Publication: Insights into the Regioselectivity of Hydroheteroarylation of Allylbenzene with Pyridine Catalyzed by Ni/AlMe<inf>3</inf>with N-Heterocyclic Carbene: The Concerted Hydrogen Transfer Mechanism
Issued Date
2020-09-04
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15206904
00223263
00223263
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2-s2.0-85092193150
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Mahidol University
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SCOPUS
Bibliographic Citation
Journal of Organic Chemistry. Vol.85, No.17 (2020), 11340-11349
Suggested Citation
Phiphob Naweephattana, Boodsarin Sawatlon, Panida Surawatanawong Insights into the Regioselectivity of Hydroheteroarylation of Allylbenzene with Pyridine Catalyzed by Ni/AlMe<inf>3</inf>with N-Heterocyclic Carbene: The Concerted Hydrogen Transfer Mechanism. Journal of Organic Chemistry. Vol.85, No.17 (2020), 11340-11349. doi:10.1021/acs.joc.0c01449 Retrieved from: https://repository.li.mahidol.ac.th/handle/20.500.14594/59931
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Title
Insights into the Regioselectivity of Hydroheteroarylation of Allylbenzene with Pyridine Catalyzed by Ni/AlMe<inf>3</inf>with N-Heterocyclic Carbene: The Concerted Hydrogen Transfer Mechanism
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Abstract
© 2020 American Chemical Society. The hydroheteroarylation of allylbenzene with pyridine as catalyzed by Ni/AlMe3 and a N-heterocyclic carbene ligand has recently been established. Density functional calculations revealed that the common stepwise pathway, which involves the C-H oxidative addition of pyridine-AlMe3 before the migratory insertion of allylbenzene, is unlikely as the migratory insertion needs to overcome a prohibitively high energy barrier. In contrast, the ligand-to-ligand hydrogen transfer pathway is more favorable in which the hydrogen is transferred directly from the para-position of pyridine-AlMe3 to C2 of allylbenzene. Our distortion-interaction analysis and natural bond orbital analysis indicate that the interaction energy is strongly correlated with the extent of the charge transfer from the alkene (hydrogen acceptor) to the pyridine-AlMe3 (hydrogen donor), which dictates the selectivity of the H-transfer to the C2 position of allylbenzene. Then, the subsequent C-C reductive elimination of the regioselective linear product is facilitated by the steric hindrance of the IPr ligand. Understanding these key factors affecting the product regioselectivity is important to the development of catalysts for hydroheteroarylation of alkenes.