82598-06-9

Upstream product

• 82572-09-6 C₂₄H₂₀NOP 
• 941-98-0 1'-naphthacetophenone 
• 942066-01-5 N-[(E)-1-(1-naphthyl)ethylidene]diphenylphosphinic amide 
• 100485-51-6 (E)-1-(naphthalen-1-yl)ethanone oxime 
• 1079-66-9 chloro-diphenylphosphine 
• 10420-89-0 (S)-1-(1-Naphthyl)ethylamine 
• 1956-40-7 1-(1-naphthalenyl)ethanone oxime 

Relevant academic research and scientific papers

Synthesis of P-stereogenic diarylphosphinic amides by directed lithiation: Transformation into tertiary phosphine oxides via methanolysis, aryne chemistry and complexation behaviour toward zinc(II)

The highly diastereoselective synthesis of P-stereogenic phosphinic amides via directed ortho lithiation (DoLi) of (SC)-P,P-diphenylphosphinic amides with t-BuLi followed by electrophilic quench reactions is described. Functionalised derivatives containing a wide variety of ortho substituents (Cl, Br, I, OH, N3, SiMe3, SnMe3, P(O)Ph2, Me, allyl, tBuOCO) have been prepared in high yields with diastereomeric ratios up to 98:2. The X-ray diffraction structure of the ortho-stannylated and ortho-iodo compounds showed that the pro-S P-phenyl ring was stereoselectively ortho-deprotonated by the organolithium base. The usefulness of the method is supported by two key transformations, the synthesis of P-stereogenic methyl phosphinates through replacement of the chiral auxiliary by a methoxy group and the first example of the insertion of benzyne into the P-N bond of a P-stereogenic phosphinic amide. A DFT study of this reaction showed that the insertion proceeds through a [2 + 2] cycloaddition and a subsequent ring-opening with retention of the P-configuration. Explorative coordination chemistry of the new P-stereogenic ligands provided access to a chiral phosphinic amide-phosphine oxide Zn(ii) complex, the crystal structure of which is reported.

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.

Enantioselective Hydrosilylation of Imines Catalyzed by Chiral Zinc Acetate Complexes

A series of zinc acetate complexes with optically pure diphenylethanediamine (DPEDA)-derived ligands have been employed as enantioselective catalyst for the hydrosilylation of various imines. High control of stereoselectivity (up to 97% ee) and excellent yields (up to 96%) were gained for a broad range of N-phosphinoylimines by using (R,R)-N,N′-dibenzyl-1,2-diphenylethane-1,2-diamine. This is the first successful application of an air-stable and environmentally friendly chiral Zn(OAc)2 complex instead of the previously used harmful diethylzinc in the asymmetric reduction of the C=N double bond.

Asymmetric Reduction of Phosphinyl Imines with Hydride Reagents. Enantioselective Synthesis of Chiral Primary Amines

Prochiral diphenylphosphinyl imines are asymmetrically reduced by chiral hydride reagents to chiral diphenylphosphinylamines.For dialkyl examples, the enantioselectivities obtained are the highest thus far for hydride reductions of imine derivatives.