α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compoun...α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.展开更多
The title compound has been synthesized by the addition reaction of N-（4-cyanopyrazole-3-yl）-3,5-difluorophenyl-imine and diisopropyl phosphate. Its structure was confirmed by means of IR, ^1H NMR and elemental anal...The title compound has been synthesized by the addition reaction of N-（4-cyanopyrazole-3-yl）-3,5-difluorophenyl-imine and diisopropyl phosphate. Its structure was confirmed by means of IR, ^1H NMR and elemental analysis. The single-crystal structure of the title compound was determined by X-ray crystallography. The compound crystallizes in monoclinic, space group C2/c with a = 18.9959（14）, b = 9.2212（7）, c = 22.1108（16）A^°, β= 90.1540（10）°, V = 3873.0（5） A^°^3, Dc = 1.366 g/cm^3, Z = 8, μ = 0.185, F（000） = 1664, and the final R = 0.0503 and wR = 0.1539 for 2996 observed reflections （I 〉 2σ（I））. The results demonstrate that the dihedral angle between the pyrazole and benzene rings is 105.5°, and there is a full delocalized pyrazole system with sp^2 hydridization of N（3）. The crystal structure is stabilized by two intermolecular hydrogen bonds of N（1）-H（1）…O（3） and N（3）-H（3A）…N（4）. The preliminary biological test shows that the title compound has a moderate antifungal activity.展开更多
An environmentally benign and highly efficient one-pot preparation of α-aminophosphonates under solvent-free conditions was developed. By employing this method, 5-aminophosphonate substituted pyrimidine nucleosides w...An environmentally benign and highly efficient one-pot preparation of α-aminophosphonates under solvent-free conditions was developed. By employing this method, 5-aminophosphonate substituted pyrimidine nucleosides were synthesized in good to excellent yields starting from 5-forrnyl-2＇-deoxyuridine, aniline and dimethylphosphite.展开更多
An efficient asymmetric Friedel-Crafts reaction has been developed for the synthesis of optically active quaternaryα‐aminophosphonates with up to98%ee.The synthesis involves the reaction of cyclicα‐ketiminophospho...An efficient asymmetric Friedel-Crafts reaction has been developed for the synthesis of optically active quaternaryα‐aminophosphonates with up to98%ee.The synthesis involves the reaction of cyclicα‐ketiminophosphonates with indoles using an H8‐BINOL‐derived chiral phosphoric acid(CPA)catalyst that bears electron‐withdrawing3,5‐ditrifluoromethylphenyl substituents on its3‐and3′‐positions.This Friedel-Crafts reaction of cyclicα‐ketiminophosphonates was also successful with pyrrole.展开更多
The limit ability of traditional antibiotics to treat drug resistant bacteria calls for new therapeutic alter natives.A class of unique sul-fanilamide aminophosphonates as new potential agents against microbes was syn...The limit ability of traditional antibiotics to treat drug resistant bacteria calls for new therapeutic alter natives.A class of unique sul-fanilamide aminophosphonates as new potential agents against microbes was synthesized by one-pot three-component reaction.展开更多
Chiral α-aminophosphonates were synthesized using （R） or （S）-1-phenylethylamine in the presence of BF3·Et2O under microwave irradiation in moderate to good yields. The new compounds were identified by ^1H NM...Chiral α-aminophosphonates were synthesized using （R） or （S）-1-phenylethylamine in the presence of BF3·Et2O under microwave irradiation in moderate to good yields. The new compounds were identified by ^1H NMR, ^19F NMR, IR and elemental analysis. Their antifungal activities were evaluated and some compounds were found to exhibit excellent antifungal activities. To the best of our knowledge, this is the first report on antifungal activity of chiral α-aminophosphonates containing fluorine moiety.展开更多
Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative...Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative α-phosphonylation of amines with P_(4) and alcohols has been developed.With the use of copper(Ⅱ)as the catalyst and air as the safe oxidant,structurally sophisticated α-aminophosphonates have been prepared in high yields.Furthermore,this method is also suitable for selective construction of P-O-P compounds.The reaction is characterized by a complete conversion of P_(4).The activation of P_(4) with transition metals often leads to formation of complexes[M_(x)P_(y)]_(n) associated with the deactivation of transition metals.This breakthrough showcases the potential of transition-metal-catalyzed reactions in elemental phosphorus chemistry.展开更多
