Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions: Allylation or 2-propynylation and aldol reaction

Teruhiko Ishikawa, Toshiaki Aikawa, Eiko Ohata, Takako Iseki, Satoshi Maeda, Takashi Matsuo, Tatsuo Fujino, Seiki Saito

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.

Original languageEnglish
Pages (from-to)435-441
Number of pages7
JournalJournal of Organic Chemistry
Volume72
Issue number2
DOIs
Publication statusPublished - Jan 19 2007

ASJC Scopus subject areas

  • Organic Chemistry

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