Category: 1435-43-4

Leroux, Frederic R.; Bonnafoux, Laurence; Heiss, Christophe; Colobert, Francoise; Lanfranchi, Don Antoine published the artcile< A practical transition metal-free aryl-aryl coupling method: arynes as key intermediates>, HPLC of Formula: 1435-43-4, the main research area is dihalobenzene organolithium lithiation; haloaryl lithium preparation elimination; aryne preparation nucleophilic addition haloaryl lithium; halobiaryl preparation metal halogen exchange dicyclohexylchlorophosphorous; biaryl phosphine ligand preparation; aryl coupling reaction.

Upon treatment of various aryllithium intermediates with 1,2-dibromobenzene or 1-bromo-2-iodobenzene, dissym. ortho,ortho’-di-, tri- and even tetrasubstituted bromo- or iodobiaryls, e.g., I, become readily available. The crucial steps in all these reactions were the nucleophilic addition of the organolithium precursor to a transient aryne species released from it by β-elimination of a lithium halide and, stabilization of the resulting 2-biaryllithium intermediate by in situ transfer of bromine or iodine from the starting material. This straightforward transition metal-free access to biaryls allows the preparation of highly valuable halobiaryls on a gram scale in excellent yields. These precursors can be subsequently functionalized by highly regioselective halogen/metal permutations into a vast variety of target mols. This was demonstrated in the synthesis of several mono- and diphosphine ligands, e.g., II.

Advanced Synthesis & Catalysis published new progress about Alkynes, arynes Role: FMU (Formation, Unclassified), FORM (Formation, Nonpreparative). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, HPLC of Formula: 1435-43-4.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Graves, Alan P.; Shivakumar, Devleena M.; Boyce, Sarah E.; Jacobson, Matthew P.; Case, David A.; Shoichet, Brian K. published the artcile< Rescoring Docking Hit Lists for Model Cavity Sites: Predictions and Experimental Testing>, Category: chlorides-buliding-blocks, the main research area is protein ligand docking mol mechanics generalized Born surface area; virtual screening rescoring ligand crystal structure protein conformation.

Mol. docking computationally screens thousands to millions of organic mols. against protein structures, looking for those with complementary fits. Many approximations are made, often resulting in low “”hit rates.””. A strategy to overcome these approximations is to rescore top-ranked docked mols. using a better but slower method. One such is afforded by mol. mechanics-generalized Born surface area (MM-GBSA) techniques. These more phys. realistic methods have improved models for solvation and electrostatic interactions and conformational change compared to most docking programs. To investigate MM-GBSA rescoring, the authors reranked docking hit lists in three small buried sites: a hydrophobic cavity that binds apolar ligands, a slightly polar cavity that binds aryl and hydrogen-bonding ligands, and an anionic cavity that binds cationic ligands. These sites are simple; consequently, incorrect predictions can be attributed to particular errors in the method, and many likely ligands may actually be tested. In retrospective calculations, MM-GBSA techniques with binding-site minimization better distinguished the known ligands for each cavity from the known decoys compared to the docking calculation alone. This encouraged us to test rescoring prospectively on mols. that ranked poorly by docking but that ranked well when rescored by MM-GBSA. A total of 33 mols. highly ranked by MM-GBSA for the three cavities were tested exptl. Of these, 23 were observed to bind-these are docking false negatives rescued by rescoring. The 10 remaining mols. are true negatives by docking and false positives by MM-GBSA. X-ray crystal structures were determined for 21 of these 23 mols. In many cases, the geometry prediction by MM-GBSA improved the initial docking pose and more closely resembled the crystallog. result; yet in several cases, the rescored geometry failed to capture large conformational changes in the protein. Intriguingly, rescoring not only rescued docking false positives, but also introduced several new false positives into the top-ranking mols. The authors consider the origins of the successes and failures in MM-GBSA rescoring in these model cavity sites and the prospects for rescoring in biol. relevant targets.

