- Synthesis and crystal structures of imidazolium salts for quadratic optical nonlinearities
-
We have developed a new organic cation core structure, trans-1-[p-(N, N-dimethylamino) styryl]-3-methylimidozalium for second order nonlinear optical (NLO) applications. Among the eight crystals of imidozalium salts with various counter anions, trans-1-[p
- Guo, Dan,Ren, Yan,Liu, Jie,Tao, Xutang
-
-
Read Online
- Synthesis, physical properties, and chemistry of donor-acceptor-substituted pentacenes
-
Pentacenes bearing electron-donating and (or) -withdrawing groups, namely methoxy-, dialkylamino-, and nitroaryl moieties, are synthesized to afford polarized pentacenes. The optical, electrochemical, and chemical properties of these derivatives are explo
- Lehnherr, Dan,Adam, Matthias,Murray, Adrian H.,McDonald, Robert,Hampel, Frank,Tykwinski, Rik R.
-
-
Read Online
- Cobalt-Catalyzed Hydroalkynylation of Vinylaziridines
-
Transition metal-catalyzed hydroalkynylation reactions are efficient transformations allowing the straightforward formation of functionalized alkynes. Therein, we disclose the cobalt-catalyzed hydroalkynylation of vinylaziridines giving rise to both linea
- Biletskyi, Bohdan,Kong, Lingyu,Tenaglia, Alphonse,Clavier, Hervé
-
supporting information
p. 2578 - 2585
(2021/03/18)
-
- Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches
-
Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi-homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene-based photoswitches. The facile sepa
- Lorenz, Patrick,Luchs, Tobias,Hirsch, Andreas
-
supporting information
p. 4993 - 5002
(2021/02/26)
-
- Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
-
We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
- Zhang, Yanmeng,Zhang, He,Gao, Ke
-
supporting information
p. 8282 - 8286
(2021/10/25)
-
- Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO2for consecutiveN-methylation of amines
-
A mesoionic N-heterocyclic olefin (mNHO) was introduced as a metal-free catalyst for the reductive functionalization of CO2leading to consecutive doubleN-methylation of primary amines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN). A wide range of secondary amines and primary amines were successfully methylated under mild conditions. The catalyst sustained over six successive cycles ofN-methylation of secondary amines without compromising its activity, which encouraged us to check its efficacy towards doubleN-methylation of primary amines. Moreover, this method was utilized for the synthesis of two commercially available drug molecules. A detailed mechanistic cycle was proposed by performing a series of control reactions along with the successful characterisation of active catalytic intermediates either by single-crystal X-ray study or by NMR spectroscopic studies in association with DFT calculations.
- Das, Arpan,Maji, Subir,Mandal, Swadhin K.
-
p. 12174 - 12180
(2021/09/28)
-
- Preparation method of N-alkylated derivative of primary amine compound
-
The invention relates to a preparation method of an N-alkylated derivative of a primary amine compound. The method comprises the following steps: uniformly mixing a primary amine compound, an alcohol compound and a catalyst in a reactor, and heating to react for a period of time to generate an N-alkylated substituted tertiary amine compound; wherein the catalyst is a copper-cobalt bimetallic catalyst, and the carrier of the catalyst is Al2O3. According to the method, alcohol is adopted as an alkylating reagent and is low in price and easy to obtain, a byproduct is water, no pollution is caused to the environment, and the overall reaction atom economy is high; the catalyst is simple in preparation method, low in cost, high in reaction activity and good in structural stability; meanwhile, by using the copper-cobalt bimetallic catalyst, the use of strong base additives can be avoided, and the requirement on reaction equipment is low; and the reaction post-treatment is convenient, and the catalyst can be recycled and is environment-friendly.
- -
-
Paragraph 0021; 0044
(2021/07/09)
-
- Near-Infrared Fluorescent Probes with Rotatable Polyacetylene Chains for the Detection of Amyloid-β Plaques
-
The plaques of accumulated β-amyloid (Aβ) in the parenchymal brain are accepted as an important biomarker for the early diagnosis of Alzheimer's disease (AD). Many near-infrared (NIR) probes, which were based on the D-π-A structure and bridged by conjugat
- Zhang, Longfei,Gong, Xin,Tian, Chuan,Fu, Hualong,Tan, Hongwei,Dai, Jiapei,Cui, Mengchao
-
p. 497 - 506
(2021/01/26)
-
- Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
-
The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
- Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
-
supporting information
p. 10422 - 10428
(2021/07/26)
-
- Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines
-
A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.
