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Palladium-Catalyzed Arylation of α,α-Disubstituted Arylmethanols via Cleavage of a C−C or a C−H Bond To Give Biaryls

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posted on 22.05.2003, 00:00 by Yoshito Terao, Hiroyuki Wakui, Michiyo Nomoto, Tetsuya Satoh, Masahiro Miura, Masakatsu Nomura
The palladium-catalyzed arylation of α,α-disubstituted arylmethanols with aryl halides proceeds not only via C−H bond cleavage at the ortho-position, but also via cleavage of the sp2−sp3 C−C bond with the liberation of ketones (β-carbon elimination) to give the corresponding biaryls. Both reactions appear to occur through common arylpalladium(II) alcoholate intermediates. The results of systematic studies with respect to which C−C or C−H bond is preferentially cleaved in the arylation are reported. Among the important findings is the selective elimination of ortho-substituted aryl groups even from aryl(diphenyl)methanols due to steric reasons. Thus, various biaryls having ortho-substituents can be produced efficiently by treatment of the corresponding aryl(diphenyl or dimethyl)methanols with aryl bromides and chlorides.