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Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes

Publication ,  Journal Article
Widenhoefer, RA; Buchwald, SL
Published in: Journal of the American Chemical Society
July 8, 1998

Thermal decomposition of the palladium (aryl)neopentoxide complexes [P-P]Pd(Ar)OCH2CMe3 [P-P =Tol-BINAP or BINAP; Ar p-C6H4CHO (1b), p-C6H4COPh (1c), p-C6H4NO2 (1d), o-C6H4NO2 (1e), o-C6H4CN (1F)] possessing substituents on the palladium-bound aryl group suitable for delocalization of negative charge led to quantitative (≤95%) formation of aryl ether without detectable β-hydride elimination. Thermal decomposition of 1b-f obeyed first-order kinetics, and the rate of reductive elimination decreased in the order o-NO2 > p-NO2 > p-CHO > p-COPh > o-CN. Conversely, thermal decomposition of the related derivatives [P-P]Pd(Ar)OCH2CMe3 [P-P = Tol-BINAP or BINAP; Ar p-C6H4Cl (1g), m-C6H4NO2 (1h), m-C6H4CN (1i)] which did not possess a resonance stabilizing group on the palladium-bound aryl group led to no detectable formation of aryl ether. These and related data point to the buildup of negative charge in the palladium-bound aryl group in the transition state for C-O reductive elimination and are consistent with a mechanism initiated by inner-sphere nucleophilic attack of the alkoxide ligand at the ipso-carbon atom of the palladium-bound aryl group through a zwitterionic Meisenheimer-type intermediate or transition state.

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Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

July 8, 1998

Volume

120

Issue

26

Start / End Page

6504 / 6511

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

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Widenhoefer, R. A., & Buchwald, S. L. (1998). Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes. Journal of the American Chemical Society, 120(26), 6504–6511. https://doi.org/10.1021/ja9806581
Widenhoefer, R. A., and S. L. Buchwald. “Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes.” Journal of the American Chemical Society 120, no. 26 (July 8, 1998): 6504–11. https://doi.org/10.1021/ja9806581.
Widenhoefer RA, Buchwald SL. Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes. Journal of the American Chemical Society. 1998 Jul 8;120(26):6504–11.
Widenhoefer, R. A., and S. L. Buchwald. “Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes.” Journal of the American Chemical Society, vol. 120, no. 26, July 1998, pp. 6504–11. Scopus, doi:10.1021/ja9806581.
Widenhoefer RA, Buchwald SL. Electronic dependence of C-O reductive elimination from palladium (aryl)neopentoxide complexes. Journal of the American Chemical Society. 1998 Jul 8;120(26):6504–6511.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

ISSN

0002-7863

Publication Date

July 8, 1998

Volume

120

Issue

26

Start / End Page

6504 / 6511

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences