scholarly journals Tuning of tetrathiafulvalene properties: versatile synthesis of N-arylated monopyrrolotetrathiafulvalenes via Ullmann-type coupling reactions

2015 ◽  
Vol 11 ◽  
pp. 860-868 ◽  
Author(s):  
Vladimir A Azov ◽  
Diana Janott ◽  
Dirk Schlüter ◽  
Matthias Zeller
Keyword(s):  
Hydrogen Bonds ◽  
Electrochemical Properties ◽  
Crystal Packing ◽  
Coupling Reaction ◽  
Coupling Reactions ◽  
Electronic Nature ◽  
Weak Hydrogen Bonds ◽  
Type Coupling ◽  
Variable Substitution

An Ullmann-type coupling reaction was employed for the preparation of several N-arylated monopyrrolotetrathiafulvalenes with variable substitution patterns. Spectroscopic and electrochemical properties of the coupling products strongly depend on the electronic nature of the aromatic substituents due to their direct conjugation with the tetrathiafulvalene chromophore. The crystal packing of the arylated monopyrrolotetrathiafulvalenes is primarily defined by networks of C–H···X weak hydrogen bonds and short S···S contacts involving the tetrathiafulvalene moieties.

scholarly journals Crystal structure and Hirshfeld surface analysis of 1-[(E)-2-(5-chloro-2-hydroxyphenyl)hydrazin-1-ylidene]naphthalen-2(1H)-one

2021 ◽  
Vol 77 (6) ◽  
pp. 672-676
Author(s):  
Hassiba Bougueria ◽  
Souheyla Chetioui ◽  
Mohammed Abdellatif Bensegueni ◽  
Jean-Pierre Djukic ◽  
Nesrine Benarous
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Surface Analysis ◽  
Crystal Packing ◽  
Coupling Reaction ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
Hydroxyl Group ◽  
Asymmetric Unit ◽  
Compound C

The title compound, C16H11ClN2O2, was obtained by diazotization of 2-amino-4-chlorophenol followed by a coupling reaction with β-naphthol. There are two molecules (A and B) in the asymmetric unit. The crystal structure features only one type of intermolecular interaction, that is strong hydrogen bonds involving the hydroxyl group. The naphthol and phenol fragments attached to the C=N—N— moiety exhibit an s-trans conformation. In addition, those fragments are almost coplanar, subtending a dihedral angle of 13.11 (2)° in molecule A and 10.35 (2)° in molecule B. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H...H (32.1%), C...H/H...C (23.1%), Cl...H/H...Cl (15.2%), O...H/H...O (12.8%) and C...C (9%) contacts.

scholarly journals Efficient pyrazole moiety-containing ligands for Cu-catalyzed O-arylation of phenols

2019 ◽  
Author(s):  
Yingying Zhao ◽  
Xiangyong Wang ◽  
Ryo Kaneyama ◽  
Koichi Kodama ◽  
Takuji Hirose
Keyword(s):  
Steric Hindrance ◽  
Binding Sites ◽  
Coupling Reaction ◽  
Aryl Halides ◽  
Catalyst Loading ◽  
Radical Mechanism ◽  
Coupling Reactions ◽  
Electronic Effects ◽  
Electronic Nature ◽  
Imine Nitrogen

Seven N2- and N3-ligands (L1–L7) were developed for the ligand-assisted CuI-catalyzed coupling reactions of aryl halides with phenols. The structural and electronic effects were studied for various combinations of pyridine and/or imine nitrogen binding sites in the ligands. 2-(1-Pyrazolyl)pyridine (L1) featuring two types of binding sites gave the best results, with yields of up to 90% at 100 °C at a catalyst loading of 10 mol% (CuI/L in 1:1 ratio). A non-radical mechanism, proposed for the L1-promoted coupling reaction, well explained the different effects of electronic nature of the substituent and steric hindrance on phenols and aryl halides.

scholarly journals Synthesis of substituted Z-styrenes by Hiyama-type coupling of oxasilacycloalkenes: application to the synthesis of a 1-benzoxocane

