Abstract
Ab initio method is employed to study the structures of twelve aromatic ketones at HF/3-21G, HF/6-31G and HF/6-31G* levels, respectively. A theoretical analysis is also carried out to study the regioselectivity and reactivity of aromatic ketones in the addition with olefin catalyzed by RuH2(CO)(PPh3)3. The results indicate that a U shape LUMO conjugation of aromatic ketones in a plane plays an important role in regioselectivity on the cleavage of β C-H bond and is a necessary factor to success of addition with olefin, and that steric effect is an indispensable factor in forming additional ortho-product. Meanwhile, electronic effect may influence the rate of addition for the structures alike which only have different replacements in the same site of aromatic ring, such as furan, thiophene and pyrole. A possible catalytic reaction mechanism is proposed that the addition of C-H bond may be carried out by a coordination of aromatic ketones with Ru complex.
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Keiman, J. P., Dubeck, M., The preparation of cyclopentadienyl [o-(phenylazo) phenyl] nickel, J. Am. Chem. Soc., 1963, 85(10): 1544.
Chatt, J., Davidson, J. M., The tautomerism of arene and ditertiary phosphine complexes of ruthenium (0), and the preparation of new types of hydrido-complexes of ruthenium (II), J. Chem. Soc., 1965, February: 843.
Ryabov, A. D., Mechanisms of intramolecular activation of C-H bonds in transition-metal complexes, Chem. Rev., 1990, 90(2): 403.
Pfeffer, M., Selected applications to organic synthesis of intramolecular C-H activation reactions by transition metals, Pure Appl. Chem., 1992, 64(3): 335.
Newkome, G. R., Puckett, W. E., Gupta, V. K. et al., Cyclometalation of the platinum metals with nitrogen and alkyl, alkenyl, and benzyl carbon donors, Chem. Rev., 1986, 86(2): 451.
Murai, S., Kakiuchi, F., Sekine, S. et al., Efficient catalytic addition of aromatic carbon-hydrogen bonds to olefins, Nature, 1993, 366(6455): 529.
Murai, S., Kakiuchi, F., Sekine, S. et al., Catalytic C-H/ olefin coupling, Pure Appl. Chem., 1994, 66(7): 1527.
Murai, S., Kakiuchi, F., Sekine, S. et al., Catalytic addition of aromatic carbon-hydrogen bonds to olefins with the aid of ruthenium complexes, Bull. Chem. Soc. Jpn., 1995, 68(1): 62.
Frisch, M. J., Trunks, G. W., Schlegel, H. B. et al., Gaussian 94, Pittsburgh PA: Gaussian Inc., 1995.
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Lei, M., Feng, W., Du, H. et al. Theoretical investigation on regioselectivity of aromatic ketones in the addition with olefin catalyzed by RuH2(CO)(PPh3)3 . Sc. China Ser. B-Chem. 43, 412–420 (2000). https://doi.org/10.1007/BF02969447
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DOI: https://doi.org/10.1007/BF02969447