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

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)5747-5754
Number of pages8
JournalEuropean Journal of Organic Chemistry
Volume2015
Issue number26
DOIs
Publication statusPublished - 2015 Sep 1

Keywords

  • Asymmetric synthesis
  • Chirality
  • Cyclopropanation
  • Organocatalysis
  • Small ring systems

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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