Journal of Molecular Biology published new progress about Algorithm. 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Category: chlorides-buliding-blocks.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Guo, Bin; Li, Hong-Xi; Zha, Cheng-Hao; Young, David James; Li, Hai-Yan; Lang, Jian-Ping published the artcile< Visible-Light-Enhanced Suzuki-Miyaura Reactions of Aryl Chlorides in Water with Pd NPs Supported on a Conjugated Nanoporous Polycarbazole>, COA of Formula: C6H3ClF2, the main research area is biaryl preparation; boronic acid aryl halide Suzuki Miyaura coupling palladium nanocatalyst; Suzuki-Miyaura; aryl chloride; photocatalyst; polycarbazole; visible light.

In this work, palladium nanoparticles (Pd NPs) were grown on a conjugated nanoporous polycarbazole (CNP), named Pd/CNP. The hybrid material Pd/CNP could catalyze the Suzuki-Miyaura cross-coupling reactions of aryl chlorides RCl (R = 4-cyanophenyl, quinolin-2-yl, 1-benzothiophen-3-yl, etc.) with arylboronic acids R1B(OH)2 (R1 = Ph, 4-tert-butylphenyl, 1-benzothiophen-2-yl, etc.) in water under blue LED irradiation at room temperature with high efficiency. This protocol exhibited good functional group tolerance and the catalyst could be recycled without significant loss of its catalytic activity. CNP not only provided photogenerated electrons to enrich the electron d. of the Pd NPs but also generated holes for the activation of arylboronic acids.

ChemSusChem published new progress about Aryl halides Role: RCT (Reactant), RACT (Reactant or Reagent). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, COA of Formula: C6H3ClF2.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Amani, Javad; Molander, Gary A. published the artcile< Toward Efficient Nucleophilic Azaborine Building Blocks for the Synthesis of B-N Naphthyl (Hetero)arylmethane Isosteres>, Name: 1-Chloro-3,5-difluorobenzene, the main research area is aryl chloride coupling fluoroboratomethylborazaronaphthalene preparation arylmethylborazaronaphthalene arylmethylbenzazaborine.

To develop a method for the synthesis of a class of azaborines, K 2-(trifluoroboratomethyl)-2,1-borazaronaphthalenes were synthesized to serve as nucleophilic building blocks. In Pd-catalyzed cross-coupling reactions with (hetero)aryl chlorides they serve to produce a variety of pseudobenzylic (hetero)aryl substituted azaborines. K 2-(trifluoroboratomethyl)-2,1-borazaronaphthalenes are crystalline solids that are more stable than 2-(chloromethyl)-2,1-borazaronaphthalenes and have a broader substrate scope in cross-coupling reactions compared to their pseudobenzylic chloride counterparts.

Organic Letters published new progress about Aryl chlorides Role: RCT (Reactant), RACT (Reactant or Reagent). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Name: 1-Chloro-3,5-difluorobenzene.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

El Hage, Krystel; Piquemal, Jean-Philip; Hobaika, Zeina; Maroun, Richard G.; Gresh, Nohad published the artcile< Could the ""Janus-like"" properties of the halobenzene CX bond (X=Cl, Br) be leveraged to enhance molecular recognition?>, Application of C6H3ClF2, the main research area is chlorobenzene bromobenzene bond mol recognition; anticooperativity; cooperativity; electron-donating substituents; electron-withdrawing substituents; halobenzyl ring; protein-ligand interactions; quantum chemistry; rational drug design; sigma-hole.

