80077-72-1

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 1478-53-1 Diethyl difluoromethylphosphonate 
• 65094-22-6 diethyl (bromodifluoromethyl)phosphonate 
• 94993-99-4 diethyl difluoromethylphosphonate lithium salt 
• 2857-97-8 trimethylsilyl bromide 
• 80084-30-6 (diethylphosphono)difluoromethyl cadmium bromide 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 762-04-9 phosphonic acid diethyl ester 

Downstream Products

• 83567-98-0 [1,1-Difluoro-2-hydroxy-2-(4-nitro-phenyl)-propyl]-phosphonic acid diethyl ester 
• 83568-00-7 Phosphoric acid 2,2-difluoro-1-methyl-1-(4-nitro-phenyl)-ethyl ester diethyl ester 
• 395095-62-2 C₂₀H₃₆F₂NO₁₀P 
• 83567-78-6 [1,1-difluoro-2-hydroxy-2-(4-nitro-phenyl)-ethyl]-phosphonic acid diethyl ester 
• 185965-95-1 (difluoro-p-tolylmethyl)phosphonic acid diethyl ester 
• 1605274-12-1 diethyl ((3,5-dimethoxyphenyl)difluoromethyl)phosphonate 
• 185965-97-3 diethyl [(4-chlorophenyl)difluoromethyl]phosphonate 
• 221876-80-8 diethyl ((3-bromophenyl)difluoromethyl)phosphonate 
• 1605274-14-3 diethyl (difluoro(4-(trifluoromethyl)phenyl)methyl)phosphonate 
• 177284-51-4 4-<(diethylphosphono)difluoromethyl>nitrobenzene 

Relevant academic research and scientific papers

Electrochemical synthesis of fluoro-organosilanes

The electrochemical reduction of some fluorohalocarbons in the presence of trimethylchlorosilane is followed by formation of the corresponding fluoroalkyltrimethylsilanes. CF3SiMe3, CFCl2SiMe3, CF3CCl2SiMe3 and (EtO)2P(O)CF2SiMe3 were obtained with current efficiency 20-50%. Voltammetric data are presented.

Enantioselective Lewis base catalyzed phosphonyldifluoromethylation of allylic fluorides using a: C -silyl latent pronucleophile

The first enantioselective phosphonyldifluoromethylation is enabled by the use of diethyl (difluoro(trimethylsilyl)-methyl)phosphonate reagent as a latent pronucleophile in the Lewis base catalyzed substitution of allylic fluorides. The reaction proceeds

Siladifluoromethylation and Deoxo-trifluoromethylation of PV-H Compounds with TMSCF3: Route to PV-CF2- Transfer Reagents and P-CF3 Compounds

A method for siladifluoromethylation of dialkyl phosphonates and secondary phosphine oxides with TMSCF3 to produce nucleophilic PV-CF2- transfer reagents is disclosed, with multigram scale reactions included. Condition-dependent divergent reactivity under the established conditions is demonstrated by the formation of trifluoromethylphosphines. Both one-pot transformations are operationally simple and employ inexpensive materials. Mechanistic investigations suggest the divergent reactivity originates from a common intermediate, with Li+ concentration directing the chemoselectivity.

Highly Selective Addition of a Broad Spectrum of Trimethylsilane Pro-nucleophiles to N-tert-Butanesulfinyl Imines

Addition of organotrimethylsilane reagents to chiral N-tert-butanesulfinyl imines can be achieved in good yields and with excellent diastereoselectivities by employing TMSO-/Bu4N+ as a Lewis base activator in THF. A variety of aliphatic, aromatic, heteroaromatic and organometallic chiral imines were utilised as electrophiles for the synthesis of enantioenriched N-tert-butanesulfinyl amides. Remarkably, the same sets of reaction conditions could be used with a highly diverse range of bench-stable organotrimethylsilane reagents, which highlights the generality and robustness of this methodology. Addition of organotrimethylsilane reagents to chiral N-tert-butanesulfinyl imines can be achieved in good yields and with excellent diastereoselectivities by employing TMSO-/Bu4N+ as a Lewis base activator in THF. A variety of aliphatic, aromatic, heteroaromatic and organometallic chiral imines were utilised as electrophiles for the synthesis of enantioenriched N-tert-butanesulfinyl amides, highlighting the generality and robustness of this methodology.

