On-Water Selectivity Switch in Microdroplets in the 1,2,3-Triazole Synthesis from Bromoethenesulfonyl Fluoride
Dmitry B. Eremin, Valery V. Fokin
Abstract
Water profoundly affects many organic reactions by accelerating them or changing their selectivity. Performing reactions “on-water” offers an intriguing opportunity to influence chemical reactivity. A nebulizer plume is an efficient way of generating microdroplets─the uniquely complex reaction environment which opens alternative possibilities that are not readily accessible in bulk emulsions. We describe the on-water switch of chemoselectivity in the formation of triazoles controlled by the on-water environment in dual spray. These conditions facilitate elimination of H–SO2F from the triazoline intermediate, whereas the reaction in organic solvents results in the exclusive HBr elimination. The influence of two-phase conditions was investigated to obtain the best reaction efficiency, and the crucial importance of the water/organic interface interactions was verified by pH variation and D2O use.