Total Synthesis of Aculenes B and D

Hinata Yokokawa, Seiya Ishizawa, Katsuya Saito, Yasuhiro Meguro, Shigefumi Kuwahara, Masaru Enomoto

Research output: Contribution to journalArticlepeer-review

1 Citation (Scopus)

Abstract

The first total synthesis of aculene D, a structurally rare nordaucane-type natural product exhibiting quorum sensing inhibitory activity, has been accomplished from a known five-membered hydroxy carboxylic acid. Nucleophilic addition of methallylzinc bromide to a β-keto aldehyde intermediate under Barbier conditions to install the secondary hydroxy group on the seven-membered ring of aculene D gave the corresponding alcohol with an undesired configuration predominantly. On the other hand, the protection of its keto group as the ethylene acetal induced a reversal of diastereoselectivity, affording a desired diastereomer in a selective manner. The construction of the seven-membered ring was realized by ring-closing metathesis using a triethylsilyl-protected monocyclic diene ester precursor. An additional five-step manipulation on the cyclization product including the installation of an ethyl group on the five-membered ring completed the synthesis of aculene D, whose esterification with an N-protected l-proline followed by deprotection also achieved the first total synthesis of aculene B.

Original languageEnglish
Article numbere202201482
JournalEuropean Journal of Organic Chemistry
Volume26
Issue number6
DOIs
Publication statusPublished - 2023 Feb 6

Keywords

  • Barbier reaction
  • aculene
  • nordaucane
  • ring-closing metathesis
  • synthetic methods

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