- Chen, Gong,Arai, Kenta,Morisaki, Kazuhiro,Kawabata, Takeo,Ueda, Yoshihiro
-
supporting information
p. 728 - 732
(2021/01/18)
-
- Palladium-Catalyzed Synthesis of N, N-Dimethylanilines via Buchwald-Hartwig Amination of (Hetero)aryl Triflates
-
This work delineates the synthesis of N,N-dimethylaniline derivatives from dimethylamines and aryl triflates. The palladium-catalyzed C-N bond formation proceeds in excellent yields, using an unsophisticated catalytic system, a mild base, and triflates as electrophiles, which are readily available from inexpensive phenols. N,N-Dimethylanilines are multifunctional reaction partners and represent useful but underutilized building blocks in organic synthesis.
- Pospech, Jola,Taeufer, Tobias
-
p. 7097 - 7111
(2020/06/27)
-
- A novel DMSO-assisted regioselective iodination of aniline analogues
-
A metal- and oxidant-free electrophilic iodination of aniline analogues was achieved in high to excellent yields at room temperature in MTBE with 0 or 3.5 equivalents of DMSO. Examined substituents include N-alkyl, N,N-dialkyl, N-morpholinyl and N-piperazinyl as well as methyl, Br, CN and CO2CH3 aryl ring substitutions.
- Bovonsombat, Pakorn,Lorpaiboon, Wanutcha,Laoboonchai, Sarocha,Sriprachaya-anunt, Prima,Yimkosol, Warangkana,Siriphatcharachaikul, Natthapatch,Siricharoensang, Pornpawit,Kangwannarakul, Terawee,Maeda, Jin,Losuwanakul, Satreerat,Mahesh Abhyankar, Maitraye
-
-
- Redox-Selective Iron Catalysis for α-Amino C-H Bond Functionalization via Aerobic Oxidation
-
Single-electron oxidation and α-deprotonation of tertiary anilines using Fe(phen)3(PF6)3 afford α-aminoalkyl radicals, which can be coupled with electrophilic partners to afford various tetrahydroquinolines. Mechanistically, the Fe(phen)n 2+/3+ catalytic cycle is maintained by O2 or a TBHP oxidant, and the presence of the oxygen bound iron complex, Fe(III)-OO(H), was elucidated by electron paramagnetic resonance and electrospray ionization mass spectrometry. This redox-selective nonheme iron catalyst behaves similarly to bioinspired heme iron catalysts.
- Hwang, Joon Young,Ji, A. Young,Lee, Sang Hyeok,Kang, Eun Joo
-
supporting information
p. 16 - 21
(2019/11/11)
-
- Palladium-Catalyzed Chlorocarbonylation of Aryl (Pseudo)Halides Through In Situ Generation of Carbon Monoxide
-
An efficient palladium-catalyzed chlorocarbonylation of aryl (pseudo)halides that gives access to a wide range of carboxylic acid derivatives has been developed. The use of butyryl chloride as a combined CO and Cl source eludes the need for toxic, gaseous carbon monoxide, thus facilitating the synthesis of high-value products from readily available aryl (pseudo)halides. The combination of palladium(0), Xantphos, and an amine base is essential to promote this broadly applicable catalytic reaction. Overall, this reaction provides access to a great variety of carbonyl-containing products through in situ transformation of the generated aroyl chloride. Combined experimental and computational studies support a reaction mechanism involving in situ generation of CO.
- Bismuto, Alessandro,Boehm, Philip,Morandi, Bill,Roediger, Sven
-
supporting information
p. 17887 - 17896
(2020/08/19)
-
- Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary
-
Chiral auxiliaries and asymmetric catalysis are the workhorses of enantioselective transformations, but they still remain limited in terms of either efficiency or generality. Herein, we present an alternative strategy for controlling the stereoselectivity of chemical reactions. Asymmetric catalysis is used to install a transient chiral auxiliary starting from achiral precursors, which then directs diastereoselective reactions. We apply this strategy to a palladium-catalyzed carboetherification/hydrogenation sequence on propargylic amines, providing fast access to enantioenriched chiral amino alcohols, important building blocks for medicinal chemistry and drug discovery. All stereoisomers of the product could be accessed by the choice of ligand and substituent on the propargylic amine, leading to a stereodivergent process.
