70749-06-3

Usage

Uses

Used in Catalyst and Ligand Applications:
(1S,2S)-(-)-N,N'-DIMETHYL-1,2-DIPHENYL-1,2-ETHANE DIAMINE is used as a precursor for the synthesis of chiral imidazolinium salts, which serve as catalysts for aza Diels-Alder reactions and as shift reagents for the potassium salt of Mosher's acid. This application is crucial in the field of organic chemistry, where these reactions are essential for the formation of complex molecular structures.
Used in Pharmaceutical Industry:
(1S,2S)-(-)-N,N'-DIMETHYL-1,2-DIPHENYL-1,2-ETHANE DIAMINE is used as a ligand in the preparation of 2,3-dihydrobenzofurans and indanes by reacting alkyl halides with alkyl electrophiles using nickel/diamine catalyst. This application is significant in the synthesis of various pharmaceutical compounds, as these chemical structures are often found in drugs with diverse therapeutic properties.
Used in Chemical Synthesis:
(1S,2S)-(-)-N,N'-DIMETHYL-1,2-DIPHENYL-1,2-ETHANE DIAMINE is used as a ligand in the synthesis of carbamates, sulfonamides, and sulfones through alkyl-alkyl Suzuki reaction using Ni catalyst. This application is vital in the chemical industry, as these compounds are widely used in the production of various chemicals, agrochemicals, and pharmaceuticals.

Upstream product

• 622-29-7 N-Benzylidenemethylamine 
• 100-52-7 benzaldehyde 
• 22751-68-4 (+/-)-N,N'-dimethyl-1,2-diphenyl-1,2-ethylenediamine 
• 69019-77-8 N,N'-Dimethyl-1,2-diphenyl-N,N'-bis-trimethylsilanyl-ethane-1,2-diamine 
• 951-87-1 rac-1,2-diphenylethylene-1,2-diamine 
• 60509-62-8 (R,S)-N,N'-dimethyl-1,2-diphenylethylenediamine 
• 3969-04-8 Diethyl N,N'-(1,2-diphenylethylene)biscarbamate 
• 29841-69-8 (S,S)-1,2-diphenyl-1,2-diaminoethane 
• 541-41-3 chloroformic acid ethyl ester 
• 220665-71-4 N-((1S,2S)-2-Formylamino-1,2-diphenyl-ethyl)-formamide 
• 234753-20-9 diethyl ((1S,2S)-1,2-diphenylethane-1,2-diyl)dicarbamate 

Downstream Products

• 133634-31-8 3-(1,3-Dimethyl-4(S),5(S)-diphenylimidazolidin-2-yl)pyridine 
• 119092-13-6 (4S,5S)-1,3-Dimethyl-2-(2-methyl-pentyl)-4,5-diphenyl-imidazolidine 
• 135075-64-8 Methyl (4S,5S)-(-)-(E)-3-(1,3-Dimethyl-4,5-diphenylimidazolidin-2-yl)propenoate 
• 119092-11-4 (4S,5S)-1,3-Dimethyl-4,5-diphenyl-2-(2-phenyl-propyl)-imidazolidine 
• 119092-08-9 (4S,5S)-2-Cyclohex-3-enyl-1,3-dimethyl-4,5-diphenyl-imidazolidine 
• 131035-33-1 2-((4S,5S)-1,3-Dimethyl-4,5-diphenyl-imidazolidin-2-yl)-benzaldehyde 
• 203062-94-6 (4S,5S)-2-Chloro-1,3-dimethyl-4,5-diphenyl-[1,3,2]diazaphospholidine 2-oxide 
• 234753-26-5 (S,S)-1,2-bis(N-methyl-α-chloroacetamido)-1,2-diphenylethane 

Relevant academic research and scientific papers

Development of Chiral Organosuperbase Catalysts Consisting of Two Different Organobase Functionalities

In the field of chiral Br?nsted base catalysis, a new generation of chiral catalysts has been highly anticipated to overcome the intrinsic limitation of pronucleophiles that are applicable to the enantioselective reactions. Herein, we reveal conceptually new chiral Br?nsted base catalysts consisting of two different organobase functionalities, one of which functions as an organosuperbase and the other as the substrate recognition site. Their prominent activity, which stems from the distinctive cooperative function by the two organobases in a single catalyst molecule, was demonstrated in the unprecedented enantioselective direct Mannich-type reaction of α-phenylthioacetate as a less acidic pronucleophile. The present achievement would provide a new guiding principle for the design and development of chiral Br?nsted base catalysts and significantly broaden the utility of Br?nsted base catalysis in asymmetric organic synthesis.