2017 ◽  
Vol 13 ◽  
pp. 2122-2127 ◽  
Author(s):  
James R Vyvyan ◽  
Courtney A Engles ◽  
Scott L Bray ◽  
Erik D Wold ◽  
Christopher L Porter ◽  
...  
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Cyclic Ether ◽  
Carbon Skeleton ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Aryl Iodides ◽  
Cross Coupling Reaction ◽  
Type Coupling ◽  
The Cross

Several Hiyama cross-coupling reactions of oxasilacycloalkenes and aryl iodides are described that produce trisubstituted Z-styrenes in moderate to excellent yields. Both electron-rich and electron-poor aryl iodides are tolerated in the cross-coupling reaction. The oxasilacycloalkene coupling partners were prepared by ruthenium-catalyzed intramolecular anti-hydrosilylation of alkynols. One of the cross-coupling products was converted to a 1-benzoxocane, albeit in low yield, using an intramolecular Buchwald–Hartwig etherification. The cyclic ether produced contains the carbon skeleton of heliannuol A.

scholarly journals On the significance of weak hydrogen bonds in crystal packing: a large databank comparison of polymorphic structures

CrystEngComm ◽  
2018 ◽  
Vol 20 (39) ◽  
pp. 5976-5989 ◽  
Author(s):  
Leonardo Lo Presti
Keyword(s):  
Molecular Recognition ◽  
Hydrogen Bonds ◽  
Crystal Packing ◽  
Supramolecular Assemblies ◽  
Weak Hydrogen Bonds

Weak hydrogen bonds control initial molecular recognition modes, but the structure is determined by the interactions among larger supramolecular assemblies.

scholarly journals Bis(N-adamantyl-N′-ethylimidazolium) tetrabromidomanganate(II)

IUCrData ◽  
2020 ◽  
Vol 5 (3) ◽  
Author(s):  
Niels Ole Giltzau ◽  
Martin Köckerling
Keyword(s):  
Hydrogen Bonds ◽  
Title Compound ◽  
Crystal Packing ◽  
Three Dimensional ◽  
Coulombic Interactions ◽  
Compound C ◽  
Dimensional Network ◽  
Weak Hydrogen Bonds ◽  
Type C

The title compound, (C15H23N2)2[MnBr4], comprises two N-adamantyl-N′-ethylimidazolium cations and one tetrahedral [MnBr4]2− anion. Next to Coulombic interactions, weak hydrogen bonds of the type C—H...Br consolidate the crystal packing, building up a three-dimensional network.

Chemistry of 1,2-allenyl/propargyl metal species. A personal account

2001 ◽  
Vol 73 (2) ◽  
pp. 337-341 ◽  
Author(s):  
Sheng-Ming Ma ◽  
Ai-Bin Zhang
Keyword(s):  
Coupling Reaction ◽  
Catalytic Amount ◽  
Subsequent Treatment ◽  
Metal Species ◽  
Coupling Reactions ◽  
Personal Account ◽  
Organic Halides ◽  
Formation Type ◽  
Type Coupling ◽  
Organozinc Reagents

The Pd (0) -catalyzed coupling reaction of aryl and electron-deficient alkenyl halides with the organozinc reagents formed by the subsequent treatment of 1-phenylalk-1-ynes with n-BuLi and ZnBr2 with or without a catalytic amount of HgCl2 was studied. Both the allene-formation- and the alkyne-formation-type coupling reactions were observed, depending on the structures of organic halides and 1-arylalk-1-ynes.

scholarly journals Influences of Chemical Functionalities on Crystal Structures and Electrochemical Properties of Dihydro-benzoxazine Dimer Derivatives

Crystals ◽  
2021 ◽  
Vol 11 (8) ◽  
pp. 979
Author(s):  
Natapol Suetrong ◽  
Kantapat Chansaenpak ◽  
Sarawoot Impeng ◽  
Piyanut Pinyou ◽  
Vincent Blay ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Electrochemical Properties ◽  
Crystal Structures ◽  
Crystal Packing ◽  
Structural Features ◽  
Oxidation Potential ◽  
Electrochemical Characteristics ◽  
Amine Nitrogen ◽  
Ethyl Methyl ◽  
Ring Opening Reactions

