75685-52-8Relevant articles and documents
Total syntheses of (±)-gephyrotoxin and (±)-perhydrogephyrotoxin
Shirokane, Kenji,Tanaka, Yuya,Yoritate, Makoto,Takayama, Nobuaki,Sato, Takaaki,Chida, Noritaka
, p. 522 - 537 (2015/06/17)
This article describes the full details of our total syntheses of gephyrotoxin and perhydrogephyrotoxin. Our central strategy toward the total synthesis is based on the use of an N-methoxy group as a reactivity control element. The N-methoxyamide group enabled unique transformations, involving i) the direct coupling reaction of the N-methoxyamide with an aldehyde, and ii) the amide-selective reductive allylation. These reactions were never accomplished without the assistance of the N-methoxy group. The amide-selective reductive allylation of the N-methoxyamide was especially practical, and excluded a number of extra steps including protecting group manipulations and redox reactions in the total syntheses.
Importance of allylic interactions and stereoelectronic effects in dictating the steric course of the reaction of iminium ions with nucleophiles. An efficient total synthesis of (±) gephyrotoxin
Overman,Lesuisse,Hashimoto
, p. 5373 - 5379 (2007/10/02)
A stereocontrolled total synthesis of (±)-gephyrotoxin in 15 steps and 6.5% overall yield from benzyl trans-1,3-butadiene-1-carbamate is described. A key step is reduction of octahydroquinoline 27 from the more hindered concave α face to provide decahydroquinoline 28. This unusual transformation results from the interplay of allylic (A1,2) steric interactions and stereoelectronic effects.
Total Synthesis of (+/-)-Gephyrotoxin
Fujimoto, Roger,Kishi, Yoshito,Blount, John F.
, p. 7154 - 7156 (2007/10/02)
-
