(π-Allyl)palladium Complexes Bearing Diphosphinidenecyclobutene Ligands (DPCB):  Highly Active Catalysts for Direct Conversion of Allylic Alcohols

Fumiyuki Ozawa,*† Hideyuki Okamoto,† Seiji Kawagishi,† Shogo Yamamoto,† Tatsuya Minami,† and Masaaki Yoshifuji‡
Department of Applied Chemistry, Graduate School of Engineering, Osaka City University, Osaka 558-8585, Japan, and Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
J. Am. Chem. Soc., 2002, 124 (37), pp 10968–10969
DOI: 10.1021/ja0274406
Publication Date (Web): August 20, 2002
Copyright © 2002 American Chemical Society
*

 To whom correspondence should be addressed. E-mail: ozawa@a-chem.eng.osaka-cu.ac.jp.

,
†

 Osaka City University.

,
‡

 Tohoku University.

Abstract

Abstract Image

The (π-allyl)palladium complex bearing an sp2-hybridized phosphorus ligand (DPCB-OMe:  1,2-bis(4-methoxyphenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene) efficiently catalyzes direct conversion of allylic alcohols in the absence of activating agents of alcohols such as Lewis acids. N-Allylation of aniline proceeds at room temperature to afford monoallylated anilines in 90−97% yields. C-Allylation of active methylene compounds is also successful at 50 °C using a catalytic amount of pyridine as a base, giving monoallylation products in 85−95% yields. The catalytic mechanism involving hydrido- and (π-allyl)palladium intermediates has been proposed on the basis of stoichiometric examinations using model compounds of presumed intermediates.

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History

  • Published In Issue September 18, 2002
  • Received June 24, 2002

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