- Buzzetti, Luca,Puri??, Mikus,Greenwood, Phillip D. G.,Waser, Jerome
-
supporting information
p. 17334 - 17339
(2020/11/02)
-
- One of iodinated aromatic ring by iodine chloride in hydrochloric acid (by machine translation)
-
[Problem] to one iodine chloride is used, and, stably iodinated aromatic compound can be iodinated aromatic compound production. [Solution] water containing one iodine chloride hydrogen chloride, iodine chloride content of 30% by mass of the first mass % -70, 3 mass % -20 mass % aqueous solution of hydrogen chloride content in the preparing step, a process for preparing an aromatic compound as the reaction substrate, the reaction substrate as an aqueous solution of the mixture of aromatic compounds, as the reaction substrate of one iodine chloride by reacting an aromatic compound, iodinated aromatic compound obtained in the step, the iodinated aromatic compound. [Drawing] no (by machine translation)
- -
-
Paragraph 0067-0071
(2019/09/10)
-
- Regioselectivity Influences in Platinum-Catalyzed Intramolecular Alkyne O-H and N-H Additions
-
The steric and electronic drivers of regioselectivity in platinum-catalyzed intramolecular hydroalkoxylation are elucidated. A branch point is found that divides the process between 5-exo and 6-endo selective processes, and enol ethers can be accessed in good yields for both oxygen heterocycles. The main influence arises from an electronic effect, where the alkyne substituent induces a polarization of the alkyne that leads to preferential heteroatom attack at the more electron-deficient carbon. The electronic effects are studied in other contexts, including hydroacyloxylation and hydroamination, and similar trends in directionality are predominant although not uniformly observed.
- Costello, Jeff P.,Ferreira, Eric M.
-
supporting information
p. 9934 - 9939
(2019/12/24)
-
- Electrochemical Radical Borylation of Aryl Iodides
-
Herein, we report the first electrochemical strategy for the borylation of aryl iodides via a radical pathway using current as a driving force. A mild reaction condition allows an assorted range of readily available aryl iodides to be proficiently converted into synthetically valuable arylboronic esters under transition metal catalyst-free conditions. Moreover, this method also shows good functional group tolerance. Initial control mechanistic experiments reveal the formation of aryl radical as a key intermediate and the current plays an important role in the generation of radical intermediate.
- Hong, Junting,Liu, Qianyi,Li, Feng,Bai, Guangcan,Liu, Guoquan,Li, Man,Nayal, Onkar S.,Fu, Xuefeng,Mo, Fanyang
-
supporting information
p. 347 - 351
(2019/03/07)
-
- Three-Component Aminoselenation of Arynes
-
The three-component coupling of tertiary amines, arynes, and aryl selenium bromide or diaryl diselenide as an electrophilic selenium source allowing the synthesis of 2-selanyl aniline derivatives is reported. This aminoselenation reaction of arynes installs a C-N and C-Se bond under mild conditions, and the products are formed in moderate to good yields. This reaction is compatible with various functional groups, and the preliminary studies on the mechanism of the reaction is also provided.
- Gaykar, Rahul N.,Guin, Avishek,Bhattacharjee, Subrata,Biju, Akkattu T.
-
supporting information
p. 9613 - 9617
(2019/11/28)
-
- Copper-Mediated Deacylative Coupling of Ynones via C-C Bond Activation under Mild Conditions
-
The intermolecular deacylative coupling of unstrained ynones via C-C bond activation was accomplished by a CuCl-bpy system under mild reaction conditions. This protocol features facile cleavage of the C-C bond at room temperature, broad substrate scope, and efficient construction of important symmetric and unsymmetrical 1,3-diyne adducts through homo or cross coupling of ynones, respectively. The preliminary mechanistic investigations indicated that an acyl copper(III) complex is likely involved in this process.
- Feng, Lili,Hu, Tingjun,Zhang, Saisai,Xiong, Heng-Ying,Zhang, Guangwu
-
supporting information
p. 9487 - 9492
(2019/12/02)
-
- Competing dehalogenation versus borylation of aryl iodides and bromides under transition-metal-free basic conditions
-
In this work, selectivity-controllable base-promoted transition-metal-free borylation and dehalogenation of aryl halides are described. Under the conditions of borylation, the dehalogenation which emerges as a competitive side reaction has been well-controlled by carefully controlling the borylation conditions. On the other hand, the dehalogenation using benzaldehyde as a hydrogen source has also been accomplished. The applications of direct radical borylation and dehalogenation of aryl halides demonstrate their synthetic practicability in pharmaceutical-oriented organic synthesis. Based on the experimental evidences, the tBuOK/1,10-Phen-triggered radical nature of both competitive reactions has been revealed.
- Niu, Yi-Jie,Sui, Guo-Hui,Zheng, Hong-Xing,Shan, Xiang-Huan,Tie, Lin,Fu, Jia-Le,Qu, Jian-Ping,Kang, Yan-Biao
-
p. 10805 - 10813
(2019/09/30)
-
- Environmentally benign indole-catalyzed position-selective halogenation of thioarenes and other aromatics
-
Halogenated aromatic compounds are the cores of many pharmaceutical, agricultural and chemical products but they are commonly prepared using electrophilic halogenation reactions in non-green chlorinated solvents under harsh conditions. A separate problem happens in the aromatic halogenation of thioarenes because they readily undergo oxidative side-reactions. Herein we report an environmentally benign electrophilic bromination of aromatics using an indole-catalytic protocol, which is suitable for a wide range of substrates including thioarenes.
