Tags

Type your tag names separated by a space and hit enter

Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions.
J Comput Chem. 2008 Apr 15; 29(5):686-93.JC

Abstract

The reaction mechanism of the Rh-catalyzed [4 + 2] annulation of 4-alkynals with isocyanates is unraveled using density functional calculations. The reaction mechanisms of the model system and the real substituted system have been investigated and the results are compared. From our theoretical results based on the model and real substituted system, it is shown that (a) the rate-determining step is the Rh-H addition to the alkyne, (b) the formation of the cyclopentenone G and glutarimide K represents a severe competition, and (c) the product selectivity should be controlled by the amount of the isocyanates. In addition, it is demonstrated that there exist steric effects in the real substituted system, but missed in model system. Our calculations also show that although the results obtained on the model system could explain the mechanism in principle, the real substituted system could reflect the mechanism more exactly and make the reaction proceed with regioselectivity.

Authors+Show Affiliations

State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

17849391

Citation

Geng, Cai-Yun, et al. "Theoretical Elucidation of the Rhodium-catalyzed [4 + 2] Annulation Reactions." Journal of Computational Chemistry, vol. 29, no. 5, 2008, pp. 686-93.
Geng CY, Li JL, Huang XR, et al. Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions. J Comput Chem. 2008;29(5):686-93.
Geng, C. Y., Li, J. L., Huang, X. R., Liu, H. L., Li, Z., & Sun, C. C. (2008). Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions. Journal of Computational Chemistry, 29(5), 686-93.
Geng CY, et al. Theoretical Elucidation of the Rhodium-catalyzed [4 + 2] Annulation Reactions. J Comput Chem. 2008 Apr 15;29(5):686-93. PubMed PMID: 17849391.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Theoretical elucidation of the rhodium-catalyzed [4 + 2] annulation reactions. AU - Geng,Cai-Yun, AU - Li,Ji-Lai, AU - Huang,Xu-Ri, AU - Liu,Hui-Ling, AU - Li,Zhuo, AU - Sun,Chia-Chung, PY - 2007/9/13/pubmed PY - 2008/6/12/medline PY - 2007/9/13/entrez SP - 686 EP - 93 JF - Journal of computational chemistry JO - J Comput Chem VL - 29 IS - 5 N2 - The reaction mechanism of the Rh-catalyzed [4 + 2] annulation of 4-alkynals with isocyanates is unraveled using density functional calculations. The reaction mechanisms of the model system and the real substituted system have been investigated and the results are compared. From our theoretical results based on the model and real substituted system, it is shown that (a) the rate-determining step is the Rh-H addition to the alkyne, (b) the formation of the cyclopentenone G and glutarimide K represents a severe competition, and (c) the product selectivity should be controlled by the amount of the isocyanates. In addition, it is demonstrated that there exist steric effects in the real substituted system, but missed in model system. Our calculations also show that although the results obtained on the model system could explain the mechanism in principle, the real substituted system could reflect the mechanism more exactly and make the reaction proceed with regioselectivity. SN - 1096-987X UR - https://www.unboundmedicine.com/medline/citation/17849391/Theoretical_elucidation_of_the_rhodium_catalyzed_[4_+_2]_annulation_reactions_ L2 - https://doi.org/10.1002/jcc.20824 DB - PRIME DP - Unbound Medicine ER -