Novel transformations utilizing [1, 2]-phospha-brook rearrangement under bronsted base catalysis

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Abstract

The [1, 2]-phospha-Brook rearrangement involves the migration of the phosphorus moiety of the alkoxide of an α-hydroxyphosphonate from carbon to oxygen to generate an α-oxygenated carbanion. We have been focusing on the [1, 2]-phospha-Brook rearrangement as a useful tool for the development of novel synthetic reactions under Brønsted base catalysis. For instance, we utilized the rearrangement for the catalytic generation of carbanions of less acidic compounds through the formal umpolung process from the corresponding carbonyl compounds. We have developed catalytic addition reactions of carbanions, such as enolates derived from less acidic amides and esters, a-oxygenated allyl anions that can serve as homoenolate equivalents and benzyl anions, as nucleophiles. We have also developed new efficient syntheses of functionalized allenes involving the generation of propargyl anions followed by regioselective protonation. The allenes were further applied to cycloisomerization to afford heterocyclic compounds, such as 2-aminofuran derivatives and indolizine derivatives. On the other hand, we utilized the [1, 2]-phospha-Brook rearrangement for facilitating catalyst turnover in Brønsted base-mediated processes. Specifically, the [2, 3]-Wittig rearrangement and the a-oxygenation of carbonyl compounds, which generally require a stoichiometric amount of Brønsted bases, have been successfully combined with the [1, 2]-phospha-Brook rearrangement to proceed in a catalytic fashion.

Original languageEnglish
Pages (from-to)151-163
Number of pages13
JournalYuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume76
Issue number2
DOIs
Publication statusPublished - 2018

Keywords

  • Brønsted base catalysis
  • Carbon-carbon bond formation
  • Catalyst turnover
  • Heterocycles
  • Rearrangement
  • Tandem reaction
  • Umpolung

ASJC Scopus subject areas

  • Organic Chemistry

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