論文

査読有り
2017年3月

Radical-polar crossover reactions of vinylboron ate complexes

SCIENCE
  • Marvin Kischkewitz
  • ,
  • Kazuhiro Okamoto
  • ,
  • Christian Mueck-Lichtenfeld
  • ,
  • Armido Studer

355
6328
開始ページ
936
終了ページ
+
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1126/science.aal3803
出版者・発行元
AMER ASSOC ADVANCEMENT SCIENCE

Vinyl boronic esters are valuable substrates for Suzuki-Miyaura cross-coupling reactions. However, boron-substituted alkenes have drawn little attention as radical acceptors, and the radical chemistry of vinylboron ate complexes is underexplored. We show here that carbon radicals add efficiently to vinylboron ate complexes and that their adduct radical anions undergo radical-polar crossover: A 1,2-alkyl/aryl shift from boron to the alpha-carbon sp(2) center provides secondary or tertiary alkyl boronic esters. In contrast to the Suzuki-Miyaura coupling, a transition metal is not required, and two carbon-carbon bonds are formed. The valuable boronic ester moiety remains in the product and can be used in follow-up chemistry, enlarging the chemical space of the method. The cascade uses commercial starting materials and provides access to perfluoroalkylated alcohols, gamma-lactones, gamma-hydroxy alkylnitriles, and compounds bearing quaternary carbon centers.

Web of Science ® 被引用回数 : 100

リンク情報
DOI
https://doi.org/10.1126/science.aal3803
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000395181700035&DestApp=WOS_CPL

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