33432-53-0

Upstream product

• 33432-47-2 Aethyl(4-p-nitrophenyl-2-methyl-3-butyn-2-yl)acetal (IIIc) 
• 115-19-5 2-methyl-but-3-yn-2-ol 
• 586-78-7 para-nitrophenyl bromide 
• 636-98-6 p-nitrobenzene iodide 
• 100-00-5 4-chlorobenzonitrile 

Downstream Products

• 937-31-5 (4-Nitrophenyl)acetylene 
• 1942-30-9 4-(phenylethynyl)nitrobenzene 
• 952527-71-8 carbonic acid 1,1-dimethyl-3-(4-nitro-phenyl)-prop-2-ynyl ester methyl ester 
• 952527-28-5 4-methyl-2-(4-nitro-phenyl)-penta-2,3-dienoic acid methyl ester 
• 35487-34-4 3-(4-nitrophenyl)prop-2-ynal 
• 83758-93-4 3-(4-nitrophenyl)prop-2-ynal diethyl acetal 
• 7642-33-3 1-(buta-1,3-diyn-1-yl)-4-nitrobenzene 
• 100727-43-3 2-methyl-6-(4-nitrophenyl)hexa-3,5-diyn-2-ol 
• 1374593-83-5 2-amino-5,5-dimethyl-4-(4-nitrobenzylidene)-2-oxazoline 
• 1415694-18-6 1,1-dimethyl-8-(4-nitrophenyl)-3-phenyl-1H-indeno[1,2-c]furan 
• 39082-40-1 1-[2-(4-methoxyphenyl)ethynyl]-4-nitrobenzene 
• 1621104-66-2 3-hydroxy-3-methyl-1-(4-nitrophenyl)butan-2-one 
• 1621104-49-1 1-(4-aminophenyl)-3-hydroxy-3-methylbutan-2-one 
• 1621104-50-4 3-methyl-1-(4-nitrophenyl)butane-2,3-diol 

Relevant academic research and scientific papers

Reaction of 4-aryl-2-methylbut-3-yn-2-ols with thiourea as a new approach to the synthesis of 4-arylmethylidene-5,5-dimethyl-4,5-dihydrothiazole-2-amines

A reaction of thiourea with 4-aryl-2-methylbut-3-yn-2-ols in refluxing pyridine led to the synthesis of 4-arylmethylidene-5,5-dimethyl-4,5- dihydrothiazole-2-amines.

Rip It off: Nitro to Nitroso Reduction by Iron Half-Sandwich Complexes

Activation of [FeCl(dppe)Cp] (1) by chloride abstraction with Na[BArX4] (X = F, [B(3,5-(CF3)2-C6H3)4]; X = Cl, [B(3,5-Cl2-C6H3)4]) permits reactions with a range of nitro aromatics, RC6H4NO2 (R = halogen, Me, OMe, NO2 or NMe2), to give the cationic iron nitroso complexes [Fe{N(O)-C6H4R}(dppe)Cp][BArX4]) ([3][BArX4]). Similar reactions of 1 and Na[BArX4] with [Fe(NCC6H4NO2)(dppe)Cp][BArX4] gave bimetallic [{Fe(dppe)Cp}2{μ-NCC6H4N(O)}][BArF4]2. However, reactions of 1 and Na[BArX4] with 4-nitrophenol gave the first example of the bench-stable iron half-sandwich phenolate complex [Fe(OC6H4NO2)(dppe)Cp]+ rather than NO2 activation. The formation of complexes [3]+ likely proceeds via the unusual blue bimetallic species [{Fe(dppe)Cp}2{μ,κ2O,O′-O2NAr}]2+. This compound undergoes N-O bond cleavage, resulting in [3]+ and a FeIV=O species, which reacts via an internal C-H activation of the dppe ligand to give [FeIII(κ3O,P,P′-P(2-O-C6H4)(Ph)-C2H4-PPh2)Cp]+. Complexes [3]+ are stable under ambient conditions, are readily purified by column chromatography and can be isolated in up to 50% yield, considering that 0.5 equiv of 1 is required as the oxygen acceptor.

