cas 5271-67-0, 2-Thiophenecarbonyl chloride

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Three step, one-pot process to prepare thiophene-2-carbonyl chloride (TCC), a key raw material in the manufacture of tioxazafen (Nemastrike)
Nematodes are parasitic organisms that cause significant damage to crops. Tioxazafen (Nemastrike), is a proprietary seed treatment being developed by Bayer AG as a broad-spectrum nematicide. Thiophene-2-carbonyl chloride (TCC) is the key raw material in the manufacture of tioxazafen. Current manufacturing routes to TCC suffer from byproduct formation and significant waste generation, which leads to high manufacturing cost. A potentially more cost-effective process for preparing TCC from commercial thiophene has been developed. The advantages of this new chemical approach are illustrated in the processing details described in this Letter.
Walker, Daniel P.,Graham, Charles R.,Miller, William H.,Koeller, Kevin J.
p. 834 - 838
(2019)
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Synthesis and Antitumor Activities of Resveratrol Derivatives on Cervical Cancer Hela Cells
Using 2-thiophenecarbonyl chloride and 2-furoyl chloride to modify the structure of the natural product resveratrol, we synthesized five novel resveratrol derivatives. The target compounds were evaluated for their antitumor activities against cervical cancer HeLa cells by the MTT method. The results indicated that the compound 3a displayed the best antitumor activities, which is higher than the value of resveratrol, and its inhibition ratio was 95.1% against HeLa cells at the concentration of 75 μmol/L.
Jin, Lu,Ren, Yu-Jie,Du, Cheng
p. 652 - 655
(2015)
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Direct observation of fluorescent complex formation of acridinium-anilide-thiophene triad with poly-L-glutamic acid
Conformational changes and self-assembly process of polypeptides and proteins are important for biological processes. In order to investigate such changes, we prepared a fluorescent probe, thiophene-phenylanilide-acridinium triad, and investigated its pho
Hu, Jingqiu,Joshi, Monica,Elioff, Michael
p. 59 - 69
(2017)
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Novel analogues of ebselen - Preparation of 2-alkylthieno[2,3-d]isoselenazol-3(2H)-ones by peroxide-mediated ring-closure of 3,3′-diselenobis(N-alkylthiophencarboxamides)
Studies toward the preparation of novel thiophen analogues of the anti-inflammatory compound Ebselen are presented. We report that treatment of 3,3′-diselenobis(N-alkylthiophen-2-carboxamides) (13; R = Me, Pri, But, Ph) with benzoyl peroxide in benzene under reflux affords the corresponding 2-alkylthieno[2,3-d]isoselenazol-3(2H)-ones (7) in 10-73% yield, except for the phenyl derivative (13; R = Ph) which proved too insoluble to react. Irradiation of the PTOC imidate esters of 2-benzylseleno-N-butylthiophen-3-carboxamide (9) and 3-benzylseIeno-N-butylthiophen-2-carboxamide (12) provides none of the expected Ebselen analogues. This failure to ring-close is discussed in terms of conformational rigidity in amidyl radicals (22) and (23). CSIRO 2000.
Laws, Melissa J.,Schiesser, Carl H.,White, Jonathan M.,Zheng, Shi-Long
p. 277 - 283
(2000)
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Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
p. 6504 - 6517
(2021/05/06)

One-step Conversion of Amides and Esters to Acid Chlorides with PCl3
A general and efficient iodine-promoted chlorination of amides and esters with phosphorus trichloride is described. For the first time. Various inactivated amides including secondary and tertiary amides were directly converted to the corresponding acid chlorides in one-step. The substrate scope of methyl esters including aromatic and aliphatic esters was also explored under this system. This method is simple, scalable and wide in scope, which provides an approach to preparation of these acid chlorides.
Li, Fangshao,Wu, Xiaofang,Guo, Fengzhe,Tang, Zi-Long,Xiao, Jing
supporting information
p. 4314 - 4317
(2021/07/16)

Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides, Hydroxamic Acids and Esters
A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.
Nikitas, Nikolaos F.,Apostolopoulou, Mary K.,Skolia, Elpida,Tsoukaki, Anna,Kokotos, Christoforos G.
supporting information
p. 7915 - 7922
(2021/05/03)

Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
supporting information
p. 10140 - 10144
(2018/08/23)

PROCESSES FOR THE PREPARATION OF HETEROARYL CARBOXYLIC ACIDS
Provided herein are processes for the preparation of heteroaryl carboxylic acids.
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Paragraph 0190 - 0195

(2018/04/20)

METHOD FOR PREPARATION OF THIOPHENE-2-CARBONYL CHLORIDES WITH OXALYL CHLORIDE
The invention discloses a method for the preparation of thiophene-2-carbonyl chlorides starting from thiophenes with oxalyl chloride at elevated temperature with short reaction time.
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Page/Page column 18; 19; 20; 21

(2017/06/19)