A highly selective method for the asymmetric formation of trifluoromethyl-substituted α- and β-aminophos- phonates was described. The reaction proceeded with high yields and good to excellent diastereoselectivity. T...A highly selective method for the asymmetric formation of trifluoromethyl-substituted α- and β-aminophos- phonates was described. The reaction proceeded with high yields and good to excellent diastereoselectivity. The product can be easily converted into corresponding trifluoromethyl-substituted aminophosphoric acids.展开更多
An enzyme-stimulating catalyst( PTL) with copper ions( Cu^(2+)) as the activation center and aminophosphonate as ligand was developed and applied in low-temperature scouring/bleaching of cotton knits. The optimal weig...An enzyme-stimulating catalyst( PTL) with copper ions( Cu^(2+)) as the activation center and aminophosphonate as ligand was developed and applied in low-temperature scouring/bleaching of cotton knits. The optimal weight ratio of Cu^(2+) to aminophosphonate was 1 ∶75. Via orthodox and single-factor experiments,the most efficient formula for low-temperature scouring/bleaching was composed of 0. 4 g/L high-efficiency degreaser DM-1130,1. 5 g/L PTL,2. 0 g/L sodium hydroxide( NaOH),and 7. 0 g/L 30% hydrogen peroxide( H_2O_2). The PTL could not only increase the whiteness of cotton knits,but also remove pectin to enhance capillary effect.展开更多
Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostat...Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).展开更多
Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyc...Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.展开更多
A highly efficient and green process for the synthesis ofα-aminophosphonates has been developed through a one-pot three-component reaction of various aldehydes,amines,and phosphine oxide in the presence of indium com...A highly efficient and green process for the synthesis ofα-aminophosphonates has been developed through a one-pot three-component reaction of various aldehydes,amines,and phosphine oxide in the presence of indium complexes as competent catalysts under neat conditions at room temperature.The indium complexes[κ^(2)-{RNC(Me)[double bond,length as m-dash]CHC(Me)[double bond,length as m-dash]O}_(2)InCl](R=2,6-diisopropylphenyl(Dipp),2a;2,4,6-trimethylphenyl(Mes),2b),and[κ^(2)-{DippNC(Me)[double bond,length as m-dash]CHC(Me)[double bond,length as m-dash]O}_(2)In(OTf)][(OTf=CF_(3)SO_(3)^(−),3a)were synthesised by the reaction of protic ligandβ-ketoimine with an equivalent amount of lithium hexamethyldisilazide followed by the addition of indium trichloride in toluene.The solid-state structures of complexes 2a,2b,and 3a are established by single-crystal X-ray diffraction analysis.In all the indium complexes,the indium ion is five-fold coordinated and adopts a distorted trigonal bipyramidal geometry around it.The catalytic method offers an efficient approach with a broad range ofα-aminophosphine oxide derivatives in excellent yields with good functional group tolerance.Density functional theory based mechanistic studies demonstrate energetically affordable pathways at room temperature for the indium catalysed aminophosphorylation of benzaldehyde,phenylamine,and diphenylphosphine oxide.The rate-limiting step deduced in this aminophosphorylation is the initial step in which phenylamine reacts with indium-coordinated benzaldehyde to build a C-N bond with a concomitant transfer of a proton from phenylamine to benzaldehyde.展开更多
