Stereoselective synthesis of highly enantioenriched 3-methyl-2-cyclohexen-1-ones possessing an asymmetric quaternary carbon as C-4 or C-6

a sugar template approach

Hiroto Kubo, Ikuko Kozawa, Kenichi Takao, Kin ichi Tadano

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The 1,4-addition of the enolate generated from α-methylated acetoacetate incorporated at C-4 of methyl 6-deoxy-2,3-di-O-(tert-butyldimethylsilyl)-α-d-glucopyranoside to methyl vinyl ketone, followed by aldol condensation of the resulting 1,4-addition product under two base-mediated conditions, provided 4-O-functionalized d-glucose derivatives with high diastereoselectivity. These products install a 3-methyl-2-cyclohexen-1-one-4- (or -6-) carboxylic acid as the O-4 ester, in which C-4 or C-6 is an asymmetric quaternary carbon. Removal of the sugar template from those aldol condensation products provided synthetically useful 3,6-dimethyl-2-cyclohexen-1-one-6-carboxylic acid and 3,4-dimethyl-2-cyclohexen-1-one-4-carboxylic acid derivatives both in high enantioenriched forms.

Original languageEnglish
Pages (from-to)1203-1207
Number of pages5
JournalTetrahedron Letters
Volume49
Issue number7
DOIs
Publication statusPublished - 2008 Feb 11

Fingerprint

Carboxylic Acids
Sugars
Carbon
Condensation
Derivatives
Esters
Glucose
3-methyl-2-cyclohexen-1-one
2-cyclohexen-1-one
3-hydroxybutanal

Keywords

  • 1,4-Addition
  • Aldol condensation
  • Intramolecular cyclization
  • Sugar template

ASJC Scopus subject areas

  • Biochemistry
  • Organic Chemistry
  • Drug Discovery

Cite this

Stereoselective synthesis of highly enantioenriched 3-methyl-2-cyclohexen-1-ones possessing an asymmetric quaternary carbon as C-4 or C-6 : a sugar template approach. / Kubo, Hiroto; Kozawa, Ikuko; Takao, Kenichi; Tadano, Kin ichi.

In: Tetrahedron Letters, Vol. 49, No. 7, 11.02.2008, p. 1203-1207.

Research output: Contribution to journalArticle

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