Previous work from Garg, Shi and Itami showed that the chemoselectivity of Ni-catalyzed C-O activation of aryl ester depends highly on the choice of substrate and ligand. The monodentate phosphine ligand favors the C(aryl)-O activation, while the bidentate phosphine ligand favors the C(alkyl)-O activation. Our DFT calculations (B3LYP and M06) revealed the mechanism and origins of the switchable chemoselectivity of Ni-catalyzed C-O activations. The ligand denticity and C-O bond strength of the substrate determine the competition between the three-membered and five-membered C-O activation transition states, leading to the observed chemoselectivity. Based on our computations, we have also predicted the potential of [Ni(NHC)] complex in catalyzing the amidation of ester through similar C(acyl)-O activation. References: 1. Yu, D. –G.; Li, B. –J.; Shi, Z. –J. Acc. Chem. Res. 2010, 43, 1486. 2. Rosen, B. M.; Quasdorf, K. W.; Wilson, D. A.; Zhang, N.; Resmerita, A. –M. Garg, N. K.; Percec, V. Chen. Rev. 2011, 111, 1346. 3. Amaike, K.; Muto, K.; Yamaguchi, J.; Itami, K. J. Am. Chem. Soc. 2012, 134, 13573. 4. Hong, X.; Liang, Y.; Houk, K. N. J. Am. Chem. Soc. 2014, 136, 2017. 5. Hie, L.; Nathel, N. F. F.; Shah, T. K.; Baker, E. L.; Hong, X.; Yang, Y. –F.; Liu, P.; Houk, K. N. Garg, N. K. Nature 2015, 524, 79. 6. Muto, K.; Yamaguchi, J.; Musaev, D. G.; Itami, K. Nature Comm. 2015, 6, 7508.

Computational studies on the mechanism and switchable chemoselectivity of Ni-catalyzed C-O activations of aryl esters

251st National Meeting (2016)

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