METHOD FOR PREPARATION OF CARBOXYLIC ACID CHLORIDES FROM METHYL KETONES WITH TWO REAGENTS
The invention discloses a method for the preparation of carboxylic acid chlorides starting from methyl ketones with a sulfur chloride and a chlorinating reagent.
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(2017/01/26)

A General Cp*CoIII-Catalyzed Intramolecular C?H Activation Approach for the Efficient Total Syntheses of Aromathecin, Protoberberine, and Tylophora Alkaloids
Herein, we report a Cp*CoIII-catalyzed C?H activation approach as the key step to create highly valuable isoquinolones and pyridones as building blocks that can readily be applied in the total syntheses of a variety of aromathecin, protoberberine, and tylophora alkaloids. This particular C?H activation/annulation reaction was achieved with several terminal as well as internal alkyne coupling partners delivering a broad scope with excellent functional group tolerance. The synthetic applicability of this protocol reported herein was demonstrated in the total syntheses of two Topo-I-Inhibitors and two 8-oxyprotoberberine cores that can be further elaborated into the tetrahydroprotoberberine and the protoberberine alkaloid core. Moreover these building blocks were also transformed to six different tylophora alkaloids in expedient fashion.
Lerchen, Andreas,Knecht, Tobias,Koy, Maximilian,Daniliuc, Constantin G.,Glorius, Frank
supporting information
p. 12149 - 12152
(2017/09/13)

Synthesis and antifungal activity evaluation of new heterocycle containing amide derivatives
A series of heterocycle containing amide derivatives (1-28) were synthesised by the combination of acyl chlorides (1a, 2a) and heterocyclic/homocyclic ring containing amines, and their in vitro antifungal activity was evaluated against five plant pathogenic fungi, namely Gibberella zeae, Helminthosporium maydis, Rhizoctonia solani, Botrytis cinerea and Sclerotinia sclerotiorum. Results of antifungal activity analysis indicated that some of the products showed good to excellent antifungal activity, as compound 2 showed excellent activity against G. zeae and R. solani and potent activity against H. maydi, B. cinerea and S. sclerotiorum, and compounds 1, 8 and 10 also displayed excellent antifungal potential against H. maydi, B. cinerea and S. sclerotiorum and good activity against R. solani when compared with the standard carbendazim.
Wang, Xuesong,Gao, Sumei,Yang, Jian,Gao, Yang,Wang, Ling,Tang, Xiaorong
p. 682 - 688
(2016/01/28)

Expedient Iron-Catalyzed C-H Allylation/Alkylation by Triazole Assistance with Ample Scope
Triazole assistance set the stage for a unified strategy for the iron-catalyzed C-H allylation of arenes, heteroarenes, and alkenes with ample scope. The versatile catalyst also proved competent for site-selective methylation, benzylation, and alkylation with challenging primary and secondary halides. Triazole-assisted C-H activation proceeded chemo-, site-, and diastereo-selectively, and the modular TAM directing group was readily removed in a traceless fashion under exceedingly mild reaction conditions. One for all: A unified strategy for iron-catalyzed C-H allylation and alkylation was developed by the use of a triazole directing group that could be cleaved under exceedingly mild conditions.
Cera, Gianpiero,Haven, Tobias,Ackermann, Lutz
supporting information
p. 1484 - 1488
(2016/02/12)

RhIII-Catalyzed C-H Allylation of Amides and Domino Cycling Synthesis of 3,4-Dihydroisoquinolin-1(2H)-ones with N-Bromosuccinimide
A RhIII-catalyzed C-H allylation of electron-deficient arenes, heteroarenes, and alkenes at room temperature was developed with allyl bromide. The reaction was carried out in diethyl ether without dehydration, and C-H activation was assisted by the directing anionic nitrogen of the aniline-derived amide. Following the allylation, a domino cycling synthesis of 3,4-dihydroisoquinolin-1(2H)-ones with N-bromosuccinimide (NBS) through intramolecular aminobromination of the introduced double bond was achieved. A C-H allylation of amides with allyl halides at room temperature and a tandem synthesis of 3,4-dihydroisoquinolin-1(2H)-ones with N-bromosuccinimide (NBS) are reported.
Dai, Huimin,Yu, Chao,Lu, Changsheng,Yan, Hong
supporting information
p. 1255 - 1259
(2016/03/16)

Copper-Catalyzed Divergent Trifluoromethylation/Cyclization of Unactivated Alkenes
Most of the precedent copper-catalyzed trifluoromethylation reactions of unactivated alkenes concern terminal alkenes, and these processes are terminated in elimination, or nucleophilic addition, or semipinacol rearrangement, or C-H bond functionalization steps. In this study, we develop a trifluoromethylation method for both unactivated terminal and internal alkenes to enable divergent late-stage radical cyclization and achieve high molecular complexity. These cyclizations are well consistent with Baldwin's rule. Furthermore, a kinetic isotope effect (KIE) study and control reactions were conducted, and a plausible mechanism is proposed.
Zheng, Jing,Deng, Ziyang,Zhang, Yan,Cui, Sunliang
supporting information
p. 746 - 751
(2016/03/09)

