Origin of regioselectivity in the reactions of nitronate and enolate ambident anions
Tomomi Sakata1, Natsuko Seki, Kozue Yomogida
1Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University, Nishi-Ikebukuro, Toshima-ku 171-8501, Tokyo, Japan.
Abstract:
The reactions of nitronates of ring-substituted phenylnitromethanes and enolates of ring-substituted 1-phenyl-2-propanones with MeOBs gave exclusively the O-methylated and C-methylated products, respectively. DFT calculations suggested that two factors, namely, intrinsic barriers and metal-cation coordination, control the C/O selectivity. The kinetic preference for O-methylation in the reactions of nitronates arises from the intrinsic barriers, which are ca. 10 kcal/mol lower for O-methylation than for C-methylation. The situation is the same for the gas-phase reaction of an enolate, in which the O-methylation is more favorable than the C-methylation. The experimentally observed C-selectivity of enolate reactions in solution is due to the metal-cation coordination, which hinders O-methylation for enolates. The effects of the enolate reactivity and the solvent on the C/O selectivity are also rationalized to arise from the two factors.
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