954422-32-3

Upstream product

• 41593-58-2 diphenylphosphineborane 
• 13292-87-0 dimethylsulfide borane complex 
• 20684-82-6 (diphenylphosphinoyl)(phenyl)methanol 
• 100-52-7 benzaldehyde 
• 4559-70-0 Diphenylphosphine oxide 
• 17154-34-6 (trimethylsilyl)diphenylphosphine 
• 98-88-4 benzoyl chloride 
• 14044-65-6 borane-THF 
• 36838-04-7 α-Oxo-phenylmethan-diphenylphosphin 

Downstream Products

• 1290631-65-0 (1-hydroxy-1-(4-cyanophenyl)methyl)diphenylphosphine-borane 
• 100-52-7 benzaldehyde 

Relevant academic research and scientific papers

Reduction of functionalized tertiary phosphine oxides with BH3

A direct stereoselective conversion of tertiary hydroxyalkylphosphine oxides to the corresponding tertiary hydroxyalkylphosphine-boranes involving facile reduction of the P=O bond by BH3 under mild conditions has been developed. The unprecedented facility of reduction of the strong P=O bond by BH3, a mild reducing agent, has been achieved through an intramolecular P=O···B complexation directed by proximal aα- or β-hydroxy groups present in the phosphine oxide structures. As established by two chemical correlations, the developed transformation of hydroxyalkylphosphine oxides into hydroxyalkylphosphine-boranes takes place with complete inversion of configuration at P.

Asymmetric synthesis of α-chiral hydroxyalkylphosphines by a catalytic enantioselective reduction of acylphosphines

Enantioselective reduction of acylphosphines, after precomplexation with borane, proceeded smoothly in the presence of a chiral oxazaborolidine catalyst and catecholborane. α-Hydroxyalkylphosphine products were obtained as phosphine-borane complexes in good yield and enantioselectivity. One of the products of the enantioselective reduction was successfully applied as an optically active phosphine ligand for asymmetric catalysis after suitable derivatization.

Ph2P(BH3)Li: From ditopicity to dual reactivity

A multinuclear NMR study shows that the deprotonation of diphenylphosphine-borane by n-BuLi in THF leads to a disolvated lithium phosphido-borane Ph2P(BH3)Li of which Li+ is connected to the hydrides on the boron and two THF molecules rather than to the phosphorus. This entity behaves as both a phosphination and a reducing agent, depending on the kinetic or thermodynamic control imposed to the reaction medium. Density functional theory computations show that H2P(BH 3)Li exhibits a ditopic character (the lithium cation can be in the vicinity of the hydride or of the phosphorus). It explains its dual reactivity (H- or P-addition), both routes going through somewhat similar six-membered transition states with low activation barriers.

Synthesis and reactions of phosphine-boranes. Synthesis of new bidentate ligands with homochiral phosphine centers via optically pure phosphine-boranes

Secondary and tertiary phosphine-boranes were synthesized in one-pot from phosphine oxides or substituted chlorophosphines without isolation of the intermediate phosphines. Phosphine-boranes having a methyl group were metalated with sec-butyllithium. The generated carbanions reacted with alkyl halides or carbonyl compounds to yield various phosphine-borane derivatives. The carbanions underwent copper(II)-promoted oxidative coupling without impairment of the borane functionality. Secondary phosphine-boranes reacted with alkyl halides, aldehydes, or α,β-unsaturated carbonyl compounds to give phosphine-borane derivatives having a functional group. The boranato group of phosphine-boranes was removed in a stereospecific manner with retention of configuration by treatment with a large excess of amine such as morpholine. A new route to bidentate ligands with homochiral phosphine centers has been explored by utilizing these characteristic reactivities of phosphine-boranes. Thus, optically pure (S,S)-1,2-bis(o-anisylphenylphosphino)ethane, (R,R)-1,2-bis(tert-butylphenyl-phosphino)ethane, and (S,S)-1,4-bis(o-anisylphenylphosphino)butane have been synthesized via phosphine-boranes.