Rh(III)-Catalyzed Redox-Neutral Annulation of Primary Benzamides with Diazo Compounds: Approach to Isoquinolinones
Reported herein is a Rh-catalyzed redox-neutral annulation of primary benzamides with diazo compounds, representing an efficient and economic protocol to isoquinolinones. The procedure exhibited good functional group tolerability, scalability, and regioselectivity, obviating the need for oxidants, and only environmentally benign N2 and H2O were released. Further utilization of the method provided an alternative route to functionalized isoquinolines.
Wu, Youzhi,Sun, Peng,Zhang, Kaifan,Yang, Tie,Yao, Hequan,Lin, Aijun
p. 2166 - 2173
(2016/03/15)

2-Aminophenyl-1H-pyrazole as a Removable Directing Group for Copper-Mediated C-H Amidation and Sulfonamidation
2-Aminophenyl-1H-pyrazole was discovered as a removable bidentate directing group for copper-mediated aerobic oxidative C(sp2-H) bond amidation and sulfonamidation. When Cu(OAc)2 was employed as the copper source and 1,1,3,3-tetramet
Lee, Wan-Chen Cindy,Shen, Yuning,Gutierrez, David A.,Li, Jie Jack
supporting information
p. 2660 - 2663
(2016/06/15)

Organosilatranes with Acylthiourea Derivatives – Metal-Ion Binding, Substituent-Dependent Sensitivity, and Prospects for the Fabrication of Magnetic Hybrids
A variety of topologically interesting acylthiourea-tethered organosilatranes (AcTu-OS) were prepared, and their function as metal-ion binding sites was investigated. The prepared compounds have been characterized by elemental analysis; FTIR, UV/Vis and NMR (1H and13C) spectroscopy; and mass spectrometry. The organosilicon complexes 4a–4e possess diverse coordination abilities for the surveyed metal ions (Cu2+, Cd2+, Hg2+and Pb2+), as was appraised by the corresponding absorption shifts in the UV/Vis spectra. In addition, a facile preparatory route for the covalent grafting of the most efficient receptor 4e onto a silica-encrusted magnetic nanosupport was implemented. The resultant organic–inorganic hybrid nanoparticles (H-NPs) were characterized by physicochemical techniques such as FTIR spectroscopy, XRD, thermogravimetric analysis (TGA), TEM, field-emission SEM (FE-SEM) and energy-dispersive X-ray spectroscopy (EDX). The grafting of the sensory module afforded active sites for the adsorption of metal ions from the aqueous solution which is outlined using the Langmuir adsorption isotherm. The potential in sensing, sorbent properties and facile magnetic recovery of the hybrid evinces the separation process practical to undertake environmental issues.
Singh, Gurjaspreet,Rani, Sunita
p. 3000 - 3011
(2016/07/12)

Synthesis and in Vitro and in Vivo anticoagulant and antiplatelet activities of amidino- and non-amidinobenzamides
Three amidino- and ten non-amidinobenzamides were synthesized as 3-aminobenzoic acid scaffold-based anticoagulant and antiplatelet compounds. The anticoagulant activities of thirteen synthesized compounds 1-13, and 2b and 3b as prodrugs were preliminary evaluated by screening the prolongation of activated partial thromboplastin time (aPTT) and prothrombin time (PT) in vitro. From the aPTT results obtained, two amidinobenzamides, N-(3′-amidinophenyl)-3-(thiophen-2″-ylcarbonylamino) benzamide (1, 33.2 ± 0.7 s) and N-(4′-amidinophenyl)-3-(thiophen-2″-ylcarbonylamino) benzamide (2, 43.5 ± 0.6 s) were selected to investigate the further anticoagulant and antiplatelet activities. The aPTT results of 1 (33.2± 0.7 s) and 2 (43.5 ± 0.6 s) were compared with heparin (62.5 ± 0.8 s) in vitro at 30 μM. We investigated the effect of 1 and 2 on blood anticoagulant activity (ex vivo) and on tail bleeding time (in vivo) on mice. A tail cutting/bleeding time assay revealed that both 1 and 2 prolonged bleeding time in mice at a dose of 24.1 g/mouse and above. Compounds 1 and 2 dose-dependently inhibited thrombin-catalyzed fibrin polymerization and platelet aggregation. In addition, 1 and 2 were evaluated on the inhibitory activities of thrombin and FXa as well as the generation of thrombin and FXa in human umbilical vein endothelial cells (HUVECs). Collectively, 1 and 2 possess some antiplatelet and anticoagulant activities and offer a basis for development of a novel antithrombotic product.
Lee, Soo Hyun,Lee, Wonhwa,Bae, Jong-Sup,Ma, Eunsook
(2016/07/06)

