論文

査読有り
2017年8月

Rhodium-Catalyzed Silylative and Germylative Cyclization with Dehydrogenation Leading to 9-Sila- and 9-Germafluorenes: A Combined Experimental and Computational Mechanistic Study

CHEMISTRY-A EUROPEAN JOURNAL
  • Masahito Murai
  • ,
  • Ryo Okada
  • ,
  • Sobi Asako
  • ,
  • Kazuhiko Takai

23
45
開始ページ
10861
終了ページ
10870
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1002/chem.201701579
出版者・発行元
WILEY-V C H VERLAG GMBH

Stoichiometric amounts of oxidants are widely used as promoters (hydrogen acceptors) in dehydrogenative silylation of C-H bonds. However, the present study demonstrates that silylative and germylative cyclization with dehydrogenation can proceed efficiently, even without hydrogen acceptors. The combination of [RhCl(cod)](2) and PPh3 was effective for both transformations, and allowed a reduction in reaction temperature compared with our previous report. Monitoring of the reactions revealed that both transformations had an induction period for the early stage, and that the rate constant of dehydrogenative germylation was greater than that of dehydrogenative silylation. Competitive reactions in the presence of 3,3-dimethyl-1-butene indicated that the ratio of dehydrogenative metalation and hydrometalation was affected by reaction temperature when a hydrosilane or hydrogermane precursor was used. Further mechanistic insights of oxidant-free dehydrogenative silylation, including the origin of these unique reactivities, were obtained by density functional theory studies.

Web of Science ® 被引用回数 : 16

リンク情報
DOI
https://doi.org/10.1002/chem.201701579
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000407397300023&DestApp=WOS_CPL
URL
http://orcid.org/0000-0003-4525-5317

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