Reactions of sulfur- and phosphorus-substituted fluoroalkylating silicon reagents with imines and enamines under acidic conditions

Nucleophilic fluoroalkylation reactions of imines and enamines with α-phenylthio, α-phenylsulfonyl, and α-diethylphosphoryl substituted fluorinated silanes have been investigated. The reactions are promoted by hydrofluoric acid generated in situ from pota

Nucleophilic difluoromethylenation of aldehydes and ketones using diethyl difluoro(trimethylsilyl)methylphosphonate

A new nucleophilic difluoromethylenation of aldehydes and ketones using diethyl difluoro(trimethylsilyl)methylphosphonate (1) has been achieved. The reactive carbanion species were generated under mild reaction conditions with a catalytic amount of initiator. This methodology was compatible with non-enolizable and in some cases with enolizable aldehydes and ketones and provided a straightforward access to phosphates of syn and anti 2,2-difluoro-1,3-diols.

DFTMP, an NMR reagent for assessing the near-neutral pH of biological samples

A new NMR chemical shift standard and pH indicator, difluorotrimethylsilanylphosphonic acid (DFTMP), is described, and the utility of this reagent is demonstrated for in situ determination of pH in complex biofluids. The pH dependence of this reagent allows accurate in situ determination of aqueous solution pH to within an RMSE of 0.02 pH units over a pH range of 5 to 8. Advantages of this reagent over previously described pH-sensitive components include (1) lack of metal binding affinity, (2) minimal disturbance of endogenous spectral regions, and (3) the potential to function as a multinuclear pH indicator and chemical shift reference point for 19F, 1H, and 31P nuclei. This reagent will be generally useful for NMR experiments on biological systems where the pH needs to be accurately measured at the moment of data acquisition. Copyright

A useful magnesium reagent for the preparation of 1,1-difluoro-2-hydroxyphosphonates from diethyl bromodifluoromethylphosphonate via a metal-halogen exchange reaction

When (EtO)2P(O)CF2Br (1) is treated with isopropylmagnesium chloride in THF at low temperature it gives a magnesium species (2) which undergoes reactions with strong electrophiles (HCl, TMSCl, halogens, aldehydes and ketones). The formation of products depends strongly on the reaction conditions. With 1.5 equivalents of 2 between - 78 and 0°C, a conversion of more than 90% of aldehydes and ketones into 2-hydroxyphosphonates (7 and 8) can be achieved. These compounds (7 and 8) in the presence of base (NaH, LDA) are rearranged into 2,2-difluoroethylphosphates without concomitant formation of 1,1-difluoroolefines.

Synthesis of monofluoro- and difluoro- methylenephosphonate analogues of sn-glycerol-3-phosphate as substrates for glycerol-3-phosphate dehydrogenase and the X-ray structure of the fluoromethylenephosphonate moiety

The synthesis of the cyclohexylammonium salts of (1RS, 3S)-3,4-dihydroxy-1-fluorobutylphosphonic acid 3 and (S)-difluoro-3,4-dihydroxybutylphosphonic acid 4 is reported. These compounds are fluorinated phosphonate analogues of sn-glycerol-3-phosphate wher

Monofluorophosphonates as Phosphate Mimics in Bioorganic Chemistry: a Comparative Study of CH2-, CHF- and CF2-Phosphonate Analogues of sn-Glycerol-3-phosphate as Substrates for sn-Glycerol-3-phosphate Dehydrogenase

The synthesis of the cyclohexylammonium salts of 3-(S),4-dihydroxy-1(R,S)-fluorobutylphosphonic acid 3 and 1,1-difluoro-3-(S),4-dihydroxybutylphosphonic acid 4 is reported; 3 is a better substrate for NADH linked sn-glycerol-3-phosphate dehydrogenase than the difluoromethylenephosphonate 4; a comparative study of the CH2-, CHF- and CF2-phosphonate analogues of sn-glycerol-3-phosphate is reported.