Revisiting [3 + 3] route to 1,3-cyclohexanedione frameworks: Hidden aspect of thermodynamically controlled enolates

Teruhiko Ishikawa, Ryuichiro Kadoya, Masaki Arai, Haruka Takahashi, Yumi Kaisi, Tomohiro Mizuta, Kazusa Yoshikai, Seiki Saito

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3+3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3+3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3+3].

Original languageEnglish
Pages (from-to)8000-8009
Number of pages10
JournalJournal of Organic Chemistry
Volume66
Issue number24
DOIs
Publication statusPublished - Nov 30 2001

ASJC Scopus subject areas

  • Organic Chemistry

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