5994-87-6

Usage

Uses

Used in Pharmaceutical Industry:
Diphenylphosphinamide is used as a key intermediate for the synthesis of chiral molecules with specific biological activities. Its ability to provide 5H-oxazol-4-ones with high diastereoselectivity and enantioselectivity makes it a valuable tool in the development of new drugs with improved efficacy and selectivity.
Used in Agrochemical Industry:
Diphenylphosphinamide is also used in the synthesis of chiral agrochemicals, where its ability to provide 5H-oxazol-4-ones with high diastereoselectivity and enantioselectivity can lead to the development of more effective and selective pesticides and other agrochemicals.

InChI:InChI=1/C12H12NOP/c13-15(14,11-7-3-1-4-8-11)12-9-5-2-6-10-12/h1-10H,(H2,13,14)

Upstream product

• 1499-21-4 Diphenylphosphinic chloride 
• 98-03-3 thiophene-2-carbaldehyde 
• 82944-84-1 N-[(1E)-1-phenylethylidene]-P,P-diphenylphosphinic amide 
• 67-56-1 methanol 
• 75-18-3 dimethylsulfide 
• 4129-17-3 diphenylphosphoranyl azide 
• 60066-32-2 trimethylammonio-P,P-diphenylphosphinamidate 
• 104-87-0 4-methyl-benzaldehyde 
• 104-88-1 4-chlorobenzaldehyde 
• 89-98-5 2-chloro-benzaldehyde 
• 124730-93-4 triethylammonio-N-diphenylphosphinoylimide 
• 124730-81-0 1-benzoyl-2,2,4-triphenyl-1,3-diaza-2λ⁵-phosphapenta-1,3-diene 
• 100-52-7 benzaldehyde 
• 123-11-5 4-methoxy-benzaldehyde 

Downstream Products

• 610-15-1 2-nitrobenzamide 
• 619-56-7 4-chlorobenzamide 
• 645-09-0 3-nitrobenzamide 
• 619-80-7 4-nitrobenzamide 
• 6779-62-0 isocyanatodiphenylphosphine oxide 
• 56372-47-5 N,N-diethyl P,P-diphenylphosphinamide 
• 1110-78-7 hexaphenyl-cyclotriphosphazene 
• 27127-08-8 N-benzyl-P,P-diphenylphosphinic amide 
• 27127-09-9 N,N-dibenzyl-P,P-diphenylphosphinic amide 
• 6779-25-5 N-(diphenylphosphinyl)-N'-phenylurea 
• 6778-81-0 N-Isopropyl-N'-diphenylphosphinyl-harnstoff 
• 6230-69-9 N-propyl-P,P-diphenylphosphinic amide 
• 84718-88-7 n-diphenylphosphinyldimethylsulphilimine 
• 63528-17-6 N-ethyl-P,P-diphenylphosphinic amide 

Relevant academic research and scientific papers

A practical method for N-alkylation of phosphinic (thio)amides with alcohols via transfer hydrogenation

This manuscript describes a modular method for preparing N-alkyl phosphinic amides from primary or secondary alcohols and primary phosphinic amide (R1R2P = ONH2) nucleophiles via transfer hydrogenation. The transformation typically proceeds in excellent yields, employs conveniently available reagents, and produces water as the only byproduct.

Electrooxidation of chlorodiphenylphosphine under ammonia atmosphere. Synthesis of 2,2,4,4,6,6-hexaphenylcyclotriphosphazene and iminobis(Aminodiphenylphosphorus) chloride

Electrooxidation of MeCN solution of chlorodiphenylphosphine in the presence of Cl? under NH3 atmosphere gave a mixture of 2,2,4,4,6,6-hexaphenylcyclotriphosphazene and iminobis(aminodiphenylphosphorus) chloride.

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.

Nucleophilic addition of TMSCCl3 to N-phosphinoyl benzaldimines: A route to N-phosphinoyl-α-(trichloromethyl)benzylamines

Nucleophilic addition of readily available TMSCCl3 to N-phosphinoyl benzaldimines allows preparation of N-phosphinoyl-α-(trichloromethyl)benzylamines. Typically, the reaction in THF at room temperature using tetrabutylammonium difluorotriphenylsilicate (TBAT) as a catalytic promoter, afforded very good yields (65-95% range) for most derivatives within 1 h at room temperature.

