An expeditious and efficient bromomethylation of thiols: enabling bromomethyl sulfides as useful building blocks

A facile and highly efficient method for the bromomethylation of thiols, using paraformaldehyde and HBr/AcOH, has been developed, which advantageously minimizes the generation of highly toxic byproducts. The preparation of 22 structurally diverse alpha-bromomethyl sulfides illustrates the chemo-tolerant applicability while bromo-lithium exchange and functionalization sequences, free radical reductions, and additions of the title compounds demonstrate their synthetic utility.