Dihydro-1,3,2H-benzoxazine dimer derivatives or dihydro-benzoxazine dimers are a class of compounds typically prepared by ring-opening reactions between dihydro-benzoxazines and phenols. Dihydro-benzoxazine dimers act as chelating agents for several transition and rare-earth cations. To better understand the chelating properties, it is necessary to examine their structural features and electrochemical characteristics thoroughly. However, the electrochemical properties of dihydro-benzoxazine dimers have not been tremendously examined. Herein, eight derivatives of dihydro-benzoxazine dimers possessing different substituents on the benzene ring and the tertiary-amine nitrogen were synthesized as model compounds to investigate their influences on crystal structures and electrochemical properties. The crystal structure of the dihydro-benzoxazine dimer, namely 2,2’-(cyclohexylazanediyl)bis(methylene)bis(4-methoxyphenol) (7), is identified for the first time and further used to compare with the crystal structures of other derivatives reported previously. For all the derivatives, intermolecular O–H···O hydrogen bonds are the significant interactions to hold the crystal packing of (7) and also the other derivatives. Hirshfeld surface analyses confirm the presence of intermolecular O–H···O hydrogen bonds. Redox behavior of the eight dihydro-benzoxazine dimers was studied by cyclic voltammetry. An oxidation peak observed at 0.25–0.47 V corresponds to the oxidation of the phenolic –OH group to the phenoxonium intermediate. The shift in the electrochemical peak positions is due to the different abilities of the substituents to stabilize the phenoxonium cation intermediate. The stabilizing power is ranged in the following order: methoxy > dimethyl > ethyl ≈ methyl, and N-cyclohexyl > N-methyl. Thus, the derivative (7), which contains both the methoxy and N-cyclohexyl groups, has the lowest oxidation potential. Our work elucidates the effect of the substituents on the crystal structures and electrochemical properties of the dihydro-benzoxazine dimers.

scholarly journals Potassium 3-formyl-[1,1′-biphenyl]-4-olate monohydrate

IUCrData ◽  
2017 ◽  
Vol 2 (9) ◽  
Author(s):  
Ryoji Moriwaki ◽  
Tomoyuki Haraguchi ◽  
Takashiro Akitsu
Keyword(s):  
Hydrogen Bonds ◽  
Crystal Packing ◽  
Phenylboronic Acid ◽  
Three Dimensional ◽  
Coupling Reaction ◽  
Cross Coupling ◽  
Water Molecules ◽  
Framework Structure ◽  
Charged Species ◽  
Cross Coupling Reaction

The title salt, K+·C13H9O2−·H2O, was synthesized from 5-bromosalicylaldehyde and a phenylboronic acid derivative using the Suzuki–Miyaura cross-coupling reaction (Miyaura & Suzuki, 1979). In addition to the intermolecular interactions between the charged species, two O—H...O hydrogen bonds involving the isolated water molecules further stabilize the crystal packing of the title salt leading to the formation of a three-dimensional framework structure.

An Iron-Based Catalyst Enables The Enantioconvergent Synthesis of Chiral 1,1-Diarylalkanes Through a Suzuki-Miyaura Cross-Coupling Reaction

2020 ◽  
Author(s):  
Chet Tyrol ◽  
Nang Yone ◽  
Connor Gallin ◽  
Jeffery Byers
Keyword(s):  
Coupling Reaction ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Radical Intermediates ◽  
Cross Coupling Reactions ◽  
Cross Coupling Reaction ◽  
Boronic Esters ◽  
Carbon Centered Radical ◽  
Iron Based ◽  
High Yields

By using an iron-based catalyst, access to enantioenriched 1,1-diarylakanes was enabled through an enantioselective Suzuki-Miyaura crosscoupling reaction. The combination of a chiral cyanobis(oxazoline) ligand framework and 1,3,5-trimethoxybenzene additive were essential to afford high yields and enantioselectivities in cross-coupling reactions between unactivated aryl boronic esters and a variety of benzylic chlorides, including challenging ortho-substituted benzylic chloride substrates. Mechanistic investigations implicate a stereoconvergent pathway involving carbon-centered radical intermediates.

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