Palladium-catalyzed arylation of alpha,alpha-disubstituted arylmethanols via cleavage of a C-C or a C-H bond to give biaryls

Yoshito Terao; Hiroyuki Wakui; Michiyo Nomoto; Tetsuya Satoh; Masahiro Miura; Masakatsu Nomura

doi:10.1021/jo0344034

Palladium-catalyzed arylation of alpha,alpha-disubstituted arylmethanols via cleavage of a C-C or a C-H bond to give biaryls

J Org Chem. 2003 Jun 27;68(13):5236-43. doi: 10.1021/jo0344034.

Authors

Yoshito Terao¹, Hiroyuki Wakui, Michiyo Nomoto, Tetsuya Satoh, Masahiro Miura, Masakatsu Nomura

Affiliation

¹ Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.

PMID: 12816483
DOI: 10.1021/jo0344034

Abstract

The palladium-catalyzed arylation of alpha,alpha-disubstituted arylmethanols with aryl halides proceeds not only via C-H bond cleavage at the ortho-position, but also via cleavage of the sp(2)-sp(3) C-C bond with the liberation of ketones (beta-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.