The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized...The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized by X-ray single crystal diffraction.The determined crystal structures([C(NH_(2))_(3)]_(5)[Ln(NP_(2py))_(2)]·12H_(2)O)are the first example of a monomeric Ln^(3+)complex encapsulated by two tripodal aminophosphonic ligands.Each of the NP_(2py) anions coordinates to Ln^(3+)through two oxygen atoms from each monodentate phosphonic group,amine nitrogen and pyridine nitrogen atoms,filling thus 8 coordination sites of Ln^(3+).The luminescence properties of[C(NH_(2))_(3)]_(5)[Eu(NP_(2py))_(2)]·12H_(2)O crystals were studied and compared with those of Eu-NP_(2py) complexes in solution.Speciation analysis of Ln-NP_(2py) complexes(Ln:NP_(2py)=1:2),performed by luminescence and potentiometric methods,showed that both[Ln(NP_(2py))]^(-)and[Ln(NP_(2py))_(2)]_(5-)species may exist in solution.However,the formation of the latter one occurs in alkaline solutions at pH as high as 8.By implementing the Specific Ion Interaction Theory(SIT)it was possible to calculate the thermodynamic stability constants of the[Eu(NP_(2py))]^(-)and[Eu(NP_(2py))_(2)]^(5-)complexes.The corresponding log β_(Eul)^(0) and log β_(EuL2)^(0) values are 16.3±0.11 and 19.5±0.15,respectively.展开更多
An improved procedure for the asymmetric synthesis of α-aminoalkylphosphonic acids using S-2-anilinomethylpyrrolidine as the chiral auxiliary was described. The chemical transformations involved in this protocol coul...An improved procedure for the asymmetric synthesis of α-aminoalkylphosphonic acids using S-2-anilinomethylpyrrolidine as the chiral auxiliary was described. The chemical transformations involved in this protocol could proceed under mild reaction condition to provide good chemical and enantiomeric yields.展开更多
Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6...Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.展开更多
文摘α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.
基金supported by the Youth Foundation of Jiangxi Agricultural University (No. 20051527)
文摘The title compound has been synthesized by the addition reaction of N-（4-cyanopyrazole-3-yl）-3,5-difluorophenyl-imine and diisopropyl phosphate. Its structure was confirmed by means of IR, ^1H NMR and elemental analysis. The single-crystal structure of the title compound was determined by X-ray crystallography. The compound crystallizes in monoclinic, space group C2/c with a = 18.9959（14）, b = 9.2212（7）, c = 22.1108（16）A^°, β= 90.1540（10）°, V = 3873.0（5） A^°^3, Dc = 1.366 g/cm^3, Z = 8, μ = 0.185, F（000） = 1664, and the final R = 0.0503 and wR = 0.1539 for 2996 observed reflections （I 〉 2σ（I））. The results demonstrate that the dihedral angle between the pyrazole and benzene rings is 105.5°, and there is a full delocalized pyrazole system with sp^2 hydridization of N（3）. The crystal structure is stabilized by two intermolecular hydrogen bonds of N（1）-H（1）…O（3） and N（3）-H（3A）…N（4）. The preliminary biological test shows that the title compound has a moderate antifungal activity.
基金National Natural Science Foundation of China(Nos.20772025 and 20972042)the Program for Science & Technology Innovation Talents in Universities of Henan Province(No.2008HASTIT006)+1 种基金Innovation Scientists and Technicians Troop Construction Projects of Henan Province(No.104100510019)the Natural Science Foundation of Henan Province(Nos.092300410192 and 094300510054)
文摘An environmentally benign and highly efficient one-pot preparation of α-aminophosphonates under solvent-free conditions was developed. By employing this method, 5-aminophosphonate substituted pyrimidine nucleosides were synthesized in good to excellent yields starting from 5-forrnyl-2＇-deoxyuridine, aniline and dimethylphosphite.
基金supported by the National Natural Science Foundation of China(21532006,21690074)~~
文摘An efficient asymmetric Friedel-Crafts reaction has been developed for the synthesis of optically active quaternaryα‐aminophosphonates with up to98%ee.The synthesis involves the reaction of cyclicα‐ketiminophosphonates with indoles using an H8‐BINOL‐derived chiral phosphoric acid(CPA)catalyst that bears electron‐withdrawing3,5‐ditrifluoromethylphenyl substituents on its3‐and3′‐positions.This Friedel-Crafts reaction of cyclicα‐ketiminophosphonates was also successful with pyrrole.
基金This research was supported in part by grants from the National Natural Science Foundation of China(No.21971212)the Postdoctoral Science Foundation Project of Chongqing Science and Technology Bureau(No.cstc2019jcyj-bshX0124)+1 种基金the China Postdoctoral Science Foundation(No.2019M653821XB)the Chongqing Special Foundation for Postdoctoral Research Proposal(No.XmT2018082).
