- Visible-Light-Induced Trifluoromethylation of Highly Functionalized Arenes and Heteroarenes in Continuous Flow
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We report a continuous-flow protocol for the trifluoromethylation of arenes, heteroarenes, and benzofused heterocycles. This photoredox methodology relies on the use of solid sodium trifluoromethanesulfinate (CF 3 SO 2 Na) as the trifluoromethylating agent and the iridium complex [Ir{dF(CF 3)ppy} 2 ](dtbpy)]PF 6 as the photoredox catalyst. A diverse set of highly functionalized heterocycles proved compatible with the methodology, and moderate to good yields were obtained within 30 minutes of residence time.
- Abdiaj, Irini,Bottecchia, Cecilia,Alcazar, Jesus,No?l, Timothy
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Read Online
- Selective Solvent-Assisted Linker Exchange (SALE) in a Series of Zeolitic Imidazolate Frameworks
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Solvent-assisted linker exchange (SALE) has recently emerged as an attractive strategy for the synthesis of metal-organic frameworks (MOFs) that are unobtainable via traditional synthetic pathways. Herein we present the first example of selective SALE in which only the benzimiadazolate-containing linkers in a series of mixed-linker zeolitic imidazolate frameworks (ZIF-69, -78, and -76) are replaced. The resultant materials (SALEM-10, SALEM-10b, and SALEM-11, respectively) are isostructural to the parent framework and in each case contain trifluoromethyl moieties. We therefore evaluated each of these materials for their hydrophobicity in condensed and gas phases. We expect that selective SALE will significantly facilitate the design of improved, and potentially complex, MOF materials with new and unusual properties.
- Lalonde, Marianne B.,Mondloch, Joseph E.,Deria, Pravas,Sarjeant, Amy A.,Al-Juaid, Salih S.,Osman, Osman I.,Farha, Omar K.,Hupp, Joseph T.
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Read Online
- One-Pot Transformation of Lignin and Lignin Model Compounds into Benzimidazoles
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It is a challenging task to simultaneously achieve selective depolymerization and valorization of lignin due to their complex structure and relatively stable bonds. We herein report an efficient depolymerization strategy that employs 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as oxidant/catalyst to selectively convert different oxidized lignin models to a wide variety of 2-phenylbenzimidazole-based compounds in up to 94 % yields, by reacting with o-phenylenediamines with varied substituents. This method could take full advantage of both Cβ and/or Cγ atom in lignin structure to furnish the desirable products instead of forming byproducts, thus exhibiting high atom economy. Furthermore, this strategy can effectively transform both the oxidized hardwood (birch) and softwood (pine) lignin into the corresponding degradation products in up to 45 wt% and 30 wt%, respectively. Through a “one-pot” process, we have successfully realized the oxidation/depolymerization/valorization of natural birch lignin at the same time and produced the benzimidazole derivatives in up to 67 wt% total yields.
- Guo, Tao,He, Jianghua,Liu, Tianwei,Zhang, Yuetao
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supporting information
(2022/02/07)
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- SUBSTITUTED BENZIMIDAZOLE CARBOXAMIDES AND THEIR USE IN THE TREATMENT OF MEDICAL DISORDERS
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The invention provides substituted benzimidazole carboxamides and related compounds, compositions containing such compounds, medical kits, and methods for using such compounds and compositions to treat a medical disorder, e.g., cancer, lysosomal storage disorder, neurodegenerative disorder, inflammatory disorder, in a patient.
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Paragraph 00297; 00309-00310; 00367
(2021/04/01)
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- Sustainable Synthesis of 2-Hydroxymethylbenzimidazoles using D-Fructose as a C2 Synthon
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D-fructose, a biomass-derived carbohydrate has been identified as an environmentally benign C2 synthon in the preparation of synthetically useful 2-hydroxymethylbenzimidazole derivatives by coupling with 1,2-phenylenediamines. Proof of concept was established by synthesizing 23 examples using BF3.OEt2 (20 mol%), TBHP (5.5 M, decane) (1.0 equiv.) in CH3CN at 90 °C for 1 h. The pivotal features of this method include metal-free conditions, short time, good functional group tolerance, gram scale feasibility and the synthesis of benzimidazole fused 1,4-oxazine. Control studies with conventional C2 synthons did not produce the desired product, thus suggesting a new reaction pathway from D-fructose.
- Raja, Dineshkumar,Philips, Abigail,Sundaramurthy, Devikala,Chandru Senadi, Gopal
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supporting information
p. 3754 - 3759
(2021/10/14)
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- Reductive cyclization of o-phenylenediamine with CO2 and BH3NH3 to synthesize 1H-benzoimidazole derivatives
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A simple and green protocol was developed for the reductive cyclization of o-phenylenediamine with CO2 and BH3NH3 to yield 1H-benzimidazole. The desired 1H-benzimidazole derivatives were produced under mild conditions. Mechanism investigation indicated that the coordination of o-phenylenediamine with the boron atom of BH3NH3 promoted the transfer of the formyl group to form a stable intermediate, which facilitated the intramolecular nucleophilic addition-elimination for the formation of target product. In this process, BH3NH3 served multifunctional roles, acting as a reducing agent and a formylation catalyst.
