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Theoretical study of rhodium(III)-catalyzed synthesis of benzoxepine and coumarin.
J Mol Model. 2020 May 16; 26(6):143.JM

Abstract

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.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Zhang X
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China. zhxh135@163.com.
Wu X
School of Foreign Languages, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
Li S
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
Shi H
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
Lei Y
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.
Niu T
School of Chemical Engineering, Lanzhou University of Arts and Science, Lanzhou, 730010, Gansu, People's Republic of China.

MeSH

AcetyleneBenzoxepinsCarbon MonoxideCatalysisComputational ChemistryCoumarinsModels, ChemicalRhodium

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32417972

Citation

Zhang, Xinghui, et al. "Theoretical Study of rhodium(III)-catalyzed Synthesis of Benzoxepine and Coumarin." Journal of Molecular Modeling, vol. 26, no. 6, 2020, p. 143.
Zhang X, Wu X, Li S, et al. Theoretical study of rhodium(III)-catalyzed synthesis of benzoxepine and coumarin. J Mol Model. 2020;26(6):143.
Zhang, X., Wu, X., Li, S., Shi, H., Lei, Y., & Niu, T. (2020). Theoretical study of rhodium(III)-catalyzed synthesis of benzoxepine and coumarin. Journal of Molecular Modeling, 26(6), 143. https://doi.org/10.1007/s00894-020-04409-1
Zhang X, et al. Theoretical Study of rhodium(III)-catalyzed Synthesis of Benzoxepine and Coumarin. J Mol Model. 2020 May 16;26(6):143. PubMed PMID: 32417972.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Theoretical study of rhodium(III)-catalyzed synthesis of benzoxepine and coumarin. AU - Zhang,Xinghui, AU - Wu,Xi, AU - Li,Shanshan, AU - Shi,Haixiong, AU - Lei,Yun, AU - Niu,Teng, Y1 - 2020/05/16/ PY - 2020/3/15/received PY - 2020/4/29/accepted PY - 2020/5/18/entrez PY - 2020/5/18/pubmed PY - 2021/4/1/medline KW - 2-vinylphenol KW - Cycloaddition KW - Diphenylacetylene KW - Rhodium(III)-catalyzed SP - 143 EP - 143 JF - Journal of molecular modeling JO - J Mol Model VL - 26 IS - 6 N2 - 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. SN - 0948-5023 UR - https://www.unboundmedicine.com/medline/citation/32417972/Theoretical_study_of_rhodium_III__catalyzed_synthesis_of_benzoxepine_and_coumarin_ DB - PRIME DP - Unbound Medicine ER -