Synthesis and biological activity of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives
A series of novel N-(3-furan-2-yl-1-phenyl-1H-pyrazol-5-yl) amides derivatives were designed and synthesized. Their structures were confirmed by1H NMR,13C NMR and HRMS. All title compounds were evaluated for their herbicidal and antifungal activities. Preliminary bioassay results indicated that the title compounds showed good to moderate herbicidal activity at 1000?mg/L. Compound 6q presented the best activity against Digitaria sanguinalis (L) Scop., Amaranthus retroflexus L. and Arabidopsis thaliana with an inhibition degree of five. Compound 6d also showed an inhibition degree of five against D. sanguinalis. In addition, at 50?mg/L, most compounds exhibited good in vitro antifungal activity against Sclerotinia sclerotiorum, with compound 6c showing over 90% antifungal activity against S. sclerotiorum and Pellicularia sasakii.
Huo, Jing-Qian,Ma, Liu-Yong,Zhang, Zhe,Fan, Zhi-Jin,Zhang, Jin-Lin,Beryozkina, Tetyana V,Bakulev, Vasiliy A
p. 1547 - 1550
(2016/09/23)

Long-Lived, Emissive Excited States in Direct and Amide-Linked Thienyl-Substituted RuII Complexes
The excited state behavior of a new series of homoleptic and heteroleptic RuII complexes bearing thienyl groups appended to a 2,2′-bipyridine chelating ligand via direct, secondary and tertiary amide linkages is examined. The results of nanosecond transient absorption spectroscopy, emission lifetime measurements and bimolecular quenching experiments are correlated to determine that although the amide linkage does not act as a conjugated bridge to the peripheral substituents, it does not preclude possible electron transfer processes. Complexes bearing directly bound thienyl and bithienyl substituents exhibit long excited state and emission lifetimes (τem = 2 and 15 μs), with high emission quantum yields in solution (Φ = 0.35) and slow rates of non-radiative decay.
Majewski, Marek B.,Smith, Jeremy G.,Wolf, Michael O.,Patrick, Brian O.
supporting information
p. 1470 - 1479
(2016/04/26)

Methylene diphenyl amide compound and use thereof
The invention discloses a methylene diphenyl amide compound and application thereof and relates to the field of agricultural fungicides. The compound has a structure represented by a general formula (I) as shown in the description, wherein X is an oxygen atom or a sulfur atom; and R is a hydrogen atom, a halogen atom, C1-C4 alkyl group or an alkoxy group, or a nitro group. The methylene diphenyl amide compound is simple in structure, and has good inhibitory activity on multiple plant pathogenic fungi such as bipolaris maydis and sclerotinia sclerotiorum. The methylene diphenyl amide compound can be used for preventing and controlling plant pathogenic fungi, which is a novel application of the compound in the field of pesticides.
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Paragraph 0034

(2016/11/28)

Synthesis, characterization, and anti-inflammatory activities of methyl salicylate derivatives bearing piperazine moiety
In this study, a new series of 16 methyl salicylate derivatives bearing a piperazine moiety were synthesized and characterized. The in vivo anti-inflammatory activities of target compounds were investigated against xylol-induced ear edema and carrageenan-induced paw edema in mice. The results showed that all synthesized compounds exhibited potent anti-inflammatory activities. Especially, the anti-inflammatory activities of compounds M15 and M16 were higher than that of aspirin and even equal to that of indomethacin at the same dose. In addition, the in vitro cytotoxicity activities and anti-inflammatory activities of four target compounds were performed in RAW264.7 macrophages, and compound M16 was found to significantly inhibit the release of lipopolysaccharide (LPS)-induced interleukin (IL)-6 and tumor necrosis factor (TNF)-α in a dose-dependent manner. In addition, compound M16 was found to attenuate LPS induced cyclooxygenase (COX)-2 up-regulation. The current preliminary study may provide information for the development of new and safe anti-inflammatory agents.
Li, Jingfen,Yin, Yong,Wang, Lisheng,Liang, Pengyun,Li, Menghua,Liu, Xu,Wu, Lichuan,Yang, Hua
(2016/12/02)

Formyl amino-diphenyl amide compound and use thereof
The invention discloses a formamido diphenyl amide compound and application thereof, and relates to the field of agricultural fungicides. The structure of the compound is showed in the general formula (1), wherein X is an oxygen atom or a sulphur atom; R is a hydrogen atom, a halogen atom, a C1-C4 alkyl group or an alkoxy group. The compounds are simple in structure, have good inhibitory activity for multiple plant pathogenic fungi such as fusarium asiaticum and bipolaris maydis, can be used for preventing and curing the plant pathogenic fungi, and have novel use in the field of pesticides.
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Paragraph 0016; 0017; 0034

(2017/01/17)