- Shi, Yao,Ke, Zhihai,Yeung, Ying-Yeung
-
supporting information
p. 4448 - 4452
(2018/10/17)
-
- Nickel-Catalyzed Cross-Electrophile Coupling between Benzyl Alcohols and Aryl Halides Assisted by Titanium Co-reductant
-
A nickel-catalyzed cross-electrophile coupling reaction between benzyl alcohols and aryl halides has been developed using a homolytic C-O bond cleavage protocol that has recently been established. The treatment of a benzyl alcohol and aryl halide with a nickel catalyst and low-valent titanium reagent generated from TiCl4(lutidine) (lutidine = 2,6-lutidine) and manganese powder afforded the cross-coupled product in high yield. A mechanistic study indicated the intermediacy of the benzyl radicals that originate from the benzyl alcohols.
- Suga, Takuya,Ukaji, Yutaka
-
supporting information
p. 7846 - 7850
(2019/01/14)
-
- Dibenzo[a,e]pentalenes with Low-Lying LUMO Energy Levels as Potential n-Type Materials
-
Ambipolar organic semiconductors are of high interest for organic field-effect transistors. For n-type conduction, low LUMO energies are required. Dibenzo[a,e]pentalenes (DBPs) are promising compounds; however, few derivatives exist with energetically low-lying LUMO levels. Here, we present DBP derivatives with LUMO energies down to -3.73 eV and small bandgaps down to 1.63 eV determined through cyclic voltammetry, UV/vis absorption spectroscopy, and TDDFT calculations. Single-crystal X-ray diffraction analysis revealed a 1D π-stacking mode. The addition of arylalkynyl substituents at the five-membered rings in a facile and versatile synthetic route allowed for tuning of the band gaps and LUMO energies. The synthetic route can easily be modified to access a variety of DBP derivatives. The LUMO energies of the DBP derivatives presented herein make them attractive for an application in n-type or ambipolar field-effect transistors.
- Grenz, David C.,Schmidt, Maximilian,Kratzert, Daniel,Esser, Birgit
-
supporting information
p. 656 - 663
(2018/01/27)
-
- 2,2-Diiododimedone: A mild electrophilic iodinating agent for the selective synthesis of α-iodoketones from allylic alcohols
-
2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a new electrophilic iodinating agent that selectively iodinates electron-rich aromatics. In contrast to other common electrophilic iodinating reagents, its mild nature allows it to be used for the selective synthesis of α-iodinated carbonyl compounds from allylic alcohols through a 1,3-hydrogen shift/iodination process catalyzed by iridium(iii) complexes.
- Martinez-Erro, Samuel,Bermejo Gómez, Antonio,Vázquez-Romero, Ana,Erbing, Elis,Martín-Matute, Belén
-
supporting information
p. 9842 - 9845
(2017/09/11)
-
- Multipodal arrangement of push-pull chromophores: a fundamental parameter affecting their electronic and optical properties
-
A series of model push-pull molecules with linear, quadrupolar, and tripodal arrangements, a varyingly substituted amino donor, two acceptors, and a partially extended π-system has been prepared. Two peripheral electron acceptors, namely N,N′-dibutylbarbituric acid and dicyanovinyl, were employed. The fundamental properties of 24 push-pull chromophores were investigated by differential scanning calorimetry, electrochemistry, one-photon absorption spectroscopy, photoinduced piezooptics, and were supported by DFT calculations. Thorough structure-property relationships were elucidated, while a significant influence of the structural arrangement/branching on the electronic and optical properties has been revealed. The fundamental optoelectronic properties of push-pull molecules are affected by their arrangement (linear/quadrupolar/tripodal), the peripheral acceptor attached, extension and planarization of the π-system, and also by the type of auxiliary N-substituent.
- Klikar,Kityk,Kulwas,Mikysek,Pytela,Bure?
-
supporting information
p. 1459 - 1472
(2017/02/23)
-
- Transition-metal-free hydrogenation of aryl halides: From alcohol to aldehyde
-
A transition-metal-and catalyst-free hydrogenation of aryl halides, promoted by bases with either aldehydes or alcohols, is described. One equivalent of benzaldehyde affords an equal yield as that of 0.5 equiv of benzyl alcohol. The kinetic study reveals that the initial rate of PhCHO is much faster than that of BnOH, in the ratio of nearly 4:1. The radical trapping experiments indicate the radical nature of this reaction. Based on the kinetic study, trapping and KIE experiments, and control experiments, a tentative mechanism is proposed. As a consequence, a wide range of (hetero)aryl iodides and bromides were efficiently reduced to their corresponding (hetero)arenes. Thus, for the first time, aldehydes are directly used as hydrogen source instead of other well-established alcohol-hydrogen sources.
