Development of the First Spiro Bis(isoxazoline)Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions

Midori A. Arai, Toshio Shinohara, Takayoshi Aral, Hiroaki Sasai

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

The first chiral isoxazoline ligands bearing spiro skeleton are developed. The spiro bis(isoxazoline) ligands (SPRIXs) are readily synthesized from diethyl malonate via double intramolecular nitrile oxide cycloaddition as a key step. The complex of (M, S, S)-R-SPRIX and Pd(OCOCF3)2 promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols to give optically active cyclic ethers for the first time. Furthermore, starting from dialkenyl alcohol, the enantioselective tandem cyclization via oxy-palladation was achieved with up to 95% ee. Asymmetric ligands other than SPRIKs promote neither the Wacker-type reaction nor the tandem reaction.

Original languageEnglish
Pages (from-to)59-69
Number of pages11
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume62
Issue number1
DOIs
Publication statusPublished - 2004 Jan

Keywords

  • Isoxazoline
  • Nitrile oxide cycloaddition
  • Palladium
  • Spiro
  • Tandem reaction
  • Wacker-reaction

ASJC Scopus subject areas

  • Organic Chemistry

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