Theoretical study of rhodium(III)-catalyzed synthesis of benzoxepine and coumarin

The mechanisms of the rhodium-catalyzed cycloaddition of 2-vinylphenol with diphenylacetylene and carbon monoxide have been studied using density functional theory calculations at the B3LYP/6-31G (d, p) (Lanl2dz for Rh) level of theory. The SMD solvation model was used in MeCN solvents at M06-2X/6-3...

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Bibliographic Details
Published in:Journal of molecular modeling 2020-05, Vol.26 (6), p.143, Article 143
Main Authors: Zhang, Xinghui, Wu, Xi, Li, Shanshan, Shi, Haixiong, Lei, Yun, Niu, Teng
Format: Article
Language:English
Subjects:
Acetylene - analogs & derivatives
Acetylene - chemistry
Benzoxepins - chemical synthesis
Carbon monoxide
Carbon Monoxide - chemistry
Catalysis
Catalytic activity
Characterization and Evaluation of Materials
Chemical synthesis
Chemistry
Chemistry and Materials Science
Computational Chemistry
Computer Appl. in Life Sciences
Computer Applications in Chemistry
Coumarin
Coumarins - chemical synthesis
Cycloaddition
Density functional theory
Models, Chemical
Molecular Medicine
Original Paper
Rhodium
Rhodium - chemistry
Solvation
Solvent effect
Solvents
Theoretical and Computational Chemistry
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Summary:The mechanisms of the rhodium-catalyzed cycloaddition of 2-vinylphenol with diphenylacetylene and carbon monoxide have been studied using density functional theory calculations at the B3LYP/6-31G (d, p) (Lanl2dz for Rh) level of theory. The SMD solvation model was used in MeCN solvents at M06-2X/6-311 ++ G (d, p) (Lanl2dz (f) for Rh) levels using a single-point calculation to consider the solvent effect. The calculation results show that there are two competitive reaction pathways for the cycloaddition reaction of rhodium-catalyzed synthesis of benzohexine and coumarin. Starting from the precursor reaction complex, the reaction channel is more favorable for the carbon atoms of diphenylacetylene and carbon monoxide to attack the Rh–C bond (the barriers of 9.88 and 10.01 kcal/mol) rather than attack the Rh–O bond (the barriers of 15.37 and 30.17 kcal/mol), and carbon monoxide in two different reaction channels has a greater energy difference than diphenylacetylene. The results show that the computational study of the rhodium-catalyzed cycloaddition reaction has a high catalytic activity consistent with the high yield of the experiment of Gulías et al.
ISSN:1610-2940
0948-5023
DOI:10.1007/s00894-020-04409-1