Substrate-Induced Dimerization Assembly of Chiral Macrocycle Catalysts toward Cooperative Asymmetric Catalysis

An artificial system of substrate-induced dimerization assembly of chiral macrocycle catalysts enables a highly cooperative hydrogen-bonding activation network for efficient enantioselective transformation. These macrocycles contain two thiourea and two chiral diamine moieties and dimerize with sulfate to form a sandwich-like assembly. The macrocycles then adopt an extended conformation and reciprocally complement the hydrogen-bonding interaction sites. Inspired by the guest-induced dynamic assembly, these macrocycles catalyze the decarboxylative Mannich reaction of cyclic aldimines containing a sulfamate heading group. The imine substrate can be activated toward nucleophilic attack of β-ketoacid by a cooperative hydrogen-bonding network enabled by sulfamate-induced dimerization assembly of the macrocycle catalysts. Highly efficient (>95 % yield in most cases) and enantioselective (up to 97.5:2.5 er) transformation of a variety of substrates using only 5 mol % macrocycle was achieved.

Dynamic Kinetic Resolution of Heterobiaryl Ketones by Zinc-Catalyzed Asymmetric Hydrosilylation

A diastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile heterobiaryl ketones is described. The DKR proceeds by zinc-catalyzed hydrosilylation of the carbonyl group, thus leading to secondary alcohols bearing axial and central chirality. The strategy relies on the labilization of the stereogenic axis that takes place thanks to a Lewis acid–base interaction between a nitrogen atom in the heterocycle and the ketone carbonyl group. The synthetic utility of the methodology is demonstrated through stereospecific transformations into either N,N-ligands or appealing axially chiral, bifunctional thiourea organocatalysts.

Vanadium(I) chloride and lithium vanadium(I) dihydride as selective epimetallating reagents for π- and σ-bonded organic substrates

Subvalent vanadium(I) salts, of empirical formulas, VCl, vanadium(I) chloride and LiVH2, lithium vanadium(I) dihydride, whose efficient preparation, structural constitution and mode of reaction toward certain organic substrates have been described in a preceding article, are here evaluated in their reactions toward a wide variety of π- and σ-bonded organic substrates, namely carbonyl, imine, azo, alkene, 1,3-diene, nitrile π-bonds and C-X, C-O, C-N and N-N σ-bonds. Compared with the high reactivity of CrCl and LiCrH2 reagents in attacking both types of bonds, the VCl and LiVH2 reagents were much milder and selective in epimetallating π-bonds, often forming the 1:1 adduct of LiVH2 and π-bonded substrate as the major product. Finally, the vanadium reagents showed little tendency to cleave C-O, C-S and C-N bonds and a smaller scope in cleaving C-X bonds than their chromium counterparts. Because of their selectivity these vanadium reagents offer the following preparative promise: 1) smooth McMurry carbonyl coupling to their reductive dimers; 2) deoxygenation of epoxides; 3) selective aromatic C-X reduction; 4) high yields of epimetallated carbonyls or imines as intermediates to α-hydroxy and α-amino acids; 5) 1,4-reductions of 1,3-alkadienes; 6) reductive dimerization of nitriles to ketones; 7) 1,4 or 1,n-epimetallations leading to acyloins or indoles; and 8) reductive dimerizations of azines to produce unusual imidazole derivatives. In explaining the greater kinetic stability of the 1:1 LiVH2 adduct with carbonyl or imine substrates it is pointed out that such epimetallated adducts from LiVH2 would likely be diamagnetic, whereas such adducts from LiCrH2 have an unpaired electron on the Cr center and hence would rupture, so that the electron would be on the C center. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Synthesis, resolution, and application of 2,2′-bis(diphenylphosphino) -3,3′-binaphtho[b]furan (BINAPFu)

