14367-95-4

Upstream product

• 42428-03-5 (3-chlorophenyl)(1H-imidazol-1-yl)methanone 
• 75-52-5 nitromethane 
• 535-80-8 3-chlorobenzoate 
• 587-04-2 m-Chlorobenzaldehyde 
• 509-14-8 tetranitromethane 
• 2039-85-2 3-Chlorostyrene 
• 39220-98-9 1-(3-chlorophenyl)-2-nitroethanol 
• 25854-38-0 sodium nitromethane 
• 41998-17-8 phenyl 3-chlorobenzoate 

Downstream Products

• 90877-93-3 1-(3-Chlorophenyl)-1-ethylthio-2-nitroethylene 
• 1377577-63-3 3-chloro-N-tosylbenzamide 
• 67162-28-1 3,4-bis(3'-chlorobenzoyl)-1,2,5-oxadiazole-2-oxide 
• 90877-90-0 1-(1,1-Bis-ethylsulfanyl-2-nitro-ethyl)-3-chloro-benzene 
• 14547-40-1 1-(3-chloro-phenyl)-3-morpholin-4-yl-2-nitro-propan-1-one 

Relevant academic research and scientific papers

Synthesis of 3-nitroindoles by sequential paired electrolysis

3-Nitroindoles are synthetically versatile intermediates but current methods for the preparation hinder their widespread application. Herein, we report that nitroenamines undergo electrochemical cyclisation to 3-nitroindoles in the presence of potassium iodide. Detailed control experiments and cyclic voltammogram studies infer the reaction proceedsviaa sequential paired electrolysis process, beginning with anodic oxidation of iodide (I?) to the iodine radical (I˙), which facilitates cyclisation of the nitroenamine to give a 3-nitroindolinyl radical. Cathodic reduction and protonation generates a 3-nitroindoline that upon oxidation forms the 3-nitroindole.

Denitrative imino-diaza-Nazarov cyclization: Synthesis of pyrazoles

An iodine-catalyzed denitrative imino-diaza-Nazarov cyclization (DIDAN) methodology has been developed for the synthesis of pyrazoles with high to excellent yields by using α-nitroacetophenone derivatives and in situ generated hydrazones. The key transformation of this oxidative 4π-electrocyclization proceeds through an enamine-iminium ion intermediate. This rapid one-pot DIDAN protocol results in the selective generation of C-C and C-N bonds and cleavage of a C-N bond. This journal is

Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones

We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.

Organocatalytic asymmetric Michael/hemiacetalization/acyl transfer reaction of α-nitroketones with o-hydroxycinnamaldehydes: Synthesis of 2,4-disubstituted chromans

An organocatalytic asymmetric cascade Michael/hemiketalization/acyl transfer reaction between o-hydroxycinnamaldehydes and α-nitroketones is developed. Prolinol TMS ether catalyst in combination with benzoic acid was found to be the most effective for this reaction which proceeds through an equilibrium of lactols to provide a single diastereomer of enantiopure 2,4-disubstituted chromans.

Organocatalytic Asymmetric Domino Michael/Acyl Transfer Reaction Between α-Nitroketones and in situ-Generated ortho-Quinone Methides: Route to 2-(1-Arylethyl)phenols

An organocatalytic asymmetric domino Michael/acyl transfer reaction between α-nitroketones and o-quinone methides is disclosed. o-Quinone methides are generated in situ from 2-sulfonylmethylphenols in basic medium. With 10 mol% of bifunctional squaramide catalyst, high yields and excellent enantioselectivities are achieved for a variety of O-acyl 2-(1-arylethyl)phenols under mild reaction condition. (Figure presented.).

Asymmetric Bioreduction of β-Acylaminonitroalkenes: Easy Access to Chiral Building Blocks with Two Vicinal Nitrogen-Containing Functional Groups

The reduction of (Z)-β-acylaminonitroalkenes catalyzed by ene-reductases is described for the first time. The reaction occurs with a high conversion and excellent enantioselectivity and shows a wide substrate scope. The reduced products are valuable chiral synthons characterized by two vicinal nitrogen-containing functional groups that can be further modified by functional group inter-conversion thanks to the synthetic versatility of the nitro moiety. The chemo-enzymatic synthesis of (R)-N,N′-(1-phenylethane-1,2-diyl)diacetamide from easily accessible (Z)-N-(2-nitro-1-phenylvinyl)acetamide is herein reported as a representative application of this synthetic procedure.

Unexpected C-C bond cleavage of α-nitroketone in the presence of TsNBr2: A new pathway for C-N bond formation

A new catalyst-free protocol for C-N bond formation via the cleavage of α-nitroketone has been developed. When α-nitroketones are treated with TsNBr2 in the presence of potassium carbonate, unexpected cleavage of C(O)-CHNO2 bond of α-nitroketone was observed followed by the formation of corresponding amide. Various nitroketones could be converted to corresponding amide using this procedure.

Formation of new C-O and C-N bonds via base promoted Csp2-Csp3 bond cleavage of α-nitro ketone

A catalyst free protocol has been developed for nucleophilic Csp2-Csp3 bond cleavage of α-nitroketone in the presence of potassium carbonate to create new C-O and C-N bonds. A series of different substituted α-nitroketones could be selectively cleaved and converted into corresponding esters and tosylamides in the presence of alcohols and bromamine-T, respectively.

Rhodium-catalyzed enantioselective hydrogenation of β-acylamino nitroolefins: A new approach to chiral β-amino nitroalkanes

An efficient and highly enantioselective catalytic asymmetric hydrogenation of β-acylamino nitroolefins has been realized by using Rh-TangPhos as the catalyst. A series of β-amino nitroalkane products, which are versatile intermediates in organic synthesis, were obtained with high yield and good enantioselectivity.

Highly enantioselective reduction of β-amino nitroolefins with a simple n-sulfinyl urea as bifunctional catalyst

Simple but effective: A structurally simple N-sulfinyl urea was found to be a highly efficient bifunctional catalyst, which allows for the development of a novel pathway for the construction of chiral β-amino nitroalkanes through enantioselective reduction of β-amino nitroolefins by trichlorosilane. High yields and excellent enantioselectivities were obtained for a broad range of β-arylamino nitroolefin substrates (see scheme). Copyright