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Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to alkynes.
J Comput Chem. 2008 Aug; 29(11):1825-39.JC

Abstract

The B3LYP hybrid density functional method has been carried out to study theoretically the mechanism of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH(3))(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH(3))(2), and in path C of each reaction, the first step is the PH(3) dissociation from Pd(PH(3))(2) to form monophosphine complex Pd(PH(3)). For both reactions, path B is favored. The dissociation and recoordination of phosphine ligand are found to be very important for the entire reaction, in agreement with the experiment. In both intermolecular and intramolecular cyanoboration reactions, cyano migration is preferred to take place compared with alkenylboryl migration for the formation of the final cis products. The rate-determining step for both intermolecular and intramolecular cyanoboration reactions is found to be the insertion of carbon-carbon triple bond into Pd-B bond with the activation energy of 38.4 and 34.3 kcal/mol relative to the initial reactants, respectively. These values suggest that intramolecular reaction is relatively easy to occur.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Wang MY
Key Laboratory of Rare Earth Chemistry and Physics, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China.
Cheng L
No affiliation info available
Wu ZJ
No affiliation info available

MeSH

AcetyleneAlkynesBoranesCatalysisPalladiumThermodynamics

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

18351592

Citation

Wang, M Y., et al. "Density Functional Study On the Reaction Mechanism of Palladium-catalyzed Addition of Cyanoboranes to Alkynes." Journal of Computational Chemistry, vol. 29, no. 11, 2008, pp. 1825-39.
Wang MY, Cheng L, Wu ZJ. Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to alkynes. J Comput Chem. 2008;29(11):1825-39.
Wang, M. Y., Cheng, L., & Wu, Z. J. (2008). Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to alkynes. Journal of Computational Chemistry, 29(11), 1825-39. https://doi.org/10.1002/jcc.20944
Wang MY, Cheng L, Wu ZJ. Density Functional Study On the Reaction Mechanism of Palladium-catalyzed Addition of Cyanoboranes to Alkynes. J Comput Chem. 2008;29(11):1825-39. PubMed PMID: 18351592.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Density functional study on the reaction mechanism of palladium-catalyzed addition of cyanoboranes to alkynes. AU - Wang,M Y, AU - Cheng,L, AU - Wu,Z J, PY - 2008/3/21/pubmed PY - 2008/8/12/medline PY - 2008/3/21/entrez SP - 1825 EP - 39 JF - Journal of computational chemistry JO - J Comput Chem VL - 29 IS - 11 N2 - The B3LYP hybrid density functional method has been carried out to study theoretically the mechanism of Pd(0)-catalyzed alkyne cyanoboration reaction. Both the intermolecular and intramolecular alkyne cyanoboration reactions were studied. For each reaction, three paths were proposed. In path A of each reaction, the first step is B-CN bond oxidative addition to bisphosphine complex Pd(PH(3))(2), in path B of each reaction, the first step is alkyne coordination to bisphosphine complex Pd(PH(3))(2), and in path C of each reaction, the first step is the PH(3) dissociation from Pd(PH(3))(2) to form monophosphine complex Pd(PH(3)). For both reactions, path B is favored. The dissociation and recoordination of phosphine ligand are found to be very important for the entire reaction, in agreement with the experiment. In both intermolecular and intramolecular cyanoboration reactions, cyano migration is preferred to take place compared with alkenylboryl migration for the formation of the final cis products. The rate-determining step for both intermolecular and intramolecular cyanoboration reactions is found to be the insertion of carbon-carbon triple bond into Pd-B bond with the activation energy of 38.4 and 34.3 kcal/mol relative to the initial reactants, respectively. These values suggest that intramolecular reaction is relatively easy to occur. SN - 1096-987X UR - https://www.unboundmedicine.com/medline/citation/18351592/Density_functional_study_on_the_reaction_mechanism_of_palladium_catalyzed_addition_of_cyanoboranes_to_alkynes_ DB - PRIME DP - Unbound Medicine ER -