Hypervalent λ3-bromane strategy for Baeyer-Villiger oxidation

Selective transformation of primary aliphatic and aromatic aldehydes to formates, which is missing in the classical Baeyer-Villiger oxidation

Masahito Ochiai, Akira Yoshimura, Kazunori Miyamoto, Satoko Hayashi, Waro Nakanishi

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.

Original languageEnglish
Pages (from-to)9236-9239
Number of pages4
JournalJournal of the American Chemical Society
Volume132
Issue number27
DOIs
Publication statusPublished - 14 Jul 2010
Externally publishedYes

Fingerprint

Formic Acid Esters
Formates
Carboxylic Acids
Aldehydes
Esters
Ligands
Oxidation
Water
Carbonyl compounds
Hydrates
Carboxylic acids
Hydration
benzaldehyde
caprylic aldehyde

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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abstract = "A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent aryl-λ3-bromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of an aryl-λ3-bromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95{\%}) under our conditions, while the attempted classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.",
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AU - Ochiai, Masahito

AU - Yoshimura, Akira

AU - Miyamoto, Kazunori

AU - Hayashi, Satoko

AU - Nakanishi, Waro

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