Cyanation of Alcohols with Diethyl Cyanophosphonate and 2,6-Dimethyl-1,4-benzoquinone by a New Type of Oxidation-Reduction Condensation

• Masutani Kouta

  Center for Basic Research, The Kitasato Institute

• Minowa Tomofumi

  Center for Basic Research, The Kitasato Institute

• Hagiwara Yoshiaki

  Center for Basic Research, The Kitasato Institute

• Mukaiyama Teruaki

  Center for Basic Research, The Kitasato Institute Kitasato Institute for Life Sciences, Kitasato University

Abstract

Cyanation of various alcohols by a new type of oxidation–reduction condensation is described. Primary alkyl diphenylphosphinites, 2,6-dimethyl-1,4-benzoquinone (DMBQ), and diethyl cyanophosphonate gave the corresponding nitriles in high yields. During the above experiment on cyanation of 4-phenylbutan-2-ol, the unexpected formation of a mixture of nitrile and isocyanide was observed. After careful examination of the reaction conditions, selective synthesis of isocyanides from secondary alcohols was successfully accomplished by the use of zinc oxide (ZnO) as an additive. Reaction of tertiary alcohols provided the corresponding isocyanides exclusively in the absence of an additive. Cyanation of optically active alcohols was tried in order to clarify the stereochemistry of this reaction, and the reaction was thus proved to proceed with the inversion of configuration.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 79 (7), 1106-1117, 2006

  The Chemical Society of Japan

Keywords

• General Chemistry

Details

• CRID: 1390282679119969792
• NII Article ID: 130004152159
• NII Article ID: 10018001695
• NII Book ID: AA00580132
• DOI: 10.1246/bcsj.79.1106
• ISSN: 13480634
• ISSN: 00092673
• NDL BIB ID: 7971674
• Web Site: https://ndlsearch.ndl.go.jp/books/R000000004-I7971674
• Web Site: https://academic.oup.com/bcsj/article-pdf/79/7/1106/56266578/bcsj.79.1106.pdf
• Text Lang: en
• Data Source:
  • JaLC
  • NDL
  • Crossref
  • CiNii Articles
• Abstract License Flag: Disallowed