METHOD FOR PREPARATION OF THIOPHENECARBONYL CHLORIDES
The invention discloses a method for the preparation of thiophenecarbonyl chlorides starting from acetylthiophenes with thionyl chloride in the presence of a base.
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(2016/10/11)

METHOD FOR PREPARATION OF CARBOXYLIC ACID CHLORIDES FROM METHYL KETONES
The invention discloses a method for the preparation of carboxylic acid chlorides starting from methyl ketones with a sulfur chloride.
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(2017/01/02)

Iron-Catalyzed Directed C(sp2)-H and C(sp3)-H Functionalization with Trimethylaluminum
Conversion of a C(sp2)-H or C(sp3)-H bond to the corresponding C-Me bond can be achieved by using AlMe3 or its air-stable diamine complex in the presence of catalytic amounts of an inorganic iron(III) salt and a diphosphine along with 2,3-dichlorobutane as a stoichiometric oxidant. The reaction is applicable to a variety of amide substrates bearing a picolinoyl or 8-aminoquinolyl directing group, enabling methylation of a variety of (hetero)aryl, alkenyl, and alkyl amides. The use of the mild aluminum reagent prevents undesired reduction of iron and allows the reaction to proceed with catalyst turnover numbers as high as 6500.
Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
supporting information
p. 7660 - 7663
(2015/06/30)

Acylative Suzuki coupling of amides: Acyl-nitrogen activation via synergy of independently modifiable activating groups
A highly efficient palladium-catalyzed acylative cross-coupling of carboxylic amides with arylboronic acids has been achieved via synergistic activation of the Cacyl-N bond by independently modifiable activating groups. Coupling of amides features not only good functional group tolerance but also modifiable reactivities to overcome steric hindrance. This journal is
Li, Xijing,Zou, Gang
supporting information
p. 5089 - 5092
(2015/03/30)

Design, synthesis and antitubercular evaluation of new 2-amino-5-(4-(benzyloxy)benzyl)thiophene-3-carboxylic acid derivatives. Part 3
A series of 2-amino-5-(4-(benzyloxy)benzyl)thiophene-3-carboxylic acid derivatives was designed and synthesized. The derivatives were evaluated for antitubercular activity against M. tuberculosis ATCC 27294 using the Microplate Alamar Blue Assay (MABA). Among them, compound 8b exhibited the most potent activity with MIC value of 1.9 μM.
Lu, Xiaoyun,Tang, Jian,You, Qidong,Wan, Baojie,Franzblau, Scott G.
p. 29 - 37
(2015/03/31)

Dual role of Rh(III) catalyst enables regioselective halogenation of (electron-rich) heterocycles
The Rh(III)-catalyzed selective bromination and iodination of electron-rich heterocycles is reported. Kinetic investigations show that Rh plays a dual role in the bromination, catalyzing the directed halogenation and preventing the inherent halogenation of these substrates. As a result, this method gives highly selective access to valuable halogenated heterocycles with regiochemistry complementary to those obtained using uncatalyzed approaches, which rely on the inherent reactivity of these classes of substrates. Furans, thiophenes, benzothiophenes, pyrazoles, quinolones, and chromones can be applied.
Schr?der, Nils,Lied, Fabian,Glorius, Frank
supporting information
p. 1448 - 1451
(2015/02/19)

Nickel-catalyzed directed sulfenylation of sp2 and sp3 C-H bonds
Directed sulfenylation of both sp2 and sp3 C-H bonds was achieved through nickel catalyzed directed C-S bond formation, giving the desired product in good to excellent yield (up to 90%). Other metal cations, including Cu, Fe, Pd, Rh, Ru and Co, gave almost no reaction under identical conditions, which highlighted the unique reactivity of this Ni system.
Ye, Xiaohan,Petersen, Jeffrey L.,Shi, Xiaodong
supporting information
p. 7863 - 7866
(2015/05/13)

Carboxylate Assisted Ni-Catalyzed C-H Bond Allylation of Benzamides
A one-step synthetic method was developed for allylation of benzamides using Ni(COD)2/RCO2H and [Ni(μ-H2O)(OOCCMe3)2(HOOCCMe3)2]2 (A′) catalytic system. Efficient, well-defined, air and moisture-stable Ni-pivalate complex was isolated and employed in catalytic allylation. The influence of solvent on product selectivity was also investigated. Nickel-back: A one-step synthetic method was developed for the allylation of benzamides using in situ formed nickel carboxylate Ni(COD)2/RCO2H catalyst (see scheme). The air and moisture stable Ni-pivalate complex was isolated and employed in catalytic allylation. The influence of solvent on product selectivity is discussed.
Barsu, Nagaraju,Kalsi, Deepti,Sundararaju, Basker
supporting information
p. 9364 - 9368
(2015/06/30)

