Bosnidou Alexandra E, Fayet Agathe, Cheibas Cristina, Gayraud Oscar, Bourcier Sophie, Frison Gilles, Nay Bastien
Laboratoire de Synthèse Organique, Ecole Polytechnique, CNRS, ENSTA, Institut Polytechnique de Paris, F-91128 Palaiseau, France.
CNRS, Laboratoire de Chimie Théorique, Sorbonne Université, F-75005 Paris, France.
J Org Chem. 2023 Jul 7;88(13):9277-9282. doi: 10.1021/acs.joc.3c00845. Epub 2023 Jun 14.
The acid-catalyzed rearrangement of organic peroxides is generally associated with C-C-bond cleavages (Hock and Criegee rearrangements), with the concomitant formation of an oxocarbenium intermediate. This article describes the tandem process between a Hock or Criegee oxidative cleavage and a nucleophilic addition onto the oxocarbenium species (in particular a Hosomi-Sakurai-type allylation), under InCl catalysis. It was applied to the synthesis of 2-substituted benzoxacycles (chromanes and benzoxepanes), including a synthesis of the 2-(aminomethyl)chromane part of sarizotan, and a total synthesis of erythrococcamide B.
有机过氧化物的酸催化重排通常与碳 - 碳键的断裂（霍克和克里格重排）相关联，并伴随形成氧碳鎓中间体。本文描述了在三氯化铟催化下，霍克或克里格氧化裂解与亲核加成到氧碳鎓物种上（特别是霍索尼 - 樱井型烯丙基化）之间的串联过程。它被应用于2 - 取代苯并氧杂环（色满和苯并氧杂环庚烷）的合成，包括沙立佐坦的2 - （氨甲基）色满部分的合成以及红球菌酰胺B的全合成。
