15725-33-4

Upstream product

• 620-23-5 m-tolyl aldehyde 
• 105-53-3 diethyl malonate 

Downstream Products

• 87707-93-5 2-[(2-Amino-phenylsulfanyl)-(3-chloro-phenyl)-methyl]-malonic acid diethyl ester 
• 87707-92-4 2-[(2-Amino-phenylsulfanyl)-m-tolyl-methyl]-malonic acid diethyl ester 
• 87707-65-1 (2R,3S)-4-Oxo-2-m-tolyl-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepine-3-carboxylic acid ethyl ester 
• 1211-32-1 2-(m-tolyl)benzo[d]thiazole 
• 1374878-11-1 tert-butyl 2-(3-ethoxy-2-(ethoxycarbonyl)-3-oxo-1-m-tolylpropyl)-5-oxo-2H-pyrrole-1(5H)-carboxylate 
• 1359859-35-0 C₂₈H₃₁NO₄ 
• 1146217-33-5 (R)-ethyl 2-ethoxycarbonyl-3-(3-indolyl)-3-(m-methylphenyl)propanoate 
• 1217022-71-3 ethyl 2-carbethoxy-3-cyano-3-(3-methylphenyl)propionate 
• 87707-80-0 Toluene-4-sulfonic acid (2S,3S)-2-(3-chloro-phenyl)-4-oxo-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepin-3-ylmethyl ester 
• 87707-83-3 (2S,3S)-2-(3-Chloro-phenyl)-3-(4-methyl-piperazin-1-ylmethyl)-2,3-dihydro-5H-benzo[b][1,4]thiazepin-4-one 
• 87707-83-3 (2S,3R)-2-(3-Chloro-phenyl)-3-(4-methyl-piperazin-1-ylmethyl)-2,3-dihydro-5H-benzo[b][1,4]thiazepin-4-one 
• 87707-66-2 (2R,3S)-2-(3-Chloro-phenyl)-4-oxo-2,3,4,5-tetrahydro-benzo[b][1,4]thiazepine-3-carboxylic acid ethyl ester 
• 87707-72-0 (2S,3S)-2-(3-Chloro-phenyl)-3-hydroxymethyl-2,3-dihydro-5H-benzo[b][1,4]thiazepin-4-one 
• 22868-31-1 2-(3-chlorophenyl)benzothiazole 

Relevant academic research and scientific papers

Ball-Milling-Enabled Reactivity of Manganese Metal**

Efforts to generate organomanganese reagents under ball-milling conditions have led to the serendipitous discovery that manganese metal can mediate the reductive dimerization of arylidene malonates. The newly uncovered process has been optimized and its mechanism explored using CV measurements, radical trapping experiments, EPR spectroscopy, and solution control reactions. This unique reactivity can also be translated to solution whereupon pre-milling of the manganese is required.

Unnatural α-amino ethyl esters from diethyl malonate or ethyl β-bromo-α-hydroxyiminocarboxylate

We have explored here the scope of the age-old diethyl malonate-based accesses to α-amino esters involving Knoevenagel condensations of diethyl malonate on aldehydes, reductions of the resulting alkylidenemalonates, the preparation of the corresponding α-hydroxyimino esters and their final reduction. This synthetic pathway turned out to be general although some unexpected limitations were encountered. The synthetic modifications of some of the intermediates - using Suzuki-Miyaura coupling or cycloadditions - before undertaking the oximation step - provided accesses to further α-amino esters. Moreover, other pathways to α-hydroxyimino esters were explored including an attempt to improve the cycloadditions between ethyl β-bromo-α-hydroxyiminocarboxylate and various alkylfuranes.

Synthesis of nitrogen heterocycles via α-aminoalkyl radicals generated from α-silyl secondary amines under visible light irradiation

We have succeeded in the visible light-mediated synthetic use of α-aminoalkyl radicals derived from α-silyl secondary amines toward addition to α,β-unsaturated carbonyl compounds. The resulting γ-aminocarbonyl compounds are converted into γ-lactams and pyrroles in a one-pot process. This journal is the Partner Organisations 2014.

Nickel(ii)-catalyzed enantioselective 1,3-dipolar cycloaddition of azomethine imines with alkylidene malonates

We demonstrated an asymmetric 1,3-dipolar cycloaddition of azomethine betaines with alkylidene malonates by using a chiral N,N'-dioxide- NiII complex as a catalyst. Both aromatic- and aliphatic-substituted alkylidene malonates were found to be suitable for the reaction. A range of transpyrazolone derivatives was exclusively obtained with excellent yields (up to 99% yield) and good enantioselectivities (up to 97% ee) under mild reaction conditions. The reaction could be carried out on a gram scale with the good results being maintained. Control experiments were performed to elucidate the specific diastereoselectivity of the reaction. The formation of single trans isomers was dominated by secondary orbital interactions between the ester groups of the dipolarophile and the azomethine imine. On the basis of the experimental results and previous reports, a possible catalytic model was assumed.

Chiral-Zn(NTf2)2-complex-catalyzed diastereo- and enantioselective direct conjugate addition of arylacetonitriles to alkylidene malonates

Chiral N,N′-dioxide/Zn(NTf2)2 complexes were demonstrated to be highly effective in the direct asymmetric conjugate addition of arylacetonitriles to alkylidene malonates under mild conditions. A wide range of substrates were tolerated to afford their corresponding products in moderate-to-good yields with high diastereoselectivities (82:18->99:1 d.r.) and enantioselectivities (81-99 % ee). The reactions performed well, owing to the high Lewis acidity of the metal triflimidate and a ligand-acceleration effect. The N,N′-dioxide also benefited the deprotonation process as a Bronsted base. The catalytic reaction could be performed on the gram-scale with retention of yield, diastereoselectivity, and enantioselectivity. The products that contained functional groups were ready for further manipulation. In addition, a possible catalytic model was proposed to explain the origin of the asymmetric induction. Copyright

Asymmetric cyanation of activated olefins with ethyl cyanoformate catalyzed by a modular titanium catalyst

"Chemical Equation Presented" Asymmetric cyanation of a class of easily available olefins with a favorable cyanide source ethyl cyanoformate (CNCOOEt) was realized by an interesting modular catalyst. High yields and ee values were obtained for a range of substrates under solvent-free and mild reaction conditions. The products obtained could be easily transformed to the enantioenriched useful intermediates 5,6, and pharmaceutically Important γ-aminobutyric acid 7.

A convenient synthesis of the (E)-monoacetates of 2-alkylidenepropane-1,3- diols

Various kinds of 3-substituted (E)-2-(hydroxymethyl)prop-2-enyl acetates were conveniently obtained in excellent yields by the regiospecific acetylation of 2-alkylidenepropane-1,3-diols with 10 equivalents of vinyl acetate in the presence of 50% w/w porcine pancreatic lipase (PPL) type II; the starting materials or (Z)-monoacetate or diacetate byproducts were generally not present. Georg Thieme Verlag Stuttgart.