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The First General and Selective Palladium(II)-Catalyzed Alkoxycarbonylation of Arylboronates: Interplay among Benzoquinone-Ligated Palladium(0) Complex, Organoboron, and Alcohol Solvent

  1. Yoshihiko Yamamoto1,2

Article first published online: 10 FEB 2010

DOI: 10.1002/adsc.200900836

Issue

Advanced Synthesis & Catalysis

Advanced Synthesis & Catalysis

Volume 352, Issue 2-3, pages 478–492, February 15, 2010

Additional Information

How to Cite

Yamamoto, Y. (2010), The First General and Selective Palladium(II)-Catalyzed Alkoxycarbonylation of Arylboronates: Interplay among Benzoquinone-Ligated Palladium(0) Complex, Organoboron, and Alcohol Solvent. Adv. Synth. Catal., 352: 478–492. doi: 10.1002/adsc.200900836

Author Information

  1. 1

    Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8552, Japan

  2. 2

    Current address: Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan, Fax: (+81)-52-789-3209

Publication History

  1. Issue published online: 17 FEB 2010
  2. Article first published online: 10 FEB 2010
  3. Manuscript Revised: 30 DEC 2009
  4. Manuscript Received: 1 DEC 2009

Funded by

  • MEXT
  • Grant-in-Aid for Scientific Research (B. Grant Number: 20350045
  • Scientific Research on Priority Area “Chemistry on Concerto Catalysis”. Grant Number: 20037018

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Keywords:

  • carbonylation;
  • carboxylic esters;
  • DFT calculations;
  • organoboron compounds;
  • palladium catalysts

Abstract

Methoxycarbonylation of aryl- and alkenylboron compounds was performed using the palladium(II) acetate/triphenylphosphine [Pd(OAc)2/PPh3] catalyst with p-benzoquinone as a stoichiometric oxidant in methanol at ambient temperature to obtain the corresponding methyl esters in good yields. A wide variety of functional groups including various carbonyl functionalities, nitrile, nitro, sulfone, and unprotected pyrrole rings were tolerated in the methoxycarbonlation, while the use of higher alcohols except for tert-butanol afforded various p-chlorobenzoates in moderate to high yields. The catalytic alkoxycarbonylation proceeded without any acid or base additive, and an oxidative transmetalation step is proposed to explain the exceptional efficacy of this protocol. DFT and MP2 calculations support the proposed mechanism.

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