Total syntheses of (+)- and (-)-pestalotiopsin A

Kenichi Takao, Nobuhiko Hayakawa, Reo Yamada, Taro Yamaguchi, Hiroshi Saegusa, Masatoshi Uchida, Suguru Samejima, Kin Ichi Tadano

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

(Chemical Equation Presented) An enantioselective total synthesis of both enantiomers of caryophyllene-type sesquiterpenoid pestalotiopsin A has been achieved, thereby establishing the absolute stereochemistry of natural (+)-pestalotiopsin A. Highlights of the synthesis include a [2 + 2] cycloaddition of N-propioloyl Oppolzer's camphorsultam and ketene dialkyl acetal and subsequent highly stereoselective 1,4-hydride addition/protonation, an aldol reaction of functionalized bicyclic lactone with aldehyde, an efficient intramolecular Nozaki-Hiyama-Kishi (NHK) reaction for the construction of the highly strained (E)-cyclononene ring, and a palladium-catalyzed reduction of allylic mesylate with retention of the E configuration.

Original languageEnglish
Pages (from-to)6452-6461
Number of pages10
JournalJournal of Organic Chemistry
Volume74
Issue number17
DOIs
Publication statusPublished - 2009 Sep 4

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Acetals
Mesylates
Stereochemistry
Cycloaddition
Enantiomers
Protonation
Palladium
Lactones
Aldehydes
Hydrides
pestalotiopsin A
caryophyllene
camphorsultam
3-hydroxybutanal
ketene

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Takao, K., Hayakawa, N., Yamada, R., Yamaguchi, T., Saegusa, H., Uchida, M., ... Tadano, K. I. (2009). Total syntheses of (+)- and (-)-pestalotiopsin A. Journal of Organic Chemistry, 74(17), 6452-6461. https://doi.org/10.1021/jo9012546

Total syntheses of (+)- and (-)-pestalotiopsin A. / Takao, Kenichi; Hayakawa, Nobuhiko; Yamada, Reo; Yamaguchi, Taro; Saegusa, Hiroshi; Uchida, Masatoshi; Samejima, Suguru; Tadano, Kin Ichi.

In: Journal of Organic Chemistry, Vol. 74, No. 17, 04.09.2009, p. 6452-6461.

Research output: Contribution to journalArticle

Takao, K, Hayakawa, N, Yamada, R, Yamaguchi, T, Saegusa, H, Uchida, M, Samejima, S & Tadano, KI 2009, 'Total syntheses of (+)- and (-)-pestalotiopsin A', Journal of Organic Chemistry, vol. 74, no. 17, pp. 6452-6461. https://doi.org/10.1021/jo9012546
Takao K, Hayakawa N, Yamada R, Yamaguchi T, Saegusa H, Uchida M et al. Total syntheses of (+)- and (-)-pestalotiopsin A. Journal of Organic Chemistry. 2009 Sep 4;74(17):6452-6461. https://doi.org/10.1021/jo9012546
Takao, Kenichi ; Hayakawa, Nobuhiko ; Yamada, Reo ; Yamaguchi, Taro ; Saegusa, Hiroshi ; Uchida, Masatoshi ; Samejima, Suguru ; Tadano, Kin Ichi. / Total syntheses of (+)- and (-)-pestalotiopsin A. In: Journal of Organic Chemistry. 2009 ; Vol. 74, No. 17. pp. 6452-6461.
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