Tandem Deoxygenative Geminal Fluorosulfonimidation of 1,2-Diketones via Formal N-F Insertion Enabled by Dealkylation-Resistant Phosphoramidite

Abstract

Our group has recently developed an alpha-fluoroamine synthesis using dioxaphospholenes derived from various 1,2-diketones and the dealkylation-resistant phosphoramidite as carbene surrogates, enabling the formal insertion into the N-F bond of (PhSO2)(2)NF. This full account presents the scope and limitations in terms of the reactivity and the site selectivity; these were rationalized through computational analysis. In addition, the efforts to broaden the synthetic utility of the current process by incorporating other nitrogen nucleophiles and halogen electrophiles are described.