期刊
MOLECULAR CATALYSIS
卷 527, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.mcat.2022.112410
关键词
DFT; Reaction mechanism; Organometallic catalysis; Stereoselectivity
资金
- National Natural Science Foundation of China [21903072, 21773214]
- Natural Science Foundation for Excellent Young Scientist in Henan Province [212300410083]
- Training Plan for Young Teachers in Colleges and Universities in Henan Province [2020GGJS016]
- Outstanding Young Talent Research Fund of Zhengzhou University [1521316001]
- Startup Fund of Zhengzhou University of Light Industry [2017BSJJ036]
In this study, the mechanism of a cobalt-catalyzed hydroacylation reaction between aldehydes and 1,6-enynes and the origin of its stereoselectivity were investigated using the DFT calculational method. The aldehyde-first mechanism was found to be energetically more favorable and the alkene insertion step was identified as the key step determining the stereoselectivity.
In the present study, the mechanism of a cobalt-catalyzed hydroacylation reaction between aldehydes and 1,6enynes and the origin of its stereoselectivity have been systematically investigated using the DFT calculational method. Two possible reaction mechanisms have been investigated: one that starts with oxidative addition of the aldehyde (aldehyde-first) or one that starts with oxidative cyclization of the 1,6-enyne (enyne-first). The computational results show that the aldehyde-first mechanism is energetically more favorable than is the enynefirst mechanism. The aldehyde-first mechanism contains several steps: oxidative addition, acyl migratory insertion, alkene insertion, and reductive elimination. Based on the calculations, the alkene insertion is the stereoselectivity-determining step, generating the S-configured product preferentially. The key to inducing the observed stereoselectivity is the lesser distortion of the structure of the lower-energy transition state that leads to the S-configured product.
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