Fluoroalkanosulfonyl fluorides enabled symbiotic reaction and their application in organic synthesis—the concept and practice of symbiotic reaction

<p indent="0mm">Fluoroalkanosulfonyl fluoride (R_fSO₂F) is an industrial raw material for the production of fluoroalkyl sulfate and an important class of non-natural (or artificial) resource compounds. In the study of the reactivities of fluoroalkanosulfonyl fluorides and their applications in organic synthesis, we proposed the concept of “symbiotic reaction” based on the natural property of chemical reaction symbiosis. It is well known that in the hydrolysis reaction of fluoroalkanosulfonyl fluoride, fluoroalkanosulfonyl fluoride is only used as the raw material for the production of fluoroalkyl sulfates. However, in their “symbiotic reaction”, they not only serve as raw materials for the synthesis of fluoroalkyl sulfates, but also as key reagents for the related reactions. Symbiotic reaction not only possesses a higher value for compound resources compared to atomic economy, but also reduces the formation of wastes in the reaction. This review summarizes the research results from our two research groups in the past thirty years on the fluoroalkyl sulfonyl fluoride-participated symbiotic reactions and their application in organic synthesis. The symbiotic reactions studied involve: The symbiotic reaction between fluoroalkanosulfonyl fluoride hydrolysis and enol hydroxyl activation substitution, the symbiotic reaction with olefin epoxidation, the symbiotic reaction related to alcohol hydroxyl activation, and the symbiotic reaction with oxime hydroxyl activation, etc. Some efficient methods for organic synthesis have been developed in the course of studies and have been applied in the research and development of steroid drug epristeride, the synthesis of estrogen antagonists with novel structures, and the efficient synthesis of natural products spiniferin-1 and clausenamide compounds.