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Upstream product

• 67-56-1 methanol 
• 97730-00-2 tert-butylphenylphosphinic trifluoromethanesulfonic anhydride 
• 80918-94-1 O-methyl phenyl-t-butylphosphinothioate 
• 113502-18-4 P-(1,1-dimethylethyl)-P-phenylphosphinoselenoic acid Se-methyl ester 
• 104092-22-0 bis<(tert-butylphenyl)phosphino>phosphinic anhydride 
• 74-88-4 methyl iodide 
• 98976-30-8 tert-Butylphenylphosphine oxide 
• 890415-62-0 (+)-1-(N-benzylamino)-1-(4-pyridyl)-(S)-methyl-tert-butylphenyl-(S)-phosphine oxide 
• 82220-41-5 tert-butylphenylphosphinic imidazolidide 
• 4923-85-7 tert-butylphenylphosphinic acid chloride 
• 51584-27-1 t-butyl phenyl selenophosphinic acid 
• 84718-90-1 t-butyl(phenyl)phosphinic azide 
• 82220-43-7 tert-butylphenylphosphinic methanesulfonic anhydride 

Relevant academic research and scientific papers

Dynamic Kinetic Resolution of Phosphinic Acid Derivatives via Nucleophilic Substitution at Phosphorus Center

Reaction of racemic phosphinic acid derivatives with chiral alcohols proceeds with predominant formation of one diastereomer. The highest level of enrichment has been obtained for transesterfication of racemic methyl benzylphenylphosphinate (64% de). The

Efficient asymmetric synthesis of structurally diverse p-stereogenic phosphinamides for catalyst design

The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis.

Aminophosphine oxides in a pyridine series. Studies on the cleavage of pyridine-2- and pyridine-4-yl-(N-benzylamino)-methyldiphenylphosphine oxides in acidic solutions

The synthesis and reactions of 1-(N-benzylamino)-1-(2-pyridyl)- and 1-(N-benzylamino)-1-(4-pyridyl)-methyldiphenylphosphine oxides are described. It was found that these compounds were exceptionally easy to cleave in aqueous sulfuric acid solutions to form diphenylphosphinic acid and the corresponding N-(pyridylmethyl)-benzylamines. The structure of a single diastereoisomer, that is, the (R)-(+)-1-[N-(α-methylbenzylamino)]-1-(4-pyridyl)-(S)-methyldiphen ylphosphine oxide was determined by X-ray crystallography. The acidic alcoholysis of the selected model chiral pyridine aminophosphine oxides was investigated by means of 31P NMR spectroscopy. The cleavage kinetics were also studied. On the basis of the obtained results, a mechanism of the cleavage was formulated.

Reactivity of diacyloxyiodobenzenes toward trivalent phosphorus nucleophiles

The reaction of diacyloxyiodobenzenes and tetravalent phosphorus nucleophiles was investigated. It was established that both H-phosphonates and secondary phosphine oxides react with diacetoxyiodobenzene in alcohols in the presence of sodium alcoholates yi

The reactions of dialkyl phosphites and phosphine oxides with iodosylbenzene

The reaction of iodosylbenzene with > P(O)H type of acids (dialkyl phosphites, secondary phosphine oxides) was studied. The acids of >P(O)H type add to iodosylbenzene to yield intermediate 6 which in the aprotic solvents yields oxidation products, it means >P(O)OH acids and/or anhydride of >P(O)OP(O) P(O)OR ester is the major product.

Reductive cleavage of the halogen-phosphorus, oxygen-phosphorus and phosphorus-phosphorus bonds with alkali metals

The reduction of phosphorus acid chlorides as well as hypophosphates, pyrophosphates and mixed P(III)-P(V) anhydrides with alkali metals (Li, Na, K) in NH3 liq. / THF solution and potassium naphthalenide was investigated. It was found that this type of phosphorus compounds easily undergo reduction: a) >P(O)Cl to >P(O)H; b) >P(O)P(O)P(O)H; c) >P(O)-O-P(O)P(O)OH and >P(O)H; d) >P(O)-O-PP(O)O- and >P-. The results of our experiments strongly suggest that the mixed P(III)-P(V) anhydride is reduced by potassium naphthalenide in THF with the cleavage of the P(III)-oxygen bond.