Amide-tethered organosilatranes: Syntheses, structural characterization and photophysical properties
A series of trimethoxysilanes and silatranes coupled with distinct aromatic moieties (biphenyl, thiophene, pyrazine and pyridine) through amide linkage are reported. The synthetic approach involved the amidation of 3-aminopropyltrimethoxysilane (APTMS) with various carboxylic acids via acid chlorides (1a-1g) to generate amidopropylsilanes (2a-2g). Transesterification of the resultant silanes with triethanolamine and tris(isopropanolamine) yielded unsubstituted (3a-3g) and 3,7,10-trimethylsubstitued organosilatranes (4a-4g), respectively. The compounds were successfully characterized by various spectroscopic techniques [IR, NMR (1H, 13C) and Mass] and elemental analysis. The complete structure elucidation for compounds 3a, 3c·H2O and 3f was carried out using single crystal X-ray diffraction analysis. The photophysical response was studied by UV-Vis absorption and fluorescence spectroscopy. These organosilatranes possess metal ion binding sites and can be put forth for advanced analytical applications.
Singh, Gurjaspreet,Rani, Sunita,Saroa, Amandeep,Promila,Arora, Aanchal,Choquesillo-Lazarte, Duane
supporting information
p. 78 - 91
(2015/06/02)

Pd(OAc)2/AgOAc catalytic system based bidentate ligand directed regiocontrolled C-H arylation and alkylation of the C-3 position of thiophene- and furan-2-carboxamides
A contemporary method is reported for the Pd(OAc)2/AgOAc catalytic system based bidentate ligand directed, regioselective C-H activation and C-C bond formation at the C-3 position of thiophene- and furan-2-carboxamides, which are derived from 8
Padmavathi, Rayavarapu,Sankar, Rathinam,Gopalakrishnan, Bojan,Parella, Ramarao,Babu, Srinivasarao Arulananda
p. 3727 - 3742
(2015/06/16)

Palladium-catalyzed acylative cross-coupling of amides with diarylborinic acids and sodium tetraarylborates
Abstract A general and efficient acylative Suzuki coupling of active amides with diarylborinic acids has been achieved by using 1 mol% Pd(PCy3)2Cl2/0.6 mol% PCy3 as catalyst system taking advantage of modifiable reactivities of acyl-nitrogen bonds of amides. Both electronic and steric influences from either aryl or acyl counterparts on the coupling proved to be negligible or small. A variety of aryl ketones including sterically hindered ones could be synthesized by the coupling of diarylborinic acids in good to excellent yields. Sodium tetraarylborates could also be used as high atom-economy aryl source in the palladium-catalyzed cross-coupling with active amides.
Li, Xijing,Zou, Gang
p. 136 - 145
(2015/07/27)

Synthesis, biological activity screening and molecular modeling study of acylaminoacetamide derivatives
In this study, non-rigid analogs of thalidomide have been designed in order to develop potentially active, more effective and safer lead molecules for disorders caused or contributed by inflammation. Five different series of acylaminoacetamide compounds were synthesized, and the biological inhibitory potency of the title compounds has been determined by evaluating their effects on COX-2 isoenzyme expression and PGE2 production in A549 (human lung adenocarcinoma) cell lines. Among the studied series, N-[2-(isopropylamino)-2-oxoethyl]isonicotinamide is the most active inhibitory compound on COX-2 isoenzyme expression, and N-[2-oxo-2-(pyrolydine-1-yl)etyl]isonicotinamide is the most active inhibitory compound on the biosynthesis of PGE2. Molecular docking studies and molecular dynamics simulations were also applied to investigate non-covalent interactions of the most active compounds inside the active side of the crystal structure of murine cyclooxygenase 2 (mCOX-2) isoenzyme.
Coban, Gunes,Kose, Fadime Aydin,Kirmizibayrak, Petek Ballar,Pabuccuoglu, Varol
p. 3710 - 3729
(2015/09/07)

Catalytic Formation of α-Aryl Ketones by C-H Functionalization with Cyclic Alkenyl Carbonates and One-Pot Synthesis of Isocoumarins
We report here a method for direct catalytic introduction of simple α-acylalkyl groups via rhodium-catalyzed C-H functionalization with cyclic alkenyl carbonates, synthetic equivalents to enolates bearing leaving groups. The reaction proceeded smoothly without using bases to give α-aryl ketones in high yields. Various nitrogen-containing aromatic rings and amide groups serve as directing groups. 3-Substituted isocoumarins can also be prepared by one-pot C-H functionalization/cyclization.
Hara, Yusuke,Onodera, Shunsuke,Kochi, Takuya,Kakiuchi, Fumitoshi
supporting information
p. 4850 - 4853
(2015/10/12)

One-Step Conversion of Methyl Ketones to Acyl Chlorides
Treatment of aromatic and heteroaromatic methyl ketones with sulfur monochloride and catalytic amounts of pyridine in refluxing chlorobenzene leads to the formation of acyl chlorides. Both electron-rich and electron-poor aryl methyl ketones can be used as starting materials. The resulting C1-byproduct depends on the precise reaction conditions chosen.
Zaragoza, Florencio
p. 10370 - 10374
(2015/11/03)

