The synthesis of α-fluoroalkylphosphonates

Abstract

A general synthesis of functionalized a-fluoroalkylphosphonates is provided by reaction of the dialkyl fluoromethylphosphonate carbanion with aldehydes, ketones, alkyl halides, silyl halides, and acyl halides. Further transformation of the primary products expands the scope of the synthetic method.

Towards the mechanism of trimeric purine nucleoside phosphorylases: Stopped-flow studies of binding of multisubstrate analogue inhibitor — 2-amino-9-[2-(phosphonomethoxy)ethyl]-6-sulfanylpurine

“…This findings underline differences noted in binding of phosphonate analogues and phosphate analogues (including fluorophoshonates better mimicking phosphate esters than the corresponding phosphonates [29]) by X-ray crystallographic studies. In the phosphate binding site the side chain of Arg84 forms a putative hydrogen bond with phosphate, see e.g.…”

Crystal Structure of Calf Spleen Purine Nucleoside Phosphorylase with Two Full Trimers in the Asymmetric Unit: Important Implications for the Mechanism of Catalysis

“…3,26 The CHF and CF 2 group of the latter better mimics ester oxygen relative to the weakly electronegative CH 2 group. 27 The acyclic chain linking the purine base with the phosphonate group occupies the ribose-binding site. Oxygen O 13 of the chain is bridged via a water molecule to Tyr88, which is known to be a part of the ribose-binding site.…”

Copper‐Mediated Synthesis of Aryldifluoromethylphosphonates: A Sandmeyer Approach

“…Among fluorinated motifs, the difluoromethylphosphonate residue is of great interest as an in vivo stable phosphate mimic, as proposed by Blackburn 30 years ago. [5] In salts furnished the highly valuable aryl difluoromethylphosphonates in moderate to good yields. This represents the first general method to introduce difluoromethylphosphonates under mild conditions.…”