A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions

Takeshi Murata, Yumiko Yanagisawa, Makiko Aoyama, Hirona Tsushima, Kiichiro Totani, Shigeru Ohba, Kin Ichi Tadano

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Abstract

The reaction of (Z)-3-deoxy-3-C-[(hydroxymethyl)methylene]-1,2:5,6-di- O-isopropylidene-α-D-ribo-hexofuranose, prepared from D-glucose, with 1,1- dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)- 2,3-(isopropylidene)dioxy-5-[(1R)-1,2-(isopropylidene)dioxyethyl]-4-[(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L- Selectride® reduction of the major product gave the corresponding (S)- cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-[(1S)-2- oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3- methylated and 3-vinylated cyclohexanone derivatives, both in high yields.

Original languageEnglish
Pages (from-to)4203-4217
Number of pages15
JournalTetrahedron Asymmetry
Volume9
Issue number23
DOIs
Publication statusPublished - 1998 Dec 11

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ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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