文摘The limit ability of traditional antibiotics to treat drug resistant bacteria calls for new therapeutic alter natives.A class of unique sul-fanilamide aminophosphonates as new potential agents against microbes was synthesized by one-pot three-component reaction.
基金Project supported by the National Key Program for Basic Research （Nos. 2003CB114404, 2005CCA01500）, the National Natural Science Foundation of China （No. 20362004） and the Doctoral Program Foundation of the Ministry of Education, China （No. 20040657003）.
文摘Chiral α-aminophosphonates were synthesized using （R） or （S）-1-phenylethylamine in the presence of BF3·Et2O under microwave irradiation in moderate to good yields. The new compounds were identified by ^1H NMR, ^19F NMR, IR and elemental analysis. Their antifungal activities were evaluated and some compounds were found to exhibit excellent antifungal activities. To the best of our knowledge, this is the first report on antifungal activity of chiral α-aminophosphonates containing fluorine moiety.
基金the National Key Research and Development Program of China(grant no.2020YFA0608300)the Space Application System of China Manned Space Program(grant no.KJZ-YY-WSM01)National Natural Science Foundation of China(grant nos.21772163,21778042,and 41876072).
文摘Developing practical strategies for the synthesis of organophosphorus compounds(OPCs)from white phosphorus(P_(4))without the use of Cl_(2) and PCl_(3) remains a significant challenge.The first multicomponent oxidative α-phosphonylation of amines with P_(4) and alcohols has been developed.With the use of copper(Ⅱ)as the catalyst and air as the safe oxidant,structurally sophisticated α-aminophosphonates have been prepared in high yields.Furthermore,this method is also suitable for selective construction of P-O-P compounds.The reaction is characterized by a complete conversion of P_(4).The activation of P_(4) with transition metals often leads to formation of complexes[M_(x)P_(y)]_(n) associated with the deactivation of transition metals.This breakthrough showcases the potential of transition-metal-catalyzed reactions in elemental phosphorus chemistry.
基金Acknowledgement The authors gratefully acknowledge the financial support from National Basic Research Program of China （Nos. 2012CB821600, 2010CB126103）, the Key Program of the National Natural Science Foundation of China （No. 21032006）, National Natural Science Foun- dation of China （Nos. 21172244/21172245/B020304）, Agro-scientific Research in the Public Interest （No. 201103007）, the National Key Technologies R＆D Pro- gram （No. 2011BAE06B05）, and Shanghai Scientific Research Program （No. 10XD 1405200）.
文摘A highly selective method for the asymmetric formation of trifluoromethyl-substituted α- and β-aminophos- phonates was described. The reaction proceeded with high yields and good to excellent diastereoselectivity. The product can be easily converted into corresponding trifluoromethyl-substituted aminophosphoric acids.
基金South Wisdom Valley Innovative Research Team Program(No.2013CXTD05)
文摘An enzyme-stimulating catalyst( PTL) with copper ions( Cu^(2+)) as the activation center and aminophosphonate as ligand was developed and applied in low-temperature scouring/bleaching of cotton knits. The optimal weight ratio of Cu^(2+) to aminophosphonate was 1 ∶75. Via orthodox and single-factor experiments,the most efficient formula for low-temperature scouring/bleaching was composed of 0. 4 g/L high-efficiency degreaser DM-1130,1. 5 g/L PTL,2. 0 g/L sodium hydroxide( NaOH),and 7. 0 g/L 30% hydrogen peroxide( H_2O_2). The PTL could not only increase the whiteness of cotton knits,but also remove pectin to enhance capillary effect.
文摘Inspired by the anti-pancreatic promising results of our novel aminated cyclopropylmethylphosphonate compounds, an in vitro anti-prostate cancer activity exploration of these compounds was carried out on human prostate cancer cell line PC-3, and showed potent inhibiting activity at low micromolar concentrations (with an IC50 of approximately 45 μM).
文摘Buoyed by the extensive research on the wide-range biological activities of aminophosphonates, a novel class of aminated (cyclopropylmethyl)phosphor-nates compounds was synthesized from diethyl ((1-(3-chloropropyl)cyclopropyl)methyl)phosphonate and various amines in the presence of Hunig’s base. Upon biological activity screening these compounds demonstrated encouraging anti-pancreatic cancer properties at low micromolar concentrations.
