Semipinacol
rearrangement is a special type of Wagner–Meerwein
rearrangement that involves carbocation 1,2-rearrangement to provide
carbonyl compounds with an α-quaternary carbon center. It has
been strategically used for natural product synthesis and construction
of highly congested quaternary carbons. Herein, we report a safe and
green protocol that uses oxone/halide and Fenton bromide to achieve
halogenative semipinacol rearrangement. The key feature of this method
is the green in situ generation of reactive halogenating
species from oxidation of halide with oxone or H2O2, which produces a nontoxic byproduct (potassium sulfate or
water). Easy operation (insensitive to air and moisture) at room temperature
without using special equipment adds additional advantage over previous
methods.