HIV INTEGRASE INHIBITORS
The present invention features compounds that are HIV integrase inhibitors and therefore are useful in the inhibition of HIV replication, the prevention and/or treatment of infection by HIV, and in the treatment of AIDS and/or ARC.
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(2015/09/22)

Design, synthesis and preliminary bioactivity studies of 1,2-dihydrobenzo[d]isothiazol-3-one-1,1-dioxide hydroxamic acid derivatives as novel histone deacetylase inhibitors
Histone deacetylase (HDAC) is a clinically validated target for antitumor therapy. In order to increase HDAC inhibition and efficiency, we developed a novel series of saccharin hydroxamic acids as potent HDAC inhibitors. Among them, compounds 11e, 11m, 11
Han, Leiqiang,Wang, Lei,Hou, Xuben,Fu, Huansheng,Song, Weiguo,Tang, Weiping,Fang, Hao
p. 1529 - 1538
(2014/03/21)

Discovery of 1-aryloxyethyl piperazine derivatives as Kv1.5 potassium channel inhibitors (part I)
Kv1.5 potassium channel is an efficacious and safe therapeutic target for the treatment of atrial fibrillation (AF), the most common arrhythmia that threatens human. Herein, by modifying the hit compound 7k from an in-house database, 48 derivatives were synthesized for the assay of their Kv1.5 inhibitory effects by whole cell patch clamp technique. Six compounds which showed better potency than the positive compound dronedarone were selected for the next evaluation of their drug-like properties. Compound 8 exhibited balanced solubility and permeability. It also showed acceptable pharmacodynamics profile with very low acute toxicity. Taking all these data into account, compound 8 can serve as a promising lead for the development of novel therapeutic agent for the treatment of AF.
Guo, Xiaoke,Ma, Xianglei,Yang, Qian,Xu, Jing,Huang, Lu,Jia, Jianmin,Shan, Jiaojiao,Liu, Li,Chen, Weilin,Chu, Hongxi,Wei, Jinlian,Zhang, Xiaojin,Sun, Haopeng,Tang, Yiqun,You, Qidong
supporting information
p. 89 - 94
(2014/06/09)

C-H activation by amide chelation control: Ruthenium-catalyzed direct synthesis of 2-Aryl-3-furanamides
A new, catalytic methodology for the synthesis of heterobiaryls by the ruthenium-catalyzed C-H activation/cross-coupling of heterocyclic amides with aryl boroneopentylates is surveyed. From this survey, the highly regioselective reaction of furan-3-carboxamide to give 2-aryl-3-furanamides is optimized and generalized in scope with respect to the aryl boroneopentylate coupling partners. Established thereby is a one-step synthetic method which may supercede the broadly applied two-step directed ortho metalation (DoM)-cross coupling reaction involving cryogenic and strong base conditions and which has potential for further ortho and remote metalation chemistry.
Zhao, Yigang,Snieckus, Victor
supporting information
p. 1527 - 1532
(2014/06/09)

Discovery of aroyl piperazine derivatives as IKr & I Ks dual inhibitors for cardiac arrhythmia treatment
Combined blockade of IKr and IKs potassium channels is considered to be a promising therapeutic strategy for arrhythmia. In this study, we designed and synthesized 15 derivatives through modifying the hit compound 7 that was discovered by screening in-house database by whole-patch clamp technique. All of the compounds were evaluated on CHO and HEK 293 cell lines stably expressing hERG (IKr) and hKCNQ1/KCNE1 (IKs) potassium channels, and half of them exhibited improved dual IKr and IKs inhibitory effects compared to the hit compound. Compounds 7a and 7b with potent dual inhibitory activities were selected for further in vivo evaluations. Due to the preferable pharmacological behaviors, compound 7a deserved further optimization as a promising lead compound.
Guo, Xiaoke,Sun, Haopeng,Du, Lvpei,Huang, Lu,Xu, Jing,Zhu, Yingying,Yu, Peng,Zhang, Xiaojin,Tang, Yiqun,You, Qidong
p. 497 - 505
(2014/06/23)

Synthesis, structural and mesophase characterization of three ring based thiophene liquid crystals
Thiophene based calamitic mesogens are receiving paramount importance due to their applications in functional organic materials. The insertion of thiophene in the core unit favours a large change in mesophase characteristics as well as application properties in contrast to those mesogens with phenyl ring core alone. In this work, we report the structural as well as mesophase characterization of six mesogens which are built with a core of three phenyl rings and thiophene ring. The thiophene ring is placed at one end of the core and varied the other end with alkyl/alkoxy chains to investigate the mesophase characteristics. The molecular structures of representative mesogens are confirmed by means of FT-IR and Two-dimensional solution NMR techniques. An enantiotropic nematic phase is observed in all the cases as supported by HOPM and DSC techniques. The mesophase characteristics such as melting and clearing temperatures and phase stability are discussed. A dramatic increase in nematic phase stability for the synthesised mesogens is noticed in contrast to two phenyl ring based thiophene mesogens reported in literature.
Reddy, M. Kesava,Reddy, K. Subramanyam,Kumar, B.V.N. Phani,Narasimhaswamy
p. 1 - 24
(2014/07/07)

