Chemoselective activation of sp(3) vs sp(2) C-H bonds with Pd(II)

Pd(II)对sp(3)与sp(2) CH键的化学选择性活化

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Abstract

The first selective coupling of a carbon nucleophile with methyl, ethyl, propyl, and butyl arenes in the absence of a directing group is described. Pd(OAc)2 double C-H activation displays remarkable selectivity for the terminal methyl sites in alkyl arenes, rather than the more commonly observed arene sp(2) C-H activation. Mechanistic studies indicate the intermediacy of an azlactone dimer, obtained from oxidation with Pd(OAc)2, and are consistent with a Pd-catalyzed C-H activation vs a radical process. The observed reactivity establishes that typical reaction solvents (e.g., toluene) can readily participate in C-H activation chemistry.

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