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

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...

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Veröffentlicht in:Journal of organic chemistry 2003-06, Vol.68 (13), p.5236-5243
Hauptverfasser: Terao, Yoshito, Wakui, Hiroyuki, Nomoto, Michiyo, Satoh, Tetsuya, Miura, Masahiro, Nomura, Masakatsu
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Sprache:eng
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Zusammenfassung: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0344034