基金supported by the Science and Engineering Research Board(SERB),Government of India,under project no.(EMR/2016/005150)the Faculty Initiation Grant(FIG–100810)and computational facilities provided by IIT Roorkee.
文摘A highly efficient and green process for the synthesis ofα-aminophosphonates has been developed through a one-pot three-component reaction of various aldehydes,amines,and phosphine oxide in the presence of indium complexes as competent catalysts under neat conditions at room temperature.The indium complexes[κ^(2)-{RNC(Me)[double bond,length as m-dash]CHC(Me)[double bond,length as m-dash]O}_(2)InCl](R=2,6-diisopropylphenyl(Dipp),2a;2,4,6-trimethylphenyl(Mes),2b),and[κ^(2)-{DippNC(Me)[double bond,length as m-dash]CHC(Me)[double bond,length as m-dash]O}_(2)In(OTf)][(OTf=CF_(3)SO_(3)^(−),3a)were synthesised by the reaction of protic ligandβ-ketoimine with an equivalent amount of lithium hexamethyldisilazide followed by the addition of indium trichloride in toluene.The solid-state structures of complexes 2a,2b,and 3a are established by single-crystal X-ray diffraction analysis.In all the indium complexes,the indium ion is five-fold coordinated and adopts a distorted trigonal bipyramidal geometry around it.The catalytic method offers an efficient approach with a broad range ofα-aminophosphine oxide derivatives in excellent yields with good functional group tolerance.Density functional theory based mechanistic studies demonstrate energetically affordable pathways at room temperature for the indium catalysed aminophosphorylation of benzaldehyde,phenylamine,and diphenylphosphine oxide.The rate-limiting step deduced in this aminophosphorylation is the initial step in which phenylamine reacts with indium-coordinated benzaldehyde to build a C-N bond with a concomitant transfer of a proton from phenylamine to benzaldehyde.
文摘The Eu^(3+)and Gd^(3+)complexes with an N-(methylene-2-pyridine)-N,N-di(methylenephosphonate)ligand(H_(4)NP_(2py)),an analogue of nitrilotri(methylphosphonic)acid(H6NTP),were synthesized and structurally characterized by X-ray single crystal diffraction.The determined crystal structures([C(NH_(2))_(3)]_(5)[Ln(NP_(2py))_(2)]·12H_(2)O)are the first example of a monomeric Ln^(3+)complex encapsulated by two tripodal aminophosphonic ligands.Each of the NP_(2py) anions coordinates to Ln^(3+)through two oxygen atoms from each monodentate phosphonic group,amine nitrogen and pyridine nitrogen atoms,filling thus 8 coordination sites of Ln^(3+).The luminescence properties of[C(NH_(2))_(3)]_(5)[Eu(NP_(2py))_(2)]·12H_(2)O crystals were studied and compared with those of Eu-NP_(2py) complexes in solution.Speciation analysis of Ln-NP_(2py) complexes(Ln:NP_(2py)=1:2),performed by luminescence and potentiometric methods,showed that both[Ln(NP_(2py))]^(-)and[Ln(NP_(2py))_(2)]_(5-)species may exist in solution.However,the formation of the latter one occurs in alkaline solutions at pH as high as 8.By implementing the Specific Ion Interaction Theory(SIT)it was possible to calculate the thermodynamic stability constants of the[Eu(NP_(2py))]^(-)and[Eu(NP_(2py))_(2)]^(5-)complexes.The corresponding log β_(Eul)^(0) and log β_(EuL2)^(0) values are 16.3±0.11 and 19.5±0.15,respectively.
基金Project supported by the National Natural Science Foundation of China （Nos. 20272075 and 20072052）.
文摘An improved procedure for the asymmetric synthesis of α-aminoalkylphosphonic acids using S-2-anilinomethylpyrrolidine as the chiral auxiliary was described. The chemical transformations involved in this protocol could proceed under mild reaction condition to provide good chemical and enantiomeric yields.
基金Project supported by the National Natural Science Foundation of China （Nos. 20272075. 20372076）. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.
