Total Synthesis of (−)-Histrionicotoxin through a Stereoselective Radical Translocation-Cyclization Reaction

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• 作者：Manabu Sato ; Dr. Hiroki Azuma ; Akihiro Daigaku ; Dr. Sota Sato ; Prof. Dr. Kiyosei Takasu ; Dr. Kentaro Okano and Prof. Dr. Hidetoshi Tokuyama
• 刊名：Angewandte Chemie International Edition
• 出版年：2017
• 出版时间：January 19, 2017
• 年：2017
• 卷：56
• 期：4
• 页码：1087-1091
• 全文大小：849K
• ISSN：1521-3773

文摘

Stereoselective total syntheses of (−)-histrionicotoxin and (−)-histrionicotoxin 235A are described. The 1-azaspiro[5.5]undecane skeleton was constructed diastereoselectively by a radical translocation–cyclization reaction involving a chiral cyclic acetal; the use of tris(trimethylsilyl)silane was crucial for the high diastereoselectivity. The cyclization product was converted into (−)-histrionicotoxin 235A through a one-pot partial-reduction–allylation reaction of a derivative containing an unprotected lactam. Finally, two terminal alkenes were transformed into enynes with the 1,3-amino alcohol protected as an oxathiazolidine oxide to complete the total synthesis of (−)-histrionicotoxin.