A single-step one pot synthesis of dialkyl fluorophosphates from dialkylphosphites

Purohit, Ajay Kumar; Pardasani, Deepak; Kumar, Ajeet; Goud, D. Raghavender; Jain, Rajiv; Dubey, D. K.

doi:10.1016/j.tetlet.2015.06.014

Cited by 19 publications

(10 citation statements)

References 24 publications

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“…Transition‐metal‐catalyzed cross‐coupling of an unprotected propargylic alcohol and terminal alkyne afforded 6 d [27] and 6 e [28] in 58 % and 79 % yields, respectively, under ligand‐ and base‐free conditions. Moreover, fluorophosphate 6 f [29] was synthesized in 75 % yield by the direct fluorination of R 2 P(O)H under mild conditions. In addition, P(O)H compounds can be used to construct C(sp 2 )−P bonds with a high efficiency ( 6 g – 6 i , 65–85 %).…”

Section: Resultsmentioning

confidence: 99%

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition‐Metal‐ and Photocatalyst‐Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

et al. 2022

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Developing practical and mild strategies for the direct functionalization of white phosphorus (P 4 ) without chlorination is an appealing but formidable challenge. To this end, we report a breakthrough in the preparation of structurally diverse dialkylphosphines and trialkylphosphines that rely on the successive generation of carbon-centered radicals from N-hydroxyphthalimide (NHPI) esters and the controllable alkylation of the P 4 molecule under transition-metal-and photocatalyst-free conditions. To facilitate separation and prevent product losses during purification, the corresponding oxidation products dialkylphosphine oxides (DAPOs) and trialkylphosphine oxides (TAPOs) were isolated. This photoinduced phosphorylation reaction features one-pot operation, high product selectivity, and tolerates a broad range of alkyl NHPI esters, including derivatives of complex natural products and pharmaceuticals. Further diversified transformation of DAPOs to construct PÀ F, PÀ C, PÀ N, and PÀ O bonds was also demonstrated.

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Section: Resultsmentioning

confidence: 99%

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition‐Metal‐ and Photocatalyst‐Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

et al. 2022

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“…H ‐phosphonate diesters are phosphorus compounds that are characterised by the presence of multiple functional groups: P−OR, P−H and P=O [1] . These molecules have attracted attention in both organic and inorganic chemistry for the creation of new phosphorus element bonds, such as P−N, [2] P−O−P and P−P, [3] P−F, [4] P−S, P−Se and P−Te, [5] and P−C bonds [6] due to their interesting reactivity as both the phosphorus centre and α‐carbon can be subject to nucleophilic attack. More recently, H ‐phosphonate diesters have been used in the formation of molecules [7] and macromolecules [8] with interesting architectures and useful potential applications.…”

Section: Introductionmentioning

confidence: 99%

The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H‐Phosphonate Salts

Lee

Feld

Hume

et al. 2020

Chemistry A European J

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A series of ammonium monosubstituted H‐phosphonate salts were synthesized by combining H‐phosphonate diesters with amines in the absence of solvent at 80 °C. Variation of the ester substituent and amine produced a range of ionic liquids with low melting points. The products and by‐products were analyzed by spectroscopic and spectrometric techniques in order to get a better mechanistic picture of the dealkylation and formal dearylation observed. For dialkyl H‐phosphonate diesters, (RO)2P(O)H (R=alkyl), the reaction proceeds via direct dealkylation with the reactivity increasing in the order R=iPr<Et<Me corresponding to DFT calculated activation enthalpies of 22.6, 20.8, and 17.9 kcal mol−1. For the diphenyl H‐phosphonate diesters, (PhO)2P(O)H, the dearylation was found to proceed via phenol‐assisted formation of a 5‐coordinate intermediate, (PhO)3PH(OH), from which P(OPh)3 and water were eliminated. The presence of an equivalent of water then facilitated the formation of P(OH)2OPh and the amine, R'NH2, subsequently abstracted a proton from it to yield [(PhO)PH(O)O]‐[R'NH3]+.

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“…H ‐phosphonate diesters are useful synthons in a variety of reactions . Selected specific examples include, reactants in the catalytic cross coupling of P−N, P−O−P, P−P, P−F, P−C, P−O−C, P−Se and P−S bonds, base‐catalyzed hydrophosphination of azobenzene to form N−N−P units, organophosphorus ligands in metal complexes, in addition to precursors to phosphines, P−Cl, and biologically active phosphorus compounds . Furthermore, H ‐phosphonate diesters are reactants in transesterification, alkylation reactions and in P−O−Si polymer synthesis .…”

Section: Introductionmentioning

confidence: 99%

Facile Substituent Exchange at H‐Phosphonate Diesters Limiting an Effective Synthesis of D‐Phosphonate Diesters

et al. 2019

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Research on using H-phosphonate diesters to introduce phosphorus functionality into molecules and polymers, some of which have medicinal applications, has recently attracted a lot of attention. Deuterium labelling to yield the corresponding D-phosphonate diesters, although desirable in order to help with the mechanistic elucidation of reactions containing H-phosphonate diesters, has been demonstrated to be a challenge. Deuterium exchange at Hphosphonate diesters using D 2 O, MeOD and ND 2 Bn has shown competitive behavior with hydrolysis, alcoholysis and aminolysis reactions, respectively. This facile substituent exchange for the addition of D 2 O and MeOD can be attributed to the similar energy required to eliminate ROH or H 2 O (ROD or HOD, R = iPr, Et, Me) from a pentavalent P(V) intermediate which is generated from axial delivery of an OD or OR group from D 2 O and MeOD, respectively. The trend in reaction rate for the exchange processes follows the order of R = Me > Et > iPr in (RO) 2 P(O)H and also depends on the nucleophilicity of the incoming group. Attempted synthesis of D-phosphonate diesters directly from PCl 3 and alcohols or via lithiation reactions further demonstrated just how sensitive the H/D-scrambling process is. These results have implications for the general reactivity of H-phosphonate diesters towards water, alcohol, and amines and their potential to selectively undergo substitution at either P-OR or P-H. Moreover, insight into the mechanism(s) of selective deuterium exchange, for example to give D-phosphonate diesters via the direct exchange of D for H, was illuminated through this research. at 101 MHz and are given in parts per million relative to CDCl 3 (δ = 77.0 ppm). Chemical shifts for 31 P NMR spectra are recorded at 161.97 MHz and given relative to external 85% phosphoric acid (δ = 0 ppm). Data are represented as follows: chemical shift, multiplicity (app = apparent, br = broad, s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet), coupling constants in Hertz (Hz), and integration.

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A single-step one pot synthesis of dialkyl fluorophosphates from dialkylphosphites

Cited by 19 publications

References 24 publications

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition‐Metal‐ and Photocatalyst‐Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

Decarboxylative Selective Phosphorylation of Aliphatic Acids: A Transition‐Metal‐ and Photocatalyst‐Free Avenue to Dialkyl and Trialkyl Phosphine Oxides from White Phosphorus

The Synthesis and Mechanistic Considerations of a Series of Ammonium Monosubstituted H‐Phosphonate Salts

Facile Substituent Exchange at H‐Phosphonate Diesters Limiting an Effective Synthesis of D‐Phosphonate Diesters

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