New route to α-adducts of homoallylic alcohols by an acid-catalyzed stereospecific allyl-transfer reaction from γ-adducts

Junzo Nokami, Laurence Anthony, Shin Ichi Sumida

Research output: Contribution to journalArticle

54 Citations (Scopus)

Abstract

Allylation of aldehydes by an allyl-transfer reaction from the γ-adducts of homoallylic alcohols has been successfully carried out to give the corresponding α-adducts regiospecifically. The reaction proceeds via a hemiacetal (11), derived from an aldehyde and the homoallylic alcohol, followed by a six-membered cyclic transition state (2-oxonia[3.3]-sigmatropic rearrangement) in the presence of a Lewis acid. Moreover, the γ-adducts are restructured into the corresponding α-adducts via a similar transition state by an acid catalyst, in which chirality in both anti- and syn-γ-adducts is stereospecifically transferred to the corresponding E- and Z-α-adducts, respectively, with > 98 % ee.

Original languageEnglish
Pages (from-to)2909-2913
Number of pages5
JournalChemistry - A European Journal
Volume6
Issue number16
Publication statusPublished - 2000 Aug 18
Externally publishedYes

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Aldehydes
Alcohols
Allylation
Acrolein
Lewis Acids
Acids
Chirality
Catalysts
Oxonia Active

Keywords

  • Alcohols
  • Allyl complexes
  • Allyl-transfer
  • Allylations
  • Homoallylic alcohols
  • Reaction mechanisms

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

New route to α-adducts of homoallylic alcohols by an acid-catalyzed stereospecific allyl-transfer reaction from γ-adducts. / Nokami, Junzo; Anthony, Laurence; Sumida, Shin Ichi.

In: Chemistry - A European Journal, Vol. 6, No. 16, 18.08.2000, p. 2909-2913.

Research output: Contribution to journalArticle

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N2 - Allylation of aldehydes by an allyl-transfer reaction from the γ-adducts of homoallylic alcohols has been successfully carried out to give the corresponding α-adducts regiospecifically. The reaction proceeds via a hemiacetal (11), derived from an aldehyde and the homoallylic alcohol, followed by a six-membered cyclic transition state (2-oxonia[3.3]-sigmatropic rearrangement) in the presence of a Lewis acid. Moreover, the γ-adducts are restructured into the corresponding α-adducts via a similar transition state by an acid catalyst, in which chirality in both anti- and syn-γ-adducts is stereospecifically transferred to the corresponding E- and Z-α-adducts, respectively, with > 98 % ee.

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