- Zheng, Hong-Xing,Shan, Xiang-Huan,Qu, Jian-Ping,Kang, Yan-Biao
-
supporting information
p. 5114 - 5117
(2017/11/07)
-
- NOVEL RECYCLABLE IODINATING AGENT AND ITS APPLICATIONS
-
The present invention provides a novel recyclable catalysts of formula A, [Formula A should be inserted here] wherein X is selected from the group consisting of [Formula should be inserted here] The present invention also provides a novel recyclable iodinating agent of formula I, II or III and a process for the synthesis thereof. [ Formula I, II & III should be inserted here] Further, the present invention provides a process of halogenation of amines and heterocyclic compounds by employing recyclable catalyst of formula (I).
- -
-
Page/Page column 17
(2016/11/07)
-
- Boron-Catalyzed Aromatic C-H Bond Silylation with Hydrosilanes
-
Metal-free catalytic C-H silylation of a series of aromatic compounds such as N,N-disubstituted anilines with various hydrosilanes has been achieved for the first time using commercially available B(C6F5)3 as a catalyst. This protocol features simple and neutral reaction conditions, high regioselectivity, wide substrate scope (up to 40 examples), Si-Cl bond compatibility, and no requirement for a hydrogen acceptor.
- Ma, Yuanhong,Wang, Baoli,Zhang, Liang,Hou, Zhaomin
-
p. 3663 - 3666
(2016/04/09)
-
- Catalyst-free hydrochlorination protocol for terminal arylalkynes with hydrogen chloride
-
We present a simple and straightforward protocol for hydrochlorination of terminal arylalkynes to vinyl chlorides using hydrogen chloride under mild reaction conditions. This protocol does not involve any metal catalysts or additives. It is simple, inexpensive, and easy to prepare, and exhibits good reaction activity. The hydrochlorination proceeds smoothly to yield unique regioselective products via the Markovnikov addition rule.
- Xu, Cai-Xia,Ma, Cun-Hua,Xiao, Fu-Rong,Chen, Hong-Wei,Dai, Bin
-
supporting information
p. 1683 - 1685
(2016/11/12)
-
- Base-oxidant promoted metal-free N-demethylation of arylamines
-
A metal-free oxidative N-demethylation of arylamines with triethylamine as a base and tert-butyl hydroperoxide (TBHP) as oxidant is reported in this paper. The reaction is general, practical, inexpensive, non-toxic, and the method followed is environmentally benign, with moderate to good yields. [Figure not available: see fulltext.]
- Botla, Vinayak,Barreddi, Chiranjeevi,Daggupati, Ramana V,Malapaka, Chandrasekharam
-
p. 1469 - 1473
(2016/09/19)
-
- Regioselective iodination of aryl amines using 1,4-dibenzyl-1,4-diazoniabicyclo [2.2.2] octane dichloroiodate in solution and under solvent-free conditions
-
1,4-Dibenzyl-1,4-diazoniabicyclo[2.2.2]octane dichloroiodate is an efficient and regioselective reagent for iodination of aryl amines. A wide variety of aryl amines in reaction with this reagent afforded regioselectively iodinated products. The iodination reaction can be carried out in solution or under solvent-free condition at room temperature.
- Alikarami, Mohammad,Nazarzadeh, Somayeh,Soleiman-Beigi, Mohammad
-
p. 157 - 162
(2015/01/30)
-
- Systematic variation of cyanobuta-1,3-dienes and expanded tetracyanoquinodimethane analogues as electron acceptors in photoactive, rigid porphyrin conjugates
-
We report on a homologous series of nine electron donor-acceptor systems featuring push-pull chromophores as electron acceptors, which are accessible by a cycloaddition-retroelectrocyclization (CA-RE) reaction. The conjugates comprise a ZnII porphyrin as electron donor, which is connected through either a rigid phenylene-ethynylene-phenylene (PEP)-bicyclo[2.2.2]octane or a PEP-trans-decahydroquinoline spacer to different anilino-substituted multicyanobutadienes or extended tetracyanoquinodimethane analogues with first reduction potentials ranging from-1.78 to-0.58 V vs. Fc+/Fc. Characterization of the conjugates includes X-ray crystallography, electrochemistry, DFT calculations, and fluorescence spectroscopy. The extent of ZnII porphyrin fluorescence quenching correlates with the strength of the electron acceptor. Overall, we demonstrate the synthetic feasibility of rationally modulating the acceptor strength by means of the CA-RE reaction in geometrically well-defined electron donor-acceptor conjugates.
