14111-33-2Relevant articles and documents
Programmed Sequential Additions to Halogenated Mucononitriles
Zahara, Adam J.,Hinds, Elsa M.,Nguyen, Andrew L.,Wilkerson-Hill, Sidney M.
, p. 8065 - 8069 (2020)
Dihalomucononitriles were synthesized and their reactivity evaluated to assess their ability to function as linchpin reagents. Bis(2-chloroacrylonitrile) and bis(2-bromoacrylonitrile) were synthesized from 2,1,3-benzothiadiazole and undergo conjugate addition/elimination reactions with both nitrogen (40-95% yield) and carbon nucleophiles (72-93% yield). Secondary amines undergo monosubstitutions, while carbon nucleophiles are added twice. The sequence of addition of the nucleophiles could be controlled to give mixed addition products. The multicomponent coupling products could then be converted to natural product like motifs using intramolecular cyclization reactions.
Ball-Milling-Enabled Reactivity of Manganese Metal**
Bolt, Robert R. A.,Browne, Duncan L.,Howard, Joseph L.,Khan, Adam,Magri, Giuseppina,Morrill, Louis C.,Nicholson, William I.,Richards, Emma,Seastram, Alex C.
supporting information, p. 23128 - 23133 (2021/09/20)
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.
Divergent Rearrangements of Vinylcyclopropane into Skipped Diene and Cyclopentene: Mechanism, Scope, and Limitations
Delbrassinne, Arnaud,Richald, Maximilien,Janssens, Julien,Robiette, Rapha?l
supporting information, p. 2862 - 2868 (2021/06/11)
Vinylcyclopropanes are versatile intermediates in organic synthesis which undergo various rearrangements. We report a new rearrangement of vinylcyclopropane into skipped diene. A detailed mechanistic study revealed that this transformation involves regioselective ring-opening of the cyclopropane ring followed by 1,2-migration of one of the cyclopropane substituents. Interestingly, our investigations showed that skipped diene is the kinetic product of the process but formation of a more stable cyclopentene is also accessible. The fundamental understanding of the processes involved enabled the development of divergent methodologies allowing to obtain cyclopentene or skipped diene from vinylcyclopropane in a selective and controlled manner.
Electricity Driven 1,3-Oxohydroxylation of Donor-Acceptor Cyclopropanes: a Mild and Straightforward Access to β-Hydroxy Ketones
Banerjee, Prabal,Maajid Taily, Irshad,Saha, Debarshi
supporting information, p. 5053 - 5057 (2021/09/30)
An unprecedented external oxidant-free electrochemical protocol for 1, 3-oxohydroxylation of donor-acceptor cyclopropane is disclosed. The strategy encompasses the activation of the labile π-electron cloud of the aryl ring to cleave the strained Csp3?Csp3 bond of cyclopropane to afford the β-hydroxy ketones via insertion of molecular oxygen. More significantly, based on the detailed mechanistic investigations and cyclic voltammetry experiments, a plausible mechanism is proposed.
COMPOUND HAVING BET INHIBITORY ACTIVITY AND PREPARATION METHOD AND USE THEREFOR
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Paragraph 0164-0166, (2020/12/22)
The invention relates to the field of pharmaceutical chemistry. Specifically, the present invention relates to a series of BET (bromodomain and extra-terminal domain) inhibitors having a novel structure, particularly inhibitors targeting BRD4 (Bromodomain-containing protein 4), and a preparation method and use therefor. The structure thereof is shown in the following general formula (I). Said compounds or a stereoisomer, racemate, geometric isomer, tautomer, prodrug, hydrate, solvate, or crystal form thereof, or a pharmaceutically acceptable salt thereof, and the pharmaceutical compsosition thereof can be used for the treatment and/or prevention of related diseases mediated by bromodomain proteins.
