21713-54-2

Upstream product

• 10259-20-8 4-nitrophenyl diphenylphosphinate 
• 2042-41-3 p-bromophenoxide ion 
• 106-41-2 4-bromo-phenol 
• 1499-21-4 Diphenylphosphinic chloride 
• 1707-03-5 diphenyl-phosphinic acid 
• 1079-66-9 chloro-diphenylphosphine 
• 5467-74-3 4-Bromophenylboronic acid 
• 4559-70-0 Diphenylphosphine oxide 
• 829-85-6 diphenylphosphane 

Relevant academic research and scientific papers

Electrochemical Enabled Cascade Phosphorylation of N?H/O?H/S?H Bonds with P?H Compounds: An Efficient Access to P(O)-X Bonds

An electrochemical three component cascade phosphorylation reaction of various heteroatoms-containing nucleophiles including carbazoles, indoles, phenols, alcohols, and thiols with Ph2PH has been established. Electricity is used as the “traceless” oxidant and water and air are utilized as the “green” oxygen source. All kinds of structurally diverse organophosphorus compounds with P(O)-N/P(O)-O/P(O)-S bonds are assembled in moderate to excellent yields (three categories of phosphorylation products, 50 examples, up to 97 % yield). A tentative free radical course is put forward to rationalize the reaction procedure.

Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates

A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.

Base-promoted selective O-phosphorylation of aryl triflates with P(O)-H compounds

Compared to previous transition metal-catalyzed C-phosphorylation reactions for constructing C–P bonds, in the absence of transition metal catalysts and ligands, a direct O-phosphorylation of aryl triflates selectively occurred with P(O)-H compounds in the presence of a base via the construction of O–P bonds. This transformation proceeds under simple and mild conditions, and provides a new method for the preparation of valuable organophosphoryl compounds from readily available P(O)-H compounds and triflates.

Highly Efficient and Convenient Access to Phosphinates via CHCl3-Assisted Direct Phosphorylation between R2P(O)H and ROH by Phosphonium Salt Catalysis

A mild, efficient, convenient and scalable method to synthesize phosphinates via direct phosphorylation between R2P(O)H and ROH was developed. All aromatic substrates completed this transformation with excellent yields (up to 98 %), and preliminary mechanistic studies suggest that a carbene-involving process from CHCl3 to CH2Cl2 facilitates the phosphorylation.

Preparation method of compound containing P-O bond or P-S bond

The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method comprises the following steps: a compound containing hydroxyl or sulfydryl and a phosphorus reagent are taken as initial raw materials; then, the initial raw materials are put into an inert gas atmosphere; and under the action of trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO), the compound containing hydroxyl or sulfydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide in a molar ratio of (1-5): (1-2.5): (2-3): 2 react inan organic solvent at the reaction temperature of 25-100 DEG C for 6-20 hours to obtain the compound with the structural general formula (I). The reagents used in the method are low in toxicity and environmentally friendly, and use of precious metal catalysts high in price and toxicity is avoided. The reagents trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO) used in the method are low in toxicity and very low in cost, so that the method is green, environment-friendly, high in economy and suitable for large-scale production.

A phosphoryl radical-initiated Atherton-Todd-type reaction under open air

A phosphoryl radical-initiated Atherton-Todd-type reaction using air as the radical initiator and CHCl3 as the halogenating reagent for the phosphorylation of alcohols, phenols, and amines has been developed. This novel transformation provides a highly efficient route to important phosphinates, phosphinic amides, and phosphoramidates in up to 99% yield with a broad substrate scope under very mild conditions (48 examples).

A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH

A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.

Method for preparing phosphinic acid ester/phosphorous acid ester/phosphoric acid ester from P(O)-OH compound and aryl boronic acid

The invention provides a method for high-selectivity synthesis of phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives containing different substituted functional groups; a metal salt is used as a catalyst, a P(O)-OH-containing compound and aryl boronic acid are used as reactants, and an alkali, an additive and an organic solvent are added into the reaction system. The method has the advantages that the catalyst is cheap and easy to obtain; the reaction conditions are mild, and the method is safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is as high as 90% or more. The method solves the deficiency that traditional synthetic phosphinic acid ester/phosphorous acid ester/phosphoric acid ester compounds have poor reaction selectivity, complex reaction steps and low yield and need to use reagents harmful to the environment, and has a good prospect in industrial application. The invention also provides the corresponding phosphinic acid ester/phosphorous acid ester/phosphoric acid ester derivatives correspondingly containing different substituted functional groups.

The Phenomenology of Differently Constructed Broensted-type Plots

Two different methodologies for the construction of Broensted-type plots are compared; curved plots using the traditional approach and linear plots by a novel approach are obtained for the reaction of phenoxides with p-nitrophenyl diphenylphosphinate in dimethyl sulfoxide-water media at 25 deg C.

A NOVEL SUBSTITUENT EFFECT ON 31P NMR CHEMICAL SHIFTS IN THE ARYL DIPHENYLPHOSPHINATE SERIES

The 31P NMR chemical shifts of a series of meta- and para-substituted phenyl diphenylphosphinates, Ph2P(O)OC6H4-X, have been determined.The δ 31P values exhibit an increasing downfield trend as the electron-withdrawing properties of the substituent X become greater and a reasonable correlation between δ 31P and Hammett-Taft substituent constants is obtained.This trend is opposite to that exhibited in several families of compounds of the type ArP(O)Y2, where δ 31P values show an increasing upfield trend as the electron-withdrawing ability of the substituent in Ar is increased.The results are explained by proposing varying degrees of d-orbital occupancy in the phosphorous-oxygen bonds (P-OAr and P=O) in the series of compounds as a factor influencing 31P chemical shifts.