Asymmetric Nitrocyclopropanation of α-Substituted α,β-Enals Catalyzed by Diphenylprolinol Silyl Ether for the Construction of All-Carbon Quaternary Stereogenic Centers

Yujiro Hayashi, Tatsuya Yamazaki, Yuki Nakanishi, Tsuyoshi Ono, Tohru Taniguchi, Kenji Monde, Tadafumi Uchimaru

研究成果: Article査読

6 被引用数 (Scopus)

抄録

The diphenylprolinol silyl ether mediated asymmetric nitrocyclopropanation of α-substituted α,β-unsaturated aldehydes with bromonitromethane, followed by base-promoted isomerization was found to afford trans-nitrocyclopropanecarbaldehydes with all-carbon quaternary stereogenic centers with excellent diastereo- and enantioselectivities. DFT calculations indicated that the s-trans conformer of the iminium ion intermediate is more stable than the s-cis conformer. In addition, nucleophilic attack of the bromonitromethane anion to the iminium ion intermediate was calculated to occur preferentially from the opposite side of the bulky substituents of the pyrrolidine iminium intermediate.

本文言語English
ページ(範囲)5747-5754
ページ数8
ジャーナルEuropean Journal of Organic Chemistry
2015
26
DOI
出版ステータスPublished - 2015 9 1

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

フィンガープリント 「Asymmetric Nitrocyclopropanation of α-Substituted α,β-Enals Catalyzed by Diphenylprolinol Silyl Ether for the Construction of All-Carbon Quaternary Stereogenic Centers」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

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