Total Synthesis of (−)-Enigmazole A

Keisuke Sakurai; Makoto Sasaki; Haruhiko Fuwa

doi:10.1002/anie.201801561

Total Synthesis of (−)-Enigmazole A

Keisuke Sakurai, Makoto Sasaki, Haruhiko Fuwa

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Total synthesis of (−)-enigmazole A, a marine macrolide natural product with cytotoxic activity, has been accomplished. The tetrahydropyran moiety was constructed by means of a domino olefin cross-metathesis/intramolecular oxa-Michael addition of a δ-hydroxy olefin. After coupling of advanced intermediates, the macrocycle was formed through gold-catalyzed rearrangement of a propargylic benzoate, followed by ring-closing metathesis of the resultant α,β-unsaturated ketone.

Original language	English
Pages (from-to)	5143-5146
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	18
DOIs	https://doi.org/10.1002/anie.201801561
Publication status	Published - 2018 Apr 23
Externally published	Yes

Keywords

macrocycles
metathesis
natural products
rearrangement
total synthesis

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201801561

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title = "Total Synthesis of (−)-Enigmazole A",

abstract = "Total synthesis of (−)-enigmazole A, a marine macrolide natural product with cytotoxic activity, has been accomplished. The tetrahydropyran moiety was constructed by means of a domino olefin cross-metathesis/intramolecular oxa-Michael addition of a δ-hydroxy olefin. After coupling of advanced intermediates, the macrocycle was formed through gold-catalyzed rearrangement of a propargylic benzoate, followed by ring-closing metathesis of the resultant α,β-unsaturated ketone.",

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author = "Keisuke Sakurai and Makoto Sasaki and Haruhiko Fuwa",

note = "Funding Information: We thank Dr. Kentaro Takada (The University of Tokyo) for technical advice and Keita Sakamoto (Tohoku University) for HPLC purification of synthetic (−)-enigmazole A. This work was financially supported by the Asahi Glass Foundation.",

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T1 - Total Synthesis of (−)-Enigmazole A

AU - Sakurai, Keisuke

AU - Sasaki, Makoto

AU - Fuwa, Haruhiko

N1 - Funding Information: We thank Dr. Kentaro Takada (The University of Tokyo) for technical advice and Keita Sakamoto (Tohoku University) for HPLC purification of synthetic (−)-enigmazole A. This work was financially supported by the Asahi Glass Foundation.

PY - 2018/4/23

Y1 - 2018/4/23

N2 - Total synthesis of (−)-enigmazole A, a marine macrolide natural product with cytotoxic activity, has been accomplished. The tetrahydropyran moiety was constructed by means of a domino olefin cross-metathesis/intramolecular oxa-Michael addition of a δ-hydroxy olefin. After coupling of advanced intermediates, the macrocycle was formed through gold-catalyzed rearrangement of a propargylic benzoate, followed by ring-closing metathesis of the resultant α,β-unsaturated ketone.

AB - Total synthesis of (−)-enigmazole A, a marine macrolide natural product with cytotoxic activity, has been accomplished. The tetrahydropyran moiety was constructed by means of a domino olefin cross-metathesis/intramolecular oxa-Michael addition of a δ-hydroxy olefin. After coupling of advanced intermediates, the macrocycle was formed through gold-catalyzed rearrangement of a propargylic benzoate, followed by ring-closing metathesis of the resultant α,β-unsaturated ketone.

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KW - natural products

KW - rearrangement

KW - total synthesis

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