Discovery and synthetic value of a novel, highly crowded cyclopentadienylphosphane Ph2P-CpH and its ferrocenyl-bisphosphane dppf

Base-catalysed condensation of Ph2P-C5H5 (1) with an excess of acetone leads to a fulvene-like diphenyl(4,4,6-trimethyl- 4,5-dihydropentalen-2-yl)phosphane Ph2P-C11H13 (3) as a product of double condensation. Carbometallation of 3 with MeLi, followed by aqueous work-up, results in formation of a new cyclopentadienylphosphane bearing a highly sterically demanding, anellated 1,1,3,3-tetramethylcyclopentane moiety (4, Ph2P-CpH). It reacts with chalcogene oxidants (H2O2, S8, Se) to form the corresponding phosphane chalcogenides Ph2P(=X)CpH, X = O (5), S (6), Se (7) in high yields. Quatemization of 4 with MeI gives the phosphonium salt 8 as a single isomer in high yield. Dehydrohalogenation of 8 by reaction with nBuLi gives Cp-phosphonium ylide Ph2P(Cp )Me (9). An alternative protocol towards 9 that includes deprotonation of 8 with benzylpotassium followed by P-alkylation is superior and gives 9 in more than 95% yield. Staudinger reaction of 4 with tBuN3 gives only P-arnino-cyclopentadienylidenephosphorane Ph2P(Cp)-NHtBu (10), whereas with Me3SiN3 only the tautomeric P-imino-cyclopentadienylphosphane Ph2P(NSiMe3)CpH (11) was isolated. Hydrolysis of 11 with wet MeCN leads to the new parent P-arnino-cyclopentadienyhdenephosphorane Ph2P-(Cp)NH 2 (12). Treatment of 4 with benzylpotassium followed by transmetallation with FeCl2 leads to the sterically most crowded ferrocenyl-bisphosphane [{Ph2P-Cp}2Fe] (13, dppf) in high yield. Its X-ray diffraction analysis reveals an anti-orientation of phosphane functionalities at both cyclopentadienyl rings. However, upon reaction of dppf with [PdCl2(MeCN)2], a constrained syn-orientation is achieved in the product [[dppf] PdCl2] (14). Halogen exchange by reaction of 14 with NaI leads to the corresponding [{dppf}PdI2] (15). Molecular structures of 4, 9, 13 and 15 have been confirmed by XRD studies.

Reaction prospecting by 31P NMR: enantioselective rhodium-DuPhos catalysed addition of ZnMe2 to diphenylphosphinoylimines

Chiral shift 31P NMR spectroscopy allows the identification of ligand leads in asymmetric catalyst systems for ZnMe2 addition to ArCH{double bond, long}NP(O)Ph2. Subsequent GC-based optimisation shows [RhCl(CH2{double bond, long}CH2)2]2 and (R,R)-MeDuPhos to be the optimal pre-catalyst combination (product in 78-93% ee). Transmetallation of [(MeDuPhos)Rh{N(P(O)Ph2-CHMeAr}] with ZnMe2 appears to be the rate limiting step of the catalytic cycle as competing coordination by the imine starting material leads to Ph2P(O)NHCH2Ar via MVP hydrogen-transfer. This limitation can largely be overcome by the slow addition of the imine.

Multicomponent one-pot procedure for the synthesis of free α-chiral amines from aldehydes

The synthesis of free a-chiral amines by a one-pot multi-component procedure from commercially available starting materials is described. This enantioselective reaction involves a catalytic asymmetric addition of dialkylzinc reagents to N-diphenylphosphin

Olefination reactions through phosphazenes

The first synthesis of di-, tri- and tetrasubstituted alkenes through reaction of lithium P-diphenyl(alkyl)(N-carboxymethyl)phosphazenes with aldehydes and ketones is reported.

Rearrangement of O-benzoyl-N-(diphenylphosphinothioyl) hydroxylamine: An 18O-labelling investigation of oxygen-sulfur transposition

When Ph2P(S)NHOCOPh labelled with 18O in the C=O group (43% isotopic enrichment) reacts with NaOMe in MeOH, the products are unlabelled Ph2P(O)NH2 and labelled PhCO2Me (43% isotopic enrichment). By implication, the intermediate Ph2P(O)NHSCOPh that results from rearrange- meat (translation of O and S atoms) has all the label in the C=O group and none in the P=O group.