Total Synthesis of (±)-Gephyrotoxin by Amide-Selective Reductive Nucleophilic Addition

A chemoselective approach for the total synthesis of (±)‐gephyrotoxin has been developed. The key to success was the utilization of N‐methoxyamides, which enabled the direct coupling of the amide with an aldehyde and selective reductive nucleophilic addition to the amide in the presence of a variety...

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Published inAngewandte Chemie Vol. 126; no. 2; pp. 522 - 526
Main Authors Shirokane, Kenji, Wada, Takamasa, Yoritate, Makoto, Minamikawa, Ryo, Takayama, Nobuaki, Sato, Takaaki, Chida, Noritaka
Format Journal Article
LanguageEnglish
German
Published Weinheim WILEY-VCH Verlag 07.01.2014
WILEY‐VCH Verlag
Wiley Subscription Services, Inc
Subjects
Aldehydes
Amide
Amides
Chemistry
Chemoselektivität
Esters
Functional groups
Gephyrotoxin
Joining
Nucleophile Additionen
Redox reactions
Synthesis
Totalsynthesen
Utilization
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Summary:A chemoselective approach for the total synthesis of (±)‐gephyrotoxin has been developed. The key to success was the utilization of N‐methoxyamides, which enabled the direct coupling of the amide with an aldehyde and selective reductive nucleophilic addition to the amide in the presence of a variety of sensitive and electrophilic functional groups, such as a methyl ester. This chemoselective approach minimized the use of protecting‐group manipulations and redox reactions, which resulted in the most concise and efficient total synthesis of (±)‐gephyrotoxin described to date. Selektivität als Ziel: Eine chemoselektive Methode unter Verwendung von N‐Methoxyamiden wurde zur Totalsynthese von (±)‐Gephyrotoxin entwickelt. Die N‐Methoxy‐Gruppe ermöglichte die direkte Kupplung des Amids mit einem Aldehyd sowie die Amid‐selektive reduktive Allylierung in der Anwesenheit eines elektrophileren Methylesters, was zu der bislang kürzesten und effizientesten Totalsynthese von (±)‐Gephyrotoxin führte.
Bibliography:Naito Foundation
MEXT - No. 24750045
istex:E5666684B24B630677E2AB40018C5228C9583C36
ArticleID:ANGE201308905
ark:/67375/WNG-LD0B8RD5-S
This research was supported by a Grant-in-Aid for Young Scientists (B) from MEXT (24750045), the Naito Foundation, and a JSPS fellowship to K.S. (24⋅1843). We thank Prof. Larry. E. Overman, University of California, Irvine, for providing 1H NMR spectra of related compounds. Prof. Takeshi Noda, Kanagawa Institute of Technology, is acknowledged for mass spectrometric analysis.
This research was supported by a Grant‐in‐Aid for Young Scientists (B) from MEXT (24750045), the Naito Foundation, and a JSPS fellowship to K.S. (24⋅1843). We thank Prof. Larry. E. Overman, University of California, Irvine, for providing
H NMR spectra of related compounds. Prof. Takeshi Noda, Kanagawa Institute of Technology, is acknowledged for mass spectrometric analysis.
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ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201308905