(±)-2,2′-Bis(diphenylphosphino)-3,3′-binaphtho[2,1-b] furan (BINAPFu) was synthesized from 2-naphthoxyacetic acid in a five-step sequence in 62% overall yield. A variety of reported resolution procedures for biaryl bisphosphines did not work with (±)-BINAPFu; thus, a new resolution method was developed, involving the Staudinger reaction of the aforementioned racemate of BINAPFu with an enantiopure camphor sulfonyl azide derivative. The resulting diastereomeric phosphinimines were separated by flash chromatography. Subsequent hydrolysis to the corresponding bis-phosphine oxide and trichlorosilane reduction provided enantiopure BINAPFu. The absolute stereochemical configuration of BINAPFu was established by X-ray crystallography. BINAPFu was compared with commercially available 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (BINAP) in Pd(0)-catalyzed intermolecular Heck reactions. Investigation of the Heck arylation of 2,3-dihydrofuran showed BINAPFu to be more efficacious than BINAP in dioxane at 30°C. A variety of phosphorus selenides were prepared, and the 1JP-Se coupling constants measured, to obtain a comparative scale of parent phosphine basicity. The phosphorus atoms in BINAPFu were found to be electron deficient when compared with BINAP but slightly more electron rich than trifurylphosphine.

An efficient method for the synthesis of N,N′-dimethyl-1,2-diamines

A simple method for the preparation of N,N′-dimethyl-1,2-diamines is described. The method requires the dimethylation of a diazaphospholidine oxide followed by acid-catalysed hydrolysis.

Synthesis of phosphoramides for the lewis base-catalyzed allylation and aldol addition reactions

Both chiral and achiral phosphoramides of diverse structure were prepared from diamines by the coupling to phosphorus(V) or phosphorus(III) reagents. Several enantiopure 1,2-diphenyl-1,2-ethanediamine analogues have been prepared by the reductive coupling of the corresponding N-silylimine with NbCl4(THF)2 and subsequent resolution by the formation of diastereomeric menthyl carbamates. (S,S)-N,N'-Di-(1-naphthyl)-1,2-diphenyl- 1,2-ethanediamine 15 was prepared by the arylation of (S,S)-1,2-diphenyl- 1,2-ethanediamine with naphthyl iodide.

Synthesis of chiral azamacrocycles using the bis(α-chloroacetamide)s derived from chiral 1,2-diphenylethylenediamine

Optically active diphenyl-substituted tetraaza-12-crown-4 diamide (10), tetraaza-15-crown-5 diamide (12), tetraaza-18-crown-6 diamide (11), and hexaaza-18-crown-6 diamide (9) ligands were prepared by treating the appropriate secondary diamines with the (R,R)- and (S,S)- forms of 1,2- bis(N-methyl-α-chloracetamido)-1,2diphenylethane (20). Macrocyclic diamides 9 and 10 were reduced to form the optically active diphenyl-substituted hexaaza-18-crown-6 (13) and tetraaza-12-crown-4 (14), respectively. Reduction of macrocyclic diamide ligands 11 and 12 gave a complex mixture of products from which the desired tetraaza-15-crown-5 and 18-crown-6 compounds could not be isolated. Dichloride 20 was prepared by treating the chiral forms of 1,2- diphenylethylenediamine with chloroacetic anhydride or chloroacetyl chloride. The crystal structures for the (R,R)-form of dichloride 20 and the (S,S)-forms of macrocycles 10 and 11 are reported.

Stereoselective pinacol coupling of planar chiral (benzaldehyde)Cr(Co)3, (benzaldimine)Cr(CO)3, ferrocenecarboxaldehyde and (dienal)Fe(CO)3 complexes with samarium diiodide

An intermolecular pinacol coupling of the Planar chiral tricarbonylchromium complexes of o-substituted benzaldehydes or benzaldimines with samarium(II) diiodide in THF produces exclusively threo 1.2-diols or 1,2-diamines in an optically pure form, while the corresponding racemic o- substituted benzaldehyde or benzaldimine chromium complexes give a mixture of threo and erythro pinacol coupling products in a various ratio depending upon the nature of o-substituent. Similarly, planar chiral 2-substituted ferrocenecarboxaldehydes and (dienal)Fe(CO)3 produce the corresponding 1.2- diols with high stereoselectivity. The generated transition metal-complexed ketyl radical intermediates are configurationally stable with restriction to a rotation about C(α)-C(ipso) bond.