One-carbon homologation of unsymmetrical ketones through magnesium β-oxido carbenoid rearrangement and trapping the enolate intermediates with electrophiles

Shu Tanaka, Takehiro Anai, Makoto Tadokoro, Tsuyoshi Satoh

研究成果: Article査読

12 被引用数 (Scopus)

抄録

A procedure for one-carbon homologation of unsymmetrical ketones, including one-carbon ring-expansion of 2-substituted cyclohexanones, through magnesium β-oxido carbenoid rearrangement as the key reaction is described. Addition of the α-sulfinyl carbanion of 1-chloroethyl p-tolyl sulfoxide to an unsymmetrical ketone gave two diastereomers as adducts in good yields. The adducts were treated with a base to give alkoxides, which were treated with a Grignard reagent to give magnesium β-oxido carbenoids. The β-oxido carbenoid rearrangement then took place to afford one-carbon homologated ketones having a methyl group at the α-position. Remarkable specificity or selectivity was observed in the rearrangement. The magnesium enolate intermediates of this reaction were found to be able to get trapped with several electrophiles to give one-carbon homologated α,α-disubstituted ketones. Origin of the specificity and selectivity is also discussed.

本文言語English
ページ(範囲)7199-7210
ページ数12
ジャーナルTetrahedron
64
30-31
DOI
出版ステータスPublished - 2008 7 21
外部発表はい

ASJC Scopus subject areas

  • 生化学
  • 創薬
  • 有機化学

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