction of A and B falls into two stages: the formation of homoenolate intermediate and the annulation of homoenolate with B. In the homoenolate formation stage, three possible paths are characterized. The pathway involving the DBU-assisted 1,2-proton transfer with a stepwise mechanism is kinetically more favorable, and the DBU-assisted C1 proton departure is the rate-determining step of the total reaction. The annulation of homoenolate with B involves four elementary steps. The conformational difference of homoenolate (cis and trans) leads to two slightly different reaction processes. In the total reaction, the process involving cis-conformation of A is kinetically more feasible. This can be clearly understood through the frontier molecular orbital analysis and the electronic inductive effect. The calculated results are expected to offer valuable information for further design and development of NHC-mediated reactions. Chirality 25:521-528, 2013. (c) 2013 Wiley Periodicals, Inc.
关键词[WOS]: POLARIZABLE CONTINUUM MODEL ;  GAMMA-BUTYROLACTONES ;  STEREOSELECTIVE-SYNTHESIS ;  BRESLOW INTERMEDIATE ;  BENZOIN CONDENSATION ;  HOMOENOLATE ANIONS ;  CORRELATION-ENERGY ;  NHC CATALYSIS ;  MECHANISM ;  UMPOLUNG
语种: 英语
WOS记录号: WOS:000325921900006
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/137822
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
2.Nanyang Technol Univ, Sch Phys & Math Sci, Div Chem & Biol Chem, Singapore 639798, Singapore

Recommended Citation:
Sun, Hui,Fang, Xinqiang,Chi, Yonggui Robin,et al. Theoretical Study of N-Heterocyclic Carbenes-Catalyzed Cascade Annulation of Benzodienones and Enals[J]. CHIRALITY,2013,25(9):521-528.
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