Total Synthesis of Limonin

Shuji Yamashita; Akito Naruko; Yuki Nakazawa; Le Zhao; Yujiro Hayashi; Masahiro Hirama

doi:10.1002/anie.201503794

Total Synthesis of Limonin

Shuji Yamashita, Akito Naruko, Yuki Nakazawa, Le Zhao, Yujiro Hayashi, Masahiro Hirama

SCI - Chemistry

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

44 Citations (Scopus)

Abstract

Limonoids are highly oxygenated C13α-triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)-limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet-oxygen cycloaddition and a Baeyer-Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Suárez reaction to construct the unique AA′ ring system.

Original language	English
Pages (from-to)	8538-8541
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	29
DOIs	https://doi.org/10.1002/anie.201503794
Publication status	Published - 2015 Jul 13

Keywords

cycloaddition
limonoids
oxidation
radical reactions
total synthesis

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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abstract = "Limonoids are highly oxygenated C13α-triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)-limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet-oxygen cycloaddition and a Baeyer-Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Su{\'a}rez reaction to construct the unique AA′ ring system.",

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T1 - Total Synthesis of Limonin

AU - Yamashita, Shuji

AU - Naruko, Akito

AU - Nakazawa, Yuki

AU - Zhao, Le

AU - Hayashi, Yujiro

AU - Hirama, Masahiro

PY - 2015/7/13

Y1 - 2015/7/13

N2 - Limonoids are highly oxygenated C13α-triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)-limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet-oxygen cycloaddition and a Baeyer-Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Suárez reaction to construct the unique AA′ ring system.

AB - Limonoids are highly oxygenated C13α-triterpenes and common secondary metabolites. Several hundred congeners have been isolated to date. The first total synthesis of (±)-limonin, the flagship congener of the limonoids, is now reported and features 1) a tandem radical cyclization generating the BCD ring system with the C13α configuration that is essential to the limonoids and a Robinson annulation to construct the limonoid androstane framework, 2) a singlet-oxygen cycloaddition and a Baeyer-Villiger oxidation to synthesize the highly oxidized D ring, and 3) a Suárez reaction to construct the unique AA′ ring system.

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KW - limonoids

KW - oxidation

KW - radical reactions

KW - total synthesis

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