Hydrazine Hydrate Accelerates Neocuproine–Copper Complex Generation and Utilization in Alkyne Reduction, a Significant Supplement Method for Catalytic Hydrogenation

Diimine (HN═NH) is a strong reducing agent, but the efficiency of diimine oxidized from hydrazine hydrate or its derivatives is still not good enough. Herein, we report an in situ neocuproine–copper complex formation method. The redox potential of this complex enable it can serve as an ideal redox catalyst in the synthesis of diimine by oxidation of hydrazine hydrate, and we successfully applied this technique in the reduction of alkynes. This reduction method displays a broad functional group tolerance and substrate adaptability as well as the advantages of safety and high efficiency. Especially, nitro, benzyl, boc, and sulfur containing alkynes can be reduced to the corresponding alkanes directly, which provides a useful complementary method to traditional catalytic hydrogenation. Besides, we applied this method in the preparation of the Alzheimer’s disease drug CT-1812 and studied the mechanism.

Ru(ii)-catalyzed allenylation and sequential annulation of: N -tosylbenzamides with propargyl alcohols

We hereby report Ru(ii)-catalyzed C(sp2)-H allenylation of N-tosylbenzamides to access multi-substituted allenylamides. Furthermore, the allenylamides were converted to the corresponding isoquinolone derivatives via base mediated annulation. The current protocol features low catalyst loading, mild reaction conditions, high functional group compatibility and desired scalability. The unique functionality of the afforded allenes allowed further transformations to expand the practicality of the protocol. This journal is

Rhodium-Catalyzed Annulation of Phenacyl Ammonium Salts with Propargylic Alcohols via a Sequential Dual C-H and a C-C Bond Activation: Modular Entry to Diverse Isochromenones

Given their omnipresence in natural products and pharmaceuticals, isochromenone congeners are one of the most privileged scaffolds to synthetic chemists. Disclosed herein is a dual (ortho/meta) C-H and C-C activation of phenacyl ammonium salts (acylammonium as traceless directing group) toward annulation with propargylic alcohols to accomplish rapid access for novel isochromenones by means of rhodium catalysis from readily available starting materials. This operationally simple protocol features broad substrate scope and wide functional group tolerance. Importantly, the protocol circumvents the need of any stoichiometric metal oxidants and proceeds under aerobic conditions.

Utilizing a copper-free Sonogashira reaction in the synthesis of the leukotriene a4 hydrolase modulator batatasin IV

Batatasin IV is a dihydrostilbenoid isolated from Chinese yams which was shown to have inhibitory activities against plant growth. Later studies showed that this compound may exhibit anti-inflammatory properties by inhibiting the epoxide hydrolase activity of the leukotriene A4 hydrolase enzyme. To access the dihydrostilbenoid skeleton, a copper-free SPhos-mediated Sonogashira reaction was conceived and the substrate scope was explored. Our results indicate that the reaction can tolerate the presence of free alcohols, aldehydes, nitro groups, and anilinyl groups. However, a substituent with an acidic phenol or carboxylic acid group gave significantly lower yields. Next, a total synthesis of batatasin IV was accomplished in 16% overall yield incorporating the reported copper-free Sonogashira reaction. Finally, we show that batatasin IV inhibits the hydrolysis of alanine p-nitroanilide by leukotriene A4 hydrolase with an IC50 of 91.4 μM.