Copper-mediated ortho-nitration of (hetero)arenecarboxylates
Various (hetero)arenecarboxylic acids were converted to the corresponding Daugulis amides and nitrated selectively in the ortho-position in the presence of [CuNO3(PPh3)2] and AgNO2 at 50 °C. A microwave-assisted saponification allows regenerating the carboxylate group within minutes, which may then be removed tracelessly by protodecarboxylation, or substituted by aryl- or alkoxy-groups via decarboxylative cross-coupling.
Katayev, Dmitry,Pfister, Kai F.,Wendling, Timo,Goossen, Lukas J.
supporting information
p. 9902 - 9905
(2014/08/18)

N-,C-DISUBSTITUTED AZOLES AND COMPOSITIONS AND METHODS FOR CONTROLLING NEMATODE PESTS
Provided herein are new N-,C-disubstituted azoles and derivatives thereof that exhibit nematicidal activity and are useful, for example, in methods for the control of unwanted nematodes.
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Paragraph 0189

(2014/09/29)

Iron-catalyzed C(sp2)-H bond functionalization with organoboron compounds
We report here that an iron-catalyzed directed C-H functionalization reaction allows the coupling of a variety of aromatic, heteroaromatic, and olefinic substrates with alkenyl and aryl boron compounds under mild oxidative conditions. We rationalize these results by the involvement of an organoiron(III) reactive intermediate that is responsible for the C-H bond-activation process. A zinc salt is crucial to promote the transfer of the organic group from the boron atom to the iron(III) atom.
Shang, Rui,Ilies, Laurean,Asako, Sobi,Nakamura, Eiichi
supporting information
p. 14349 - 14352
(2014/12/11)

Mild rhodium(III)-catalyzed C-H allylation with 4-vinyl-1,3-dioxolan-2-ones: Direct and stereoselective synthesis of (E)-allylic alcohols
A rhodium(III)-catalyzed C-H direct allylation reaction with 4-vinyl-1,3-dioxolan-2-ones has been developed. The reaction provides a facile and stereoselective access to substituted-(E)-allylic alcohols under mild and redox-neutral reaction conditions. Olefinic C-H activation is applicable, giving multifunctionalized skipped dienes in good yields. Minimal double-bond migration was observed.
Zhang, Shang-Shi,Wu, Jia-Qiang,Lao, Ye-Xing,Liu, Xu-Ge,Liu, Yao,Lv, Wen-Xin,Tan, Dong-Hang,Zeng, Yao-Fu,Wang, Honggen
supporting information
p. 6412 - 6415
(2015/01/09)

Nickel(II)-catalyzed direct arylation of C-H bonds in aromatic amides containing an 8-aminoquinoline moiety as a directing group
Arylation via the cleavage of the ortho C-H bonds by a nickel-catalyzed reaction of aromatic amides containing an 8-aminoquinoline moiety with aryl iodides is reported. The reaction shows a high functional group compatibility. The reaction proceeds in a highly selective manner at the less hindered C-H bonds in the reaction of meta-substituted aromatic amides, irrespective of the electronic nature of the substituents. Electron-withdrawing groups on the aromatic amides facilitate the reaction. Various mechanistic experiments, such as deuterium labeling experiments, Hammett studies, competition experiments, and radical trap experiments, have been made for better understanding the reaction mechanism. It is found that the cleavage of C-H bonds is reversible on the basis of the deuterium labeling experiments. Both Ni(II) and Ni(0) show a high catalytic activity, but the results of mechanistic experiments suggest that a Ni(0)/Ni(II) catalytic cycle is not involved. (Chemical Equation Presented).
Yokota, Ayana,Aihara, Yoshinori,Chatani, Naoto
supporting information
p. 11922 - 11932
(2015/02/19)

Ligand-promoted alkylation of C(sp3)-H and C(sp2)-H bonds
9-Methylacridine was identified as a generally effective ligand to promote a Pd(II)-catalyzed C(sp3) - H and C(sp2) - H alkylation of simple amides with various alkyl iodides. This alkylation reaction was applied to the preparation of unnatural amino acids and geometrically controlled tri- and tetrasubstituted acrylic acids.
Zhu, Ru-Yi,He, Jian,Wang, Xiao-Chen,Yu, Jin-Quan
supporting information
p. 13194 - 13197
(2015/03/30)