Ketene Recognizes 1,3-Dienes in Their s-Cis Forms through [4 + 2] (Diels−Alder) and [2 + 2] (Staudinger) Reactions. An Innovation of Ketene Chemistry

DOI Web Site 被引用文献6件
  • Takahisa Machiguchi
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan
  • Toshio Hasegawa
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan
  • Akihiro Ishiwata
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan
  • Shiro Terashima
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan
  • Shinichi Yamabe
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan
  • Tsutomu Minato
    Contribution from the Department of Chemistry, Faculty of Science, Saitama University, Urawa, Saitama 338-8570, Japan, Sagami Chemical Research Center, Nishi-Ohnuma, Sagamihara, Kanagawa 229-0012, Japan, Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan, and Institute for Natural Science, Nara University, Misasagi-cho, Nara 631-8502, Japan

書誌事項

公開日
1999-05-01
DOI
  • 10.1021/ja990072u
公開者
American Chemical Society (ACS)

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説明

The mechanism of ketene−diene reactions has been studied both experimentally and theoretically. Careful experiments of the reactions of diphenylketene (1) with cyclic (s-cis) 1,3-dienes [cyclopentadiene (2) and cyclohexa-1,3-diene (3)] lead to the first direct detection of the Diels−Alder cycloadducts (10 and 11) by low-temperature NMR spectroscopy. The initially formed cycloadducts are converted to the final Staudinger products, cyclobutanones (6 and 7), by [3,3] sigmatropic (Claisen) rearrangements. In contrast, ketene 1 reacts with open-chain 1,3-dienes [2,3-dimethyl-1,3-butadiene (4) and 1-methoxy-1,3-butadiene (5)] to afford initially both the Staudinger-type (8, 9) and Diels−Alder-type cycloadducts (12, 13). The Staudinger cycloadducts (8, 9) are converted eventually to Diels−Alder products (12, 13) by the retro-Claisen rearrangement. Thus, ketene recognizes dienes in cycloadditions as ketenophiles different from olefins. [4 + 2] and [2 + 2] cycloadducts are generated and can be intermediates or pro...

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