Electrophilic Fluorinations withN-Fluorobenzenesulfonimide: Convenient Access to α-Fluoro- and α,α-Difluorophosphonates

Synthesis and Evaluation of α-Halogenated Analogues of 3-(Acetylhydroxyamino)propylphosphonic Acid (FR900098) as Antimalarials

“…17 This straightforward onepot strategy allowed for the synthesis of both envisaged precursors 10a and 10b with just a minor modification of the desilylation conditions (vide infra) and has several advantages such as high yield, high speed, ready availability of electrophilic halogenating reagents and easy elimination of byproducts.…”

N-Fluorobenzenesulfonimide [(PhSO2)2NF] - A Neutral N-F-Containing Electrophilic Fluorinating Agent

“…It is a neutral N-F-containing electrophilic fluorinating agent that permits the incorporation of fluorine into neutral and carbanionic nucleophiles ranging from very reactive organometallic species to slightly activated aromatic compounds. 1 N-Fluorobenzenesulfonimide can be employed in the preparation of aryl (difluoromethylenephosphonates), 2 20-deoxy-20-fluorocamptothecin, 3 N-fluoro sulfonamides, 4 2-amino-5-fluorothiazole hydrochloride 5 and benzylic a,a-difluoronitriles, -tetrazoles, and -sulfonates. 6 When NFSI was associated with chiral palladium complexes an efficient method to catalytic enantioselective fluorination of b-keto esters, 7 and a-cyano acetates 8 was presented.…”

The Synthesis of Dialkyl α-Halogenated Methylphosphonates

“…32 Oxidation reaction (halogenation) : This involves oxidation of 1-lithiomethylphosphonates in THF solution by electrophilic fluorinating agents. Diethyl fluoromethylphosphonate (or mixed ethyl/methyl esters 33 ) was obtained from N-fluorobenzenesulfonimide 34,35 in 11 % yield and from perchloryl fluoride 36 (mixture of monofluoro and difluoro compounds obtained 33 ) in 46 % yield. These fluorinating reactants are explosive compounds and are not easily available.…”