288248-53-3

Upstream product

• 917-54-4 methyllithium 
• 14474-59-0 naphthalen-1-yl-lithium 
• 1354049-87-8 C₁₇H₁₅ClP⁽¹⁺⁾*Cl^(1-) 
• 55123-94-9 (+/-)-methyl(1-naphthyl)phenylphosphine oxide 
• 199396-00-4 methyl (R)-(-)-(1-naphthyl)phenylphosphinite borane complex 
• 16940-66-2 sodium tetrahydroborate 
• 90-11-9 1-Bromonaphthalene 

Downstream Products

• 81157-85-9 (S,S)-1,2-bis[(1-naphthyl)phenylphosphanyl]ethane 
• 256474-62-1 (S,S)-1,2-bis[(1-naphthyl)phenylphosphanyl]ethane-borane(P) 
• 256449-66-8 [(BH₃)(Ph)(1-naphthyl)PCH₂CH₂P(BH₃)(Ph)(1-naphthyl)] 

Relevant academic research and scientific papers

PROCESSES FOR THE STEREOSELECTIVE PREPARATION OF P-CHIRAL FOUR -COORDINATED PHOSPHORUS BORANE COMPOUNDS AND P-CHIRAL THREE-COORDINATED PHOSPHORUS COMPOUNDS

Processes for the stereoselective preparation of P-chiral four-coordinated phosphorus borane compounds and P-chiral three-coordinated phosphorus compounds.

Simple unprecedented conversion of phosphine oxides and sulfides to phosphine boranes using sodium borohydride

A variety of phosphine oxides and sulfides can be efficiently converted directly to the corresponding phosphine boranes using oxalyl chloride followed by sodium borohydride. Optically active P-stereogenic phosphine oxides can be converted stereospecifically to phosphine boranes with inversion of configuration by treatment with Meerwein's salt followed by sodium borohydride.

Allylpalladium complexes with P-stereogenic monodentate phosphines. Application in the asymmetric hydrovinylation of styrene

A group of P-stereogenic monodentate phosphines S-PPhRR' (R = 1-naphthyl, 9-phenan-thryl, or o-biphenylyl and R' = CH3-, i-C3R 3-, and Ph3SiCH2-) have been prepared by succesive substitution reactions on the oxazaphospholidineborane obtained from (-)ephedrine and bis(N,N-diethylamino)phenylphosphine. The reaction with binuclear allyl compounds [Pd(μ-Cl)(allyl)]2 gives neutral [PdCl(allyl)P*] complexes. When allyl = 2-CH3-CsH4 (5), two isomers appeared in solution due to the R- or S-geometry around the palladium atom. The discrimination effect of the phosphines is small and the maximum isomeric ratio is observed for PPh(o-Ph2)(CH 2SiPh3). The molecular structure determined by X-ray diffraction of two complexes with P* = PPh(o-Ph2)(i-Pr) and PPh(o-Ph2)(OMe) showed a very similar nonsymmetric coordination of the allyl moiety according to the greater trans influence of the phosphorus atom. When allyl = 1-C6H5-C3H4 (6), the NMR spectroscopy showed up to four isomers due to the R- or S-geometry around palladium and the Z- or E-disposition of P* and the phenyl substituent of the allyl moiety. The E-isomers are the major species in solution, unique with PPh(o-Ph2)(CH2SiPh3). The usual, well-defined dynamic exchanges by π-σ-π and pseudorotation of the allyl moiety have been observed. The codimerization reaction between styrene and ethylene has been tested using filtered CH2Cl2 solutions of [PdCl(2-CH3-C3H4)P*] (5) complexes and AgBF4 as catalytic precursors. Moderate activity (TOF -1 at 25 °C) and good selectivities to 3-Ph-l-butene (-90% at 80% conversion) are obtained. The ee is moderate (a potentially secondary coordination atom occurs only when the substitution is in the phenyl ring and without significant improvements of the ee.

Highly enantiomerically enriched chlorophosphine boranes: Synthesis and applications as P-chirogenic electrophilic blocks

The stereoselective synthesis of P-chirogenic chlorophosphine boranes 4 was investigated by HCl acidolysis of the corresponding aminophosphine boranes 10. The reaction afforded the P-N bond cleavage with inversion of the configuration at the phosphorus center, leading to the chlorophosphine boranes 4 with high to excellent enantiomeric purities (80-99% ee), except in the case of the chloro1-naphthylphenylphosphine borane 4d. Reaction conditions and workup significantly influence the enantiomeric purity of the product, with the exception of the o-anisyl- and o-tolylchlorophenylphosphine boranes, 4b and 4c, which were found to be particularly stable even after purification by chromatography on silica gel. Reaction of the chlorophosphine boranes 4 with various nucleophiles, such as carbanions, phenolates, thiophenolates, or amides, afforded the corresponding organophosphorus borane complexes via P-C, P-O, P-S, and P-N bond formation, respectively, in 34-93% yield and with up to 99% ee. This work demonstrates the importance of chlorophosphine boranes 4 as new and powerful electrophilic building blocks for the highly stereoselective synthesis of P-chirogenic organophosphorus compounds.

The Reactions of Optically Pure Menthyloxymethylphenylphosphine-Borane with Organolithium Reagents

The reactions of (Rp)-menthyloxymethylphenylphosphine-borane with several organolithium reagents are described.Less sterically hindered reagents such as m-anisyllithium and p-anisyllithium react with the phospine-borane to afford the correspond

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.