Remarkable electron-withdrawing effect of the Ph2P(O)-ethynyl group: Ph2P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings

Lifen Peng; Feng Xu; Kenta Shinohara; Takanori Nishida; Kan Wakamatsu; Akihiro Orita; Junzo Otera

doi:10.1039/C4QO00325J

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Remarkable electron-withdrawing effect of the Ph₂P(O)-ethynyl group: Ph₂P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings†‡

Lifen Peng,^a Feng Xu,^a Kenta Shinohara,^a Takanori Nishida,^a Kan Wakamatsu,^b Akihiro Orita*^a and Junzo Otera^a

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* Corresponding authors

^a Department of Applied Chemistry, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan
E-mail: orita@dac.ous.ac.jp
Fax: +81 86 256 4292

^b Department of Chemistry, Okayama University of Science, 1-1 Ridai-cho, Kita-ku, Okayama 700-0005, Japan

Abstract

The electronic effect of the Ph₂P(O)-ethynyl group in Sonogashira couplings was investigated. Ph₂P(O)-ethynylphenyl iodide showed higher reactivity than diiodobenzene because of the electron-withdrawing effect of the Ph₂P(O) group. Copper acetylide, which was prepared in situ from Ph₂P(O)-ethyne, exhibited poor nucleophilicity and reacted with aryl iodides in Sonogashira couplings, but did not react with aryl bromides. This high selectivity enabled practical syntheses of a cyclic phenyleneethynylene and unsymmetrically substituted 9,10-bis(ethynyl)anthracenes.

This article is part of the themed collection: Celebrating the 80th Birthday of Professor Ei-ichi Negishi

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Article information

DOI: https://doi.org/10.1039/C4QO00325J
Article type: Research Article
Submitted: 12 dec 2014
Accepted: 10 jan 2015
First published: 29 jan 2015

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Org. Chem. Front., 2015,2, 248-252

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Remarkable electron-withdrawing effect of the Ph₂P(O)-ethynyl group: Ph₂P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings

L. Peng, F. Xu, K. Shinohara, T. Nishida, K. Wakamatsu, A. Orita and J. Otera, Org. Chem. Front., 2015, 2, 248 DOI: 10.1039/C4QO00325J

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