The CX bond in halobenzenes (X = Cl, Br) exhibits a dual character, being electron-deficient along the CX direction, and electron-rich on its flanks. We sought to amplify both features by resorting to electron-withdrawing and electron-donating substituents, resp. This was done by quantum chem. (QC) computations in the recognition sites of three protein targets: farnesyl transferase, coagulation factor Xa, and the HIV-1 integrase. In this context, some substituents, notably fluorine, CF3, and NHCH3, afforded significant overall gains in the binding energies as compared to the parent halobenzene, in the 2-5 kcal/mol range. In fact, we found that some di- and up to tetra-substitutions enabled even larger gains than those they contribute sep. owing to many-body effects. Moreover, desolvation was also found to be a key contributor to the energy balances. As a consequence, some particular substituents, contributing to reduce the halobenzene dipole moment, accordingly reduced solvation: this factor acted in synergy with their enhancement of the intermol. interaction energies along and around the CX bond. We could thus leverage the “”Janus-like”” properties of such a bond and the fact that it can be tuned and possibly amplified by well-chosen substituents. We propose a simple yet rigorous computational strategy resorting to QC to prescreen novel substituted halobenzenes. The QC results on the recognition sites then set benchmarks to validate polarizable mol. mechanics/dynamics approaches used to handle the entirety of the inhibitor-protein complex. © 2014 Wiley Periodicals, Inc.

Journal of Computational Chemistry published new progress about Aryl bromides Role: PEP (Physical, Engineering or Chemical Process), PRP (Properties), PROC (Process). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Application of C6H3ClF2.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Riley, Kevin E.; Murray, Jane S.; Fanfrlik, Jindrich; Rezac, Jan; Sola, Ricardo J.; Concha, Monica C.; Ramos, Felix M.; Politzer, Peter published the artcile< Halogen bond tunability I: the effects of aromatic fluorine substitution on the strengths of halogen-bonding interactions involving chlorine, bromine, and iodine>, Related Products of 1435-43-4, the main research area is halogen bond tunability iodine aromatic fluorine substitution strength bonding; chlorine bromine halogen bond.

In the past several years, halogen bonds are relevant in crystal engineering and biomedical applications. One of the reasons for the utility of these types of noncovalent interactions in the development of, for example, pharmaceutical ligands is that their strengths and geometric properties are very tunable. That is, substitution of atoms or chem. groups in the vicinity of a halogen can have a very strong effect on the strength of the halogen bond. The authors study halogen-bonding interactions involving aromatically-bound halogens (Cl, Br, and I) and a carbonyl oxygen. The properties of these halogen bonds are modulated by substitution of aromatic hydrogens with fluorines, which are very electroneg. These types of substitutions have dramatic effects on the strengths of the halogen bonds, leading to interactions that can be up to 100% stronger. Very good correlations are obtained between the interaction energies and the magnitudes of the pos. electrostatic potentials (σ-holes) on the halogens. The substitution of fluorines in systems containing smaller halogens results in electrostatic potentials resembling those of systems with larger halogens, with correspondingly stronger interaction energies. Also aromatic fluorine substitutions affect the optimal geometries of the halogen-bonded complexes, often as the result of secondary interactions.

Journal of Molecular Modeling published new progress about Aryl halides Role: PEP (Physical, Engineering or Chemical Process), PRP (Properties), PROC (Process). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Related Products of 1435-43-4.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Pleschke, A.; Marhold, A.; Schneider, M.; Kolomeitsev, A.; Roschenthaler, G.-V. published the artcile< Halex reactions of aromatic compounds catalysed by 2-azaallenium, carbophosphazenium, aminophosphonium and diphosphazenium salts: a comparative study>, Computed Properties of 1435-43-4, the main research area is fluoride aryl preparation; chloride aryl halogen exchange azaallenium carbophosphazenium aminophosphonium diphosphazenium catalyst.

One of the most common methods to introduce fluorine into aromatic compounds is the well-investigated halogen-exchange (Halex) reaction, in which chloro- and bromoaroms. activated towards nucleophilic substitution, react with a fluoride source to yield the corresponding fluoroarenes. In general, the reaction is supported by phase-transfer catalysts. The new classes of compounds, I (X = C, R = Me; X = Et2NP, R = Et), were found to be active phase-transfer catalysts allowing for substitution of even weakly activated halogens.