- Urner, Lorenz M.,Sekita, Michael,Trapp, Nils,Schweizer, W. Bernd,W?rle, Michael,Gisselbrecht, Jean-Paul,Boudon, Corinne,Guldi, Dirk M.,Diederich, Franois
-
supporting information
p. 91 - 108
(2015/02/19)
-
- Recyclable ionic liquid iodinating reagent for solvent free, regioselective iodination of activated aromatic and heteroaromatic amines
-
This article describes a simple, efficient method for iodination of activated aromatic and heteroaromatic amines using recyclable 1-butyl-3-methylpyridinium dichloroiodate (BMPDCI) as an ionic liquid iodinating reagent, in the absence of any solvent. The main advantages are a simple efficient procedure, good yields and no need for any base/toxic heavy metals, or oxidizing agents. The ionic liquid was recovered and recycled in five subsequent reactions, without much loss of activity. This method was applied for the synthesis of the antiprotozoal drug iodoquinol and the antifungal drug clioquinol.
- Deshmukh, Amarsinh,Gore, Babasaheb,Thulasiram, Hirekodathakallu V.,Swamy, Vincent P.
-
p. 88311 - 88315
(2015/11/09)
-
- Practical and efficient ipso-iodination of arylboronic acids via KF/I2 system
-
A facile and effective iododeboronation of variously substituted aryl and heteroarylboronic acids through activation and subsequent ipso-introduction of iodine is presented. The use of KF and I2 at 80 °C in 1,4-dioxane furnishes iodinated compounds in high yields.
- Tramutola, Francesco,Chiummiento, Lucia,Funicello, Maria,Lupattelli, Paolo
-
p. 1122 - 1123
(2015/02/19)
-
- Photo-induced Metal-Catalyst-Free Aromatic Finkelstein Reaction
-
The facile iodination of aromatic compounds under mild conditions is a great challenge for both organic and medicinal chemistry. Particularly, the synthesis of functionalized aryl iodides by light has long been considered impossible due to their photo-lability, which actually makes aryl iodides popular starting materials in many photo-substitution reactions. Herein, a photo-induced halogen exchange in aryl or vinyl halides has been discovered for the first time. A broad scope of aryl iodides can be prepared in high yields at room temperature under exceptionally mild conditions without any metal or photo-redox catalysts. The presence of a catalytic amount of elemental iodine could promote the reaction significantly.
- Li, Lu,Liu, Wenbo,Zeng, Huiying,Mu, Xiaoyue,Cosa, Gonzalo,Mi, Zetian,Li, Chao-Jun
-
supporting information
p. 8328 - 8331
(2015/07/15)
-
- α-Cyanation of Aromatic Tertiary Amines using Ferricyanide as a Non-Toxic Cyanide Source
-
The reaction of aromatic tertiary amines with potassium ferricyanide directly provides the useful α-amino nitriles. The inexpensive iron complex functions both as an oxidant and as a cyanide source. The presence of molecular oxygen speeds up the reaction which can be performed in aqueous tert-butanol or even in ethanol-based mixtures like Tequila. While amine cyanations usually employ highly toxic cyanide sources, potassium ferricyanide is even less toxic than table salt. No expensive metal complexes are required as catalysts and the co-product of the cyanation, Prussian blue, has no known toxicity and is rather used as an antidote.
- Nauth, Alexander M.,Otto, Nicola,Opatz, Till
-
supporting information
p. 3424 - 3428
(2016/01/25)
-
- Greener iodination of arenes using sulphated ceria-zirconia catalysts in polyethylene glycol
-
An environmentally benign method for the selective monoiodination of diverse aromatic compounds has been developed using reusable sulphated ceria-zirconia under mild conditions. The protocol provides moderate to good yields and selectively introduces iodine at the para/ortho position in monosubstituted arenes. SO42-/Ce0.07Zr 0.93O2 was found to be the best choice for the synthesis of aryl iodides in high yield, presumably due to the maximum number of acid sites (4.23 mmol g-1) among the various compositions of the catalyst system.
- Kahandal, Sandeep S.,Kale, Sandip R.,Gawande, Manoj B.,Zboril, Radek,Varma, Rajender S.,Jayaram, Radha V.
-
p. 6267 - 6274
(2014/01/23)
-
- Gold(I)-catalyzed iodination of arenes
-
A wide variety of electron-rich arenes were efficiently converted into the corresponding iodinated compounds via a gold(I)-catalyzed reaction under mild conditions. Georg Thieme Verlag Stuttgart. New York.
- Leboeuf, David,Ciesielski, Jennifer,Frontier, Alison J.