Design, synthesis, antileishmanial, and antifungal biological evaluation of novel 3,5-disubstituted isoxazole compounds based on 5-nitrofuran scaffolds

Nineteen 3,5-disubstituted-isoxazole analogs were synthesized based on nitrofuran scaffolds, by a [3 + 2] cycloaddition reaction between terminal acetylenes and 5-nitrofuran chloro-oxime. The compounds were obtained in moderate to very good yields (45–91%). The antileishmanial activity was assayed against the promastigote and amastigote forms of Leishmania (Leishmania) amazonensis. Alkylchlorinated compounds 14p–r were active on both the promastigote and amastigote forms, with emphasis on compound 14p, which showed strong activity against the amastigote form (IC50 = 0.6 μM and selectivity index [SI] = 5.2). In the alkyl series, compound 14o stands out with an IC50 = 8.5 μM and SI = 8.0 on the amastigote form. In the aromatic series, the most active compounds were those containing electron-donor groups, such as trimethoxy isoxazole 14g (IC50 = 1.2 μM and SI = 20.2); compound 14h, with IC50 = 7.0 μM and SI = 6.1; and compound 14j containing the 4-SCH3 group, with IC50 = 5.7 μM and SI = 10.2. In addition, the antifungal activity of 19 nitrofuran isoxazoles was evaluated against five strains of Candida (C. albicans, C. parapsilosis, C. krusei, C. tropicalis, and C. glabrata). Eleven isoxazole derivatives were active against C. parapsilosis, and compound 14o was found to be the most active (minimal inhibitory concentration [MIC] = 3.4 μM) for this strain. Compound 14p was active against all the strains tested, with an MIC = 17.5 μM for C. glabrata, lower than that of the fluconazole used as the reference drug.

α-Hydroxy Ketones as Masked Ester Donors in Br?nsted Base Catalyzed Conjugate Additions to Nitroalkenes

The catalyst-controlled enantioselective direct addition reaction of enolizable esters and related carboxylic acid derivatives to π electrophiles remains a difficult synthetic transformation. In this study, the suitability of α-hydroxy ketones as ester equivalents capable of being activated by bifunctional Br?nsted base catalysts in the context of conjugate addition reactions to nitroolefins is demonstrated. The scope of the reaction, which affords the corresponding Michael adducts with very high stereoselectivity (diastereomeric ratio (d.r.) ≥95:5, up to 99 % enantiomeric excess (ee)), and its limitations are explored, as is the aftermath elaboration of adducts into densely functionalized enantioenriched products.

Rhodium-Catalyzed Highly Regio- and Enantioselective Hydrogenation of Tetrasubstituted Allenyl Sulfones: An Efficient Access to Chiral Allylic Sulfones

A highly regio- and enantioselective hydrogenation of challenging tetrasubstituted allenyl sulfones has been developed, affording chiral allylic sulfones in good yields with excellent regio- and enantioselectivities (up to 99 % yield and 99 % ee). This me

Synthesis and Simple Immobilization of Palladium(II) Acyclic Diaminocarbene Complexes on Polystyrene Support as Efficient Catalysts for Sonogashira and Suzuki-Miyaura Cross-Coupling

Immobilization of palladium(II) acyclic diaminocarbene (Pd(II)-ADC) complexes on a resin support surface has been easily performed by metal-mediated addition of amino groups of benzhydrylamine-polystyrene to the coordinated isocyanide ligand of cis-PdCl2(CNR)2 (R = t-Bu, Cy). The investigation of the benzhydrylamine reaction with palladium-coordinated isocyanides in solution has revealed that, depending on the reaction conditions, two carbene-type complexes can be obtained as a result of the addition to the CN triple bond, as well as a third complex which is formed via substitution of the isocyanide ligand by benzhydrylamine. Nucleophilic addition of an amino group to the isocyanide ligand has led to a cis-acyclic diaminocarbene complex or a cationic diaminocarbene complex with trans configuration and an intramolecular hydrogen-bonded chloride anion (the nature of this noncovalent interaction was analyzed by DFT calculations, including AIM analysis). The unsupported and resin-supported palladium catalysts have demonstrated high catalytic activity in both Sonogashira and Suzuki-Miyaura cross-coupling. The supported catalyst can be recovered and repeatedly reused without a significant loss in efficiency. The degree of the palladium binding with polystyrene, the oxidation state, and the palladium leaching level were investigated by XPS and XRF analyses.