Journal of Fluorine Chemistry published new progress about Aryl chlorides Role: RCT (Reactant), RACT (Reactant or Reagent). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Computed Properties of 1435-43-4.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Sun, Caocao; Yin, Guoyin published the artcile< Integrating aryl chlorides into nickel-catalyzed 1,1-difunctionalization of alkenes>, Application of C6H3ClF2, the main research area is secondary benzyl boronate preparation regioselective; alkene aryl chloride bispinacolatodiboron difunctionalization nickel catalyst.

Herein, a first achievement in 1,1-difunctionalization of alkenes RCH=CH2 (R = hexyl, cyclohexyl, 3-(1H-pyrrol-1-yl)propyl, 9H-carbazol-9-ylmethyl, etc.) with aryl chlorides ArCl (Ar = Ph, 2,4-difluorophenyl, 1-[(tert-butoxy)(oxo)methane]-1H-indol-6-yl, 2H-1,3-benzodioxol-5-yl, etc.) as coupling partners was reported. The success is predominantly ascribed to the judicious selection of 1,2-diamine ligand. This study provides an efficient protocol for the synthesis of secondary benzyl boronates RCH2CH(R1)Ar (R1 = tetramethyl-1,3,2-dioxaborolan-2-yl) from easily accessible feedstock chems. Furthermore, the distinguished features of this method include excellent 1,1-regio- and chemoselectivity, good functional group tolerance and easily-operational catalytic reaction conditions.

Chinese Chemical Letters published new progress about Alkenes Role: RCT (Reactant), RACT (Reactant or Reagent). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Application of C6H3ClF2.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Xu, Jinhui; Cao, Jilei; Wu, Xiangyang; Wang, Han; Yang, Xiaona; Tang, Xinxin; Toh, Ren Wei; Zhou, Rong; Yeow, Edwin K. L.; Wu, Jie published the artcile< Unveiling Extreme Photoreduction Potentials of Donor-Acceptor Cyanoarenes to Access Aryl Radicals from Aryl Chlorides>, Application In Synthesis of 1435-43-4, the main research area is aryl chloride boronate light cyanoarene photoreductive borylation catalyst; arylboronate preparation; phosphine aryl chloride light cyanoarene phosphorylation catalyst; arylphosphonium salt preparation.

Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN•-*, which can be used to activate reductively recalcitrant aryl chlorides (Ered ≈ -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.

Journal of the American Chemical Society published new progress about Aromatic nitriles Role: CAT (Catalyst Use), SPN (Synthetic Preparation), USES (Uses), PREP (Preparation). 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Application In Synthesis of 1435-43-4.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics

Stadler, Sonja M.; Goettker-Schnetmann, Inigo; Mecking, Stefan published the artcile< Incorporation of Radicals during Ni(II)-Catalyzed Ethylene Insertion Polymerization>, Category: chlorides-buliding-blocks, the main research area is nickel catalyzed ethylene insertion polymerization radical incorporation.

A possible involvement of radicals in catalytic insertion chain growth remains elusive, albeit it could account for thus far inconclusive exptl. observations and enable yet unachieved synthetic reaction schemes. This work shows that radicals present, deliberately generated for this purpose, are incorporated as end groups in ethylene insertion polymerizations Azo initiators (R-N = N-R’ with R = C(CH3)2COOMe, Ph, 3,5-F2C6H3) added to pressure reactor Ni(II)salicylaldiminato-catalyzed ethylene polymerizations afforded initiator-derived aryl or alkyl end groups, resp., as revealed by in-depth NMR studies of the polymer formed. The observation of addnl. solvent- derived aryl end groups, originating from radical transfer to toluene, underlines that end groups are indeed formed from radicals. Evidence for incorporation as a chain-initiating as well as -terminating end group is discussed.

ACS Catalysis published new progress about Crystal structure. 1435-43-4 belongs to class chlorides-buliding-blocks, and the molecular formula is C6H3ClF2, Category: chlorides-buliding-blocks.

Referemce:
Chloride – Wikipedia,
Chlorides – an overview | ScienceDirect Topics