336109-41-2

Upstream product

• 2475-92-5 4-methoxyacetophenone oxime 
• 1079-66-9 chloro-diphenylphosphine 
• 2475-92-5 (E)-1-(4-methoxyphenyl)ethanone oxime 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 1499-21-4 Diphenylphosphinic chloride 

Downstream Products

• 1283154-39-1 P,P-diphenyl-N-{1-[dimethyl(phenyl)silyl]-1-(4-methoxyphenyl)ethyl}phosphinic amide 
• 1008479-59-1 C₂₃H₂₆NO₂P 

Relevant academic research and scientific papers

Zinc-catalyzed enantioselective hydrosilylation of imines

The highly enantioselective reduction of imines is achieved by employing chiral Zn/diamine catalysts. This new catalytic protocol offers attractive features such as use of a non-precious metal and an inexpensive silane, easy modification of chiral diamine

Enantioselective Hydrogenation of Activated Aryl Imines Catalyzed by an Iron(II) P-NH-P′ Complex

Chiral amines are key building blocks in synthetic chemistry with numerous applications in the agricultural and pharmaceutical industries. Asymmetric imine hydrogenation, particularly with iridium catalysts, is well developed. However, imine reduction still remains challenging in the context of replacing such a precious metal with a cheap, nontoxic, and environmentally friendly substitute such as iron. Here, we report that an unsymmetrical iron P-NH-P′ catalyst that was previously shown to be effective for the asymmetric hydrogenation of aryl ketones is also a very effective catalyst for the asymmetric hydrogenation of prochiral aryl imines activated with N-diphenylphosphinoyl or N-tosyl groups. The P-NH-P′ abbreviation stands for (S,S)-PPh2CHPhCHPhNHCH2CH2PiPr2. Density functional theory results suggest that, surprisingly, the NH group on the catalyst activates and orients the imine to hydride attack by hydrogen bonding to the PO or SO group on the imine nitrogen, as opposed to the imine nitrogen itself. This may explain why N-Ph and N-Bu imines are not hydrogenated.

Asymmetric synthesis of novel (1h-benzo[d]imidazol -2-ylthio)- and (di-n-butylamino-2-ylthio)acetamides

Asymmetric synthesis of novel (1H-benzo[d]imidazol-2-ylthio)- and (di-n-butylamino)acetamides is described. The o-nitrobenzyl oxime ethers were reduced with borane in the presence of oxazaborolidenes derived from norephedrine or diphenylvalinol and diphenylphosphinic amide was reduced with modified sodium tetrahydroborate catalyzed with β-ketoiminato cobalt(II) complex to the corresponding amines with high yields and moderate enantiomeric excess. Reaction of amines with 2-chloroacetyl chloride and next with thiobenzimidazole or n-dibutylamine gave corresponding products with high yields.

Bifunctional iminophosphorane organocatalysts for enantioselective synthesis: Application to the ketimine nitro-Mannich reaction

The design, synthesis, and development of a new class of modular, strongly basic, and tunable bifunctional Bronsted base/H-bond-donor organocatalysts are reported. These catalysts incorporate a triaryliminophosphorane as the Bronsted basic moiety and are readily synthesized via a last step Staudinger reaction of a chiral organoazide and a triarylphosphine. Their application to the first general enantioselective organocatalytic nitro-Mannich reaction of nitromethane to unactivated ketone-derived imines allows the enantioselective construction of β-nitroamines possessing a fully substituted carbon atom. The reaction is amenable to multigram scale-up, and the products are useful for the synthesis of enantiopure 1,2-diamine and α-amino acid derivatives.

Activation of the Si-B Linkage: Copper-Catalyzed addition of nucleophilic silicon to imines

Activation of the Si-B bond through copper-catalyzed transmetalation quickly developed into a practical method to generate Cu-Si reagents These silicon nucleophiles cleanly add to aldehyde-derived imine electrophiles to form R-silylated amines in protic media, and no carbon-tonitrogen Brook-type rearrangement of the intermediate anion is observed. Aside from electron-withdrawing groups at the imine nitrogen atom, for example, SO2Tol and P(O)Ph2, previously delicate nitrogen substituents such as phenyl or benzhydryl are tolerated. The same protocol also allows the unprecedented addition to representative ketone-derived imines.

Enantioselective Strecker-type reaction of phosphinoyl ketimines catalyzed by a chiral Zr-bipyridyldiol catalyst

An enantioselective Strecker reaction of N-diphenylphosphinoyl ketimines with TMSCN employing a chiral zirconium complex formed from chiral bipyridyl diol 1 as catalyst is described. The catalytic efficiency of chiral ligand 1 with other Lewis acids was also explored. Higher yields (50-85%) with moderate to good enantioselectivities (30-80%) were achieved for a variety of N-diphenylphosphinoyl ketimines.

1,2-Addition of trialkylaluminium reagents to N- diphenylphosphinoylketimines in the absence of any additional reagents

Using reactive trialkylaluminium reagents for the 1,2-addition on acetophenone- and benzophenone-derived ketimines, α-trisubstituted amines were obtained in excellent yields up to 99%. The Royal Society of Chemistry.

Enantioselective reduction of imines catalyzed by a rhenium(V)-oxo complex

An air- and moisture-tolerant enantioselective hydrosilylation of N-phosphinyl imines employing a chiral Re(V)-oxo complex as a catalyst is described. The chiral catalyst is a cyanobis(oxazoline) (CNbox)-ligated rhenium-oxo complex of the general formula