Tandem InCl3-Promoted Hydroperoxide Rearrangements and Nucleophilic Additions: A Straightforward Entry to Benzoxacycles

Theacid-catalyzed rearrangement of organic peroxides is generallyassociated with C-C-bond cleavages (Hock and Criegee rearrangements),with the concomitant formation of an oxocarbenium intermediate. Thisarticle describes the tandem process between a Hock or Criegee oxidativecleavage and a nucleophilic addition onto the oxocarbenium species(in particular a Hosomi-Sakurai-type allylation), under InCl3 catalysis. It was applied to the synthesis of 2-substitutedbenzoxacycles (chromanes and benzoxepanes), including a synthesisof the 2-(aminomethyl)chromane part of sarizotan, and a total synthesisof erythrococcamide B.

Automated summary

This article describes a tandem reaction between a Hock or Criegee oxidative cleavage and a nucleophilic addition onto the oxocarbenium species (specifically a Hosomi-Sakurai-type allylation), catalyzed by InCl3. It was successfully applied to the synthesis of 2-substituted benzoxacycles (chromanes and benzoxepanes), including the synthesis of the 2-(aminomethyl)chromane part of sarizotan and the total synthesis of erythrococcamide B.