Photochemistry of aryloxiranes: free radical 1,2-alkyl migrations in a constrained system

Abstract

The photolysis of alkylidenefluorene oxides resulted in free radical 1,2-alkyl migrations.

Cascade alkyl migration in 2-alkynylanilines for the synthesis of benzenoid ring multi-functionalized indoles

“…Alkyl migration remains a transformation of central importance in synthetic chemistry because it provides numerous possibilities for the construction of molecular complexity. 1 Since the observations of the 1,2-alkyl migration in Friedel–Crafts alkylation reactions 2 and the 1,4-methyl migration during the Fischer indole synthesis, 3 alkyl migration in the arene frameworks has drawn particular attention because it affords a promising option for the synthesis of multi-functionalized aromatic molecules that are difficult to prepare by electrophilic substitution reactions. 4 For example, recently, Nakamura and Terada demonstrated a cationic N-heterocyclic carbene and copper-catalyzed domino 1,3-alkoxy rearrangement and 1,2-alkyl migration to convert N -methoxyanilines to multisubstituted ortho -anisidines (Scheme 1a).…”