-
supporting information
p. 399 - 402
(2014/03/21)
-
- A twisted-intramolecular-charge-transfer (TICT) based ratiometric fluorescent thermometer with a mega-Stokes shift and a positive temperature coefficient
-
The fluorescence intensity of N,N-dimethyl-4-((2-methylquinolin-6-yl)ethynyl)aniline exhibits an unusual intensification with increasing temperature, by activating more vibrational bands and leading to stronger TICT emissions upon heating in dimethyl sulfoxide. Based on the different temperature dependence at various wavelengths, as shown in the TICT fluorescence spectrum, this dye can be employed to ratiometrically detect temperature.
- Cao, Cheng,Liu, Xiaogang,Qiao, Qinglong,Zhao, Miao,Yin, Wenting,Mao, Deqi,Zhang, Hui,Xu, Zhaochao
-
supporting information
p. 15811 - 15814
(2015/01/08)
-
- Aryl diazonium nanomagnetic sulfate and potassium iodide: An iodination process
-
A simple and efficient procedure for the synthesis of iodoarenes is developed which involves the sequential diazotization-iodination of aromatic amines with sodium nitrite, nanomagnetic supported sulfonic acid, and potassium iodide under solvent-free conditions at room temperature.
- Kolvari, Eskandar,Amoozadeh, Ali,Koukabi, Nadiya,Otokesh, Somayeh,Isari, Mohsen
-
supporting information
p. 3648 - 3651
(2014/06/23)
-
- A general method for N-methylation of amines and nitro compounds with dimethylsulfoxide
-
DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Not just a solvent: DMSO methylates a broad range of amines in the presence of formic acid, providing a novel, green and practical method for amine methylation. The protocol also allows the one-pot transformation of aromatic nitro compounds into dimethylated amines in the presence of a simple iron catalyst. Copyright
- Jiang, Xue,Wang, Chao,Wei, Yawen,Xue, Dong,Liu, Zhaotie,Xiao, Jianliang
-
supporting information
p. 58 - 63
(2014/01/17)
-
- Tetraarylcyclobutadienecyclopentadienylcobalt complexes: Synthesis, electronic spectra, magnetic circular dichroism, linear dichroism, and TD DFT calculations
-
The known (tetraphenyl-η4-cyclobutadiene)- η5-cyclopentadienylcobalt (1) and a series of its new substituted derivatives have been prepared. The electronic states of a few representatives have been characterized by absorption and magnetic circular dichroism. Time-dependent density functional theory has been used to arrive at spectral assignments for several prominent low-energy bands. The absorption spectra of the radical ions of 1 have also been recorded.
- Kottas, Gregg S.,Brotin, Thierry,Schwab, Peter F. H.,Gala, Kamal,Havlas, Zdenek,Kirby, James P.,Miller, John R.,Michl, Josef
-
p. 3251 - 3264
(2014/08/05)
-
- Ruthenium(II) photosensitizers with electron-rich diarylamino-functionalized 2,2′-bipyridines and their application in dye-sensitized solar cells
-
New ruthenium(II) photosensitizers [Ru(dcbpy)(L)(NCS)2] (dcbpy = 4,4′-dicarboxylic acid-2,2′-bipyridine; L = 4,4′-bis{di[4-(N,N′-dimethylamino)phenyl]amino}-2,2′-bipyridine (1), 4,4′-bis[di(4-methoxyphenyl)amino]-2,2′-bipyridine (2), and 4,4′-bis[di(4-tolyl)amino]-2,2′-bipyridine (3)) were prepared and characterized and their application in dye-sensitized solar cells is presented. The optical absorption of these photosensitizers gives a peak at around 540 nm, which is very similar to that of the standard N719. The maximum incident photon-to-current conversion efficiency (IPCE) of 80.6% was obtained for 3, which corresponded to a power conversion efficiency (η) of 5.68% under standard air mass (AM) 1.5 sunlight (versus N719 at 6.76%). Molecular cosensitization of 3 with an organic dye, QS-DPP-I, yielded higher η values up to 6% relative to the cells based on individual photosensitizers, and the corresponding IPCE can reach 93.6% at 549 nm. A preliminary stability test of the devices was also conducted.
- Wang, Qiwei,Wu, Wenjun,Ho, Cheuk-Lam,Xue, Liqin,Lin, Zhenyang,Li, Hua,Lo, Yih Hsing,Wong, Wai-Yeung
-
p. 5322 - 5330
(2015/04/22)
-
- Iron(III)-catalyzed C-H functionalization: Ortho-benzoyloxylation of N,N-dialkylanilines and its application to 1,4-benzoxazepines
-
A C-O bond-formation reaction that proceeds through C-H functionalization of N,N-dialkylanilines at the ortho-position is presented. The iron-catalyzed selective ortho-benzoyloxylation follows a polar Friedel-Crafts-like mechanism and is sensitive to the nucleophilicity of the anilines. The benzoyl-oxylation of a variety of N,N-disubstituted anilines and Nphenyl heterocycles is carried out under extremely mild conditions. Furthermore, the methodology has been successfully employed for the generation of 1,4-benzoxazepines and oaminophenols.
