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

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

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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.

Original language	English (US)
Pages (from-to)	248-252
Number of pages	5
Journal	Organic Chemistry Frontiers
Volume	2
Issue number	3
DOIs	https://doi.org/10.1039/c4qo00325j
State	Published - Mar 2015

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Publisher Copyright:
© 2015 the Partner Organisations.

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10.1039/c4qo00325j

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

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.",

author = "Lifen Peng and Feng Xu and Kenta Shinohara and Takanori Nishida and Kan Wakamatsu and Akihiro Orita and Junzo Otera",

note = "Publisher Copyright: {\textcopyright} 2015 the Partner Organisations.",

year = "2015",

month = mar,

doi = "10.1039/c4qo00325j",

language = "English (US)",

volume = "2",

pages = "248--252",

journal = "Organic Chemistry Frontiers",

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TY - JOUR

T1 - Remarkable electron-withdrawing effect of the Ph2P(O)-ethynyl group

T2 - Ph2P(O)-ethynyl-substituted aryl halides and copper acetylides for tailor-made Sonogashira couplings

AU - Peng, Lifen

AU - Xu, Feng

AU - Shinohara, Kenta

AU - Nishida, Takanori

AU - Wakamatsu, Kan

AU - Orita, Akihiro

AU - Otera, Junzo

PY - 2015/3

Y1 - 2015/3

N2 - 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.

AB - 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.

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DO - 10.1039/c4qo00325j

M3 - Article

AN - SCOPUS:84946716014

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SP - 248

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JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

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