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 α-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)₂NF. 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.

Key words

fluoroamine - sulfonimide - dioxaphospholene - carbene surrogate - phosphoramidite - N–F insertion - geminal difunctionalization - 1,2-diketone

Publication History

Received: 04 November 2022

Accepted after revision: 31 December 2022

Accepted Manuscript online:
31 December 2022

Article published online:
02 February 2023

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