- Chiranjeevi, Barreddi,Vinayak, Botla,Parsharamulu, Thupakula,PhaniBabu, Vemulapalli S.,Jagadeesh, Bharatam,Sridhar, Balasubramanian,Chandrasekharam, Malapaka
-
p. 7839 - 7849
(2015/01/16)
-
- Ionic liquid iodinating reagent for mild and efficient iodination of aromatic and heteroaromatic amines and terminal alkynes
-
Hexamethylene bis(N-methylimidazolium) bis(dichloroiodate) (HMBMIBDCI), an ionic liquid iodinating reagent, have been prepared and characterized. Its ability to perform iodination reactions with a variety of substrates has been explored. In general, iodination reactions of aromatic and heteroaromatic amines proceed with good yields in the absence of solvent. Reactions of terminal alkynes in the presence of 1,8-diazabicyclo [5.4.O] undec-7-ene and tetrahydrofuran have been investigated as well.
- Nouzarian, Mahboobe,Hosseinzadeh, Rahman,Golchoubian, Hamid
-
supporting information
p. 2913 - 2925
(2013/09/02)
-
- Synthesis and properties of azulene-substituted donor-acceptor chromophores connected by arylamine cores
-
1-Ethynylazulenes connected by several arylamine cores reacted with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) in a formal [2+2] cycloaddition-cycloreversion reaction to afford the corresponding tetracyanobutadiene (TCBD) and dicyanoquinodimethane (DCNQ) chromophores, respectively, in excellent yields. The intramolecular charge-transfer (ICT) characters between the donor (azulene and arylamine cores) and acceptor (TCBD and DCNQ units) moieties were investigated by UV/Vis spectroscopy and theoretical calculations. The redox behavior of the new TCBD and DCNQ derivatives was examined by cyclic voltammetry (CV) and differential pulse voltammetry (DPV), which revealed their multistep electrochemical reduction properties. Moreover, significant color changes were observed by visible spectroscopy under the electrochemical reduction conditions. 1-Ethynylazulenes connected by several types of arylamine cores reacted with TCNE and TCNQ in formal [2+2] cycloadditions to afford corresponding tetracyanobutadiene and dicyanoquinodimethane chromophores, respectively. Cyclic voltammetry of the chromophores revealed their multistep reduction properties; significant color changes were also visible during electrochemical reduction. Copyright
- Shoji, Taku,Shimomura, Erika,Maruyama, Mitsuhisa,Maruyama, Akifumi,Ito, Shunji,Okujima, Tetsuo,Toyota, Kozo,Morita, Noboru
-
p. 7785 - 7799
(2013/12/04)
-
- Regioselective bromination and iodination of aromatic substrates promoted by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane
-
Selective and efficient bromination and iodination of aromatic compounds by ammonium bromide and ammonium iodide, respectively, under promotion of trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane have been explored. Mild reaction conditions, high selectivity and yield, and high reaction rate are some of the major advantages of this synthetic method.
- Azarifar, Davood,Khosravi, Kaveh,Najminejad, Zohreh,Soleimani, Khadijeh
-
experimental part
p. 321 - 326
(2012/08/14)
-
- A Green protocol for the bromination and iodination of the aromatic compounds using H5IO6/NaBr and H5IO 6/NaI in the water
-
Bromination and iodination of the aromatic compounds have efficiently been carried out at room temperature and 70 °C, respectively, in short reaction times using orthoperiodic acid/sodium bromide (1:2) and orthoperiodic acid/sodium iodide (1:2) in water to prepare the corresponding halo compounds with excellent yields.
- Yousefi-Seyf, Jaber,Tajeian, Kazem,Kolvari, Eskandar,Koukabi, Nadiya,Khazaei, Ardeshir,Zolfigol, Mohammad Ali
-
p. 2619 - 2622
(2012/10/29)
-
- Regioselective iodination of aromatic compounds with potassium iodide in the presence of benzyltriphenylphosphonium perchlorate
-
A simple and efficient method for the selective iodination of various aromatic compounds by using potassium iodide in the presence of benzyltriphenylphosphonium perchlorate, is reported. This method provides several advantages such as good selectivity between ortho and para positions of aromatic compounds and high yields of the products.
- Albadi, Jalal,Abedini, Masoumeh,Iravani, Nasir
-
experimental part
p. 261 - 264
(2012/05/07)
-