Phosphoric-Carboxylic Anhydrides. New Synthetic Procedures and Reactions with Nucleophiles. Reexamination of the Reaction of Se-alkyl-phosphoroselenoates with Alcohols and Mercuric Trifluoroacetate

Phosphorus trimethylsilyl esters RR'P(O)OSiMe3 react smoothly with carboxylic anhydrides to give phosphoric-carboxylic anhydrides RR'P(O)-O-COR" in excellent yield.A similar reaction proceeds between stannyl esters RR'P(O)OSnMe3 and carboxylic anhydrides.We also have found that the anhydrides RR'P(O)-O-COCF3 are formed in almost quantitative yield when the phosphorus acid halides RR'P(O)X (X=Cl,Br,I) are allowed to react with trifluoroacetic anhydride in the presence of N-methylimidazole. We were able to confirm again that acyclic phosphoric-carboxylic anhydrides exhibit acetylating properties towards amines and alcohols.Our findings contradict with those of Wozniak, Krzyzanowska and Stec relating to the reaction of Se-alkylphosphoroselenoates RR'P(O)SeR" with mercuric trifluoroacetate Hg(OCOCF3)2.Our interpretation of this reaction differs entirely from those presented by the above mentioned authors. Key words: phosphorus-carboxylic anhydrides, Se-alkyl-phosphoroselenoates

EFFICIENT OXYGENATION OF THIOPHOSPHORYL AND SELENOPHOSPHORYL GROUPS USING TRIFLUOROACETIC ANHYDRIDE

Trifluoroacetic anhydride reacts with organophosphorus compounds containing thiophosphoryl and selenophosphoryl groups converting them in high yield to the corresponding oxygenated systems.

Anhydrides of Phosphorus and Sulfur Acids, 2. Mixed Anhydrides of Phosphoric, Phosphonic, and Phosphinic Acids with Sulfonic Acids and Sulfuric Monoimidazolide. New Methods of Synthesis, Novel Structures, Phosphorylating Properties

New applications of methods leading to anhydrides RR'P(O)OSO2R'' (1) are described: a) Reaction of acids RR'P(O)OH (2) with sulfonic imidazolides. b) Reaction of phosphorus imidazolides 4 with sulfonic acids and sulfonic anhydrides.New methods of synthesis of anhydrides 1 have been developed. c) Reaction of phosphorus acid silyl esters RR'P(O)OSiMe3 (9) with methanesulfonic and trifluoromethanesulfonic anhydrides. d) Reaction of bis(trimethylsilyl) tert-butylphosphonate (10) with methanesulfonic acid leading to tBuP(O)(OSO2Me)2 (11). e) Reaction of stannyl phosphate (EtO)2P(O)OSnMe3 (15) with methanesulfonic anhydride. f) Reaction of phosphorus acid silyl esters 9 with trimethylsilyl trifluoromethanesulfonate.All methods result in high yields and can be adapted to a variety of anhydrides 1 derived from phosphoric, phosphonic, and phosphinic acids on the one hand and methanesulfonic, trifluoromethanesulfonic acids and sulfuric monoimidazolide on the other.Phosphonium intermediates have been demonstrated by low temperature FT 31P NMR spectroscopy for reaction b) and c).The anhydrides 1 are readily converted into imidazolides 4 by the reaction with N-(trimethylsilyl)imidazole which proceeds via two distinct phosphonium intermediates.With neutral and weakly basic nucleophiles, the anhydrides 1 behave as phosphorylating agents.

Photolysis of Diphenyl- and t-Butyl(phenyl)-phosphinic Azides: Dimethyl Sulphide as a Nitrene Trap, and Its Influence on the Curtius-like Rearrangement

Photolysis of Ph2P(O)N3 in benzene containing MeOH gives a high yield (72percent) of the phosphonamidate PhP(O)(OMe)NHPh (3) resulting from Curtius-like rearrangement.When some of the benzene solvent is replaced by Me2S the yield of the rearrangement prod