期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 16, 期 16, 页码 2346-2350出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.202100351
关键词
organocatalyst; N-heterocyclic carbene; stereoselectivity; mechanism
资金
- National Natural Science Foundation of China [21773214]
- Natural Science Foundation for Excellent Young Scientist in Henan Province [212300410083]
- Training Plan for Young Key Teachers in Colleges and Universities in Henan Province [2020GGJS016]
- Program for Science & Technology Innovation Talents in Universities of Henan [20HASTIT048]
- 111 Project [D20003]
- Cultivation Foundation of Zhengzhou University [JC202035022]
- National Super-computing Center in Zhengzhou
A computational study was conducted to investigate the stereoselectivity origin of NHC-mediated cyclization reaction between benzoic acid and o-phthalaldehyde. The study found that the formation of C-O bonds is crucial for determining stereoselectivity, with the R-configurational pathway being more energetically favorable than the S-configurational one. Non-covalent interaction (NCI) and atom-in-molecule (AIM) analyses revealed that hydrogen-bond interactions play a key role in controlling the stereoselectivity.
A computational study was contributed to explore the origin of stereoselectivity of NHC-mediated cyclization reaction between benzoic acid and o-phthalaldehyde for asymmetric construction of phthalidyl ester. The most energetically favorable pathway mainly includes the following steps: (1) nucleophilic attack on carbonyl carbon of o-phthalaldehyde by catalyst NHC, (2) formation of Breslow intermediate, (3) oxidation by DQ, (4) asymmetric formation of dual C-O bonds, and (5) dissociation of catalyst with the product. The C-O bond formation was testified as the stereoselectivity-determining step, the R-configurational pathway is more energetically favorable than the S-configurational one. The non-covalent interaction (NCI) and atom-in-molecule (AIM) analyses were performed to reveal that the O-H ... O and C-H ... O hydrogen-bond interactions are the key factors for controlling the stereoselectivity. The detailed mechanism and origin of stereoselectivity give useful insights for understanding organocatalytic reactions for asymmetric construction of C-O bond.
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