Green and selective toluene oxidation–Knoevenagel-condensation domino reaction over Ce- and Bi-based CeBi mixed oxide mixtures
Varga, Gábor,Kukovecz, ákos,Kónya, Zoltán,Sipos, Pál,Pálinkó, István
, p. 308 - 315 (2019/11/29)
Both Bi- and Ce-based CeBi mixed oxides were prepared by a modified sol-gel process from their precursor salts. The mixed as well as the parent oxides were characterized by X-ray diffractometry, Raman, XPS, UV–DRS and X-ray photoelectron spectroscopies, ICP–OES method, scanning and transmission electron microscopies as well as BET surface area, CO2- and NH3-temperature-programmed desorption measurements. After characterizing the morphology, the acid-base properties, the oxidation states of the cationic components and the porosity of these structures, their catalytic activities were probed in the Koevenagel condensation of benzaldehyde and diethyl malonate and the toluene oxidation to benzaldehyde reactions. Based on the catalytic activities of the oxides in the individual reactions, a catalyst mixture from the Bi- and Ce-based mixed oxides was used successfully in the toluene to benzaldehyde oxidation and benzaldehyde to benzylidene malonate Knoevenagel condensation domino reaction under environmentally benign conditions.
Co-Polymeric Nanosponges from Cellulose Biomass as Heterogeneous Catalysts for amine-catalyzed Organic Reactions
Riva, Laura,Punta, Carlo,Sacchetti, Alessandro
, p. 6214 - 6222 (2020/10/02)
Heterogeneous catalysts prepared from biomass waste sources are attracting increasing interest. The reasons rely on the possibility of combining the virtuous approach of circular economy with the consolidated advantages of heterogeneous catalysis, namely the recycling of the system and the possibility to drive selectivity towards desired products. Herein we report a highly porous cellulose-based nanosponge (CNS) and its use as a recoverable catalyst for Henry and Knoevenagel reactions, two classical amino-catalyzed transformations. The material is obtained by cross-linking between TEMPO-oxidized cellulose nanofibers (TOCNF) and branched polyethyleneimine 25 kDa (bPEI) in the presence of citric acid. CNS have been developed as sorbent materials for water remediation but their use as heterogeneous catalysts was never investigated. The fully characterized micro- and nano-porous system guarantees a complete penetration of CNS, allowing reagents to diffuse within. Indeed, by modulating reaction conditions (catalyst loading, temperature, solvent, microwave versus conventional heating, relative ratio of reagents) it was possible to drive selectivity towards the desired products, while maintaining high efficiency in terms of conversion. The catalyst could be re-used several times without losing in catalytic efficiency. In most cases the products’ distribution is quite different from homogeneous conditions, this much more emphasizing the importance of this heterogeneous solution.
Metal free biomimetic deaminative direct C-C coupling of unprotected primary amines with active methylene compounds
Ghosh, Santanu,Jana, Chandan K.
supporting information, p. 10153 - 10157 (2019/12/26)
An unprecedented direct C-C coupling reaction of unprotected primary amines with active methylene compounds is reported. The reaction involves a biomimetic deamination of amines which was achieved under conditions free of metallic reagents and strong oxidizing agents. A wide range of primary amines was reacted with different active methylene compounds to provide structurally diverse trisubstituted alkenes and dihydropyridines. A kinetic study revealed an activation barrier of 10.1 kcal mol-1 for the conversion of a key intermediate of the reaction.
Unnatural α-amino ethyl esters from diethyl malonate or ethyl β-bromo-α-hydroxyiminocarboxylate
Coutant, Eloi P.,Hervin, Vincent,Gagnot, Glwadys,Ford, Candice,Baatallah, Racha,Janin, Yves L.
supporting information, p. 2853 - 2860 (2018/11/26)
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.
Diastereoselective construction of spirocyclic pyrrolidines bearing two quaternary centers via CuII-P, N-Ligand catalyzed 1,3-dipolar cycloaddition
Tang, Li-Wei,Li, Chuan,Zhao, Bao-Jing,Lan, Li,Zhang, Man,Zhou, Zhi-Ming
supporting information, p. 923 - 930 (2017/01/28)
Here, we report a convenient access to diastereoselective synthesis of polysubstituted pyrrolidines bearing a unique spiro quaternary center at the C-2 position and another quaternary center at C-4. The synthesis system, CuII/P, N-Ligand-cataly