- Li, Xiao,Zhang, Junhua,Yang, Yue,Hong, Hailong,Han, Limin,Zhu, Ning
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supporting information
(2021/09/28)
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- Transition-metal and oxidant-free approach for the synthesis of diverse N-heterocycles by TMSCl activation of isocyanides
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A highly efficient TMSCl-mediated addition of N-nucleophiles to isocyanides has been achieved. This transition-metal and oxidant-free strategy has been applied to the construction of various N-heterocyles such as quinazolinone, benzimidazole and benzothiazole derivatives by the use of distinct amino-based binucleophiles. The notable feature of this protocol includes its mild reaction condition, broad functional group tolerance and excellent yield. This journal is
- Chen, Fen-Er,Dong, Lin,Li, Hongyan,Liu, Jinxin,Luo, Liangliang,Xiao, You-Cai,Zhou, Yuan
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p. 29257 - 29262
(2020/10/02)
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- Metal-Free Synthesis of Benzimidazoles via Oxidative Cyclization of d -Glucose with o-Phenylenediamines in Water
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d-Glucose has been identified as an efficient C1 synthon in the synthesis of benzimidazoles from o-phenylenediamines via an oxidative cyclization strategy. Isotopic studies with 13C6-d-glucose and D2O unambiguously confirmed the source of methine. The notable features of this method include the following: broad functional group tolerance, a biorenewable methine source, excellent reaction yields, a short reaction time, water as an environmentally benign solvent, and the synthesis of vitamin B12 component on the gram scale.
- Raja, Dineshkumar,Philips, Abigail,Palani, Pushbaraj,Lin, Wei-Yu,Devikala, Sundaramurthy,Senadi, Gopal Chandru
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p. 11531 - 11540
(2020/10/12)
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- Visible-light-induced aerobic oxidative desulfurization of 2-mercaptobenzimidazolesviaa sulfinyl radical
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A mild transition-metal-free non-toxic aerobic photoredox system was found to enable highly efficient desulfurization of 2-mercaptobenzimidazoles. This viable catalytic system includes Rose Bengal in a low catalyst loading as a photosensitizer and cheap, non-toxic NaCl in a catalytic amount as an additive, combined with an oxygen atmosphere. This protocol provides an important alternative access to a broad range of benzimidazole and deuterated benzimidazole products in generally high yields with good tolerance of various synthetically and pharmaceutically useful functionalities. The mechanistic studies reveal that both single electron transfer and energy transfer probably occur in the initial step and a sulfinyl radical intermediate is involved in the key desulfurization process.
- Deng, Guo-Jun,Fu, Mei,Huang, Huawen,Ji, Xiaochen,Li, Yongtong
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supporting information
p. 5594 - 5598
(2020/09/21)
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- Cobalt-catalyzed synthesis of N-containing heterocycles: Via cyclization of ortho -substituted anilines with CO2/H2
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The CO2-involved synthesis of chemicals is of great significance from the green and sustainable chemistry viewpoint. Herein, we report a non-noble metal catalytic system composed of CoF2, CsF and P(CH2CH2PPh2)3 (denoted as PP3) for the synthesis of N-containing heterocycles from ortho-substituted anilines and CO2/H2. Mechanism investigation indicates that [Co(PP3)H(CO2)]+ is a catalytically active intermediate under working conditions; and CsF plays important roles in activating ortho-substituted anilines via hydrogen bond interactions, thus promoting the formation of the final products. This catalytic system is highly efficient, and allows a wide scope of ortho-substituted anilines, together with excellent functional group tolerance, affording various N-containing heterocycles in good to excellent yields.
- Ke, Zhengang,Yu, Bo,Wang, Huan,Xiang, Junfeng,Han, Juanjuan,Wu, Yunyan,Liu, Zhenghui,Yang, Peng,Liu, Zhimin
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p. 1695 - 1701
(2019/04/10)
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- A benzimidazole and synthetic method of derivative thereof (by machine translation)
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The present invention provides a benzimidazole and its derivative synthesis method, the method through the imidazole chloride catalyzed O-phenylenediamine cyclized, realizes the multi-functional chain dibasic and imidazole and 2 - substituted benzimidazole synthesis, method is simple and economic, and the practicability is strong. This invention does not have any other catalyst or additive, synthetic method has good functional group tolerance and excellent yield and purity, reaction time is short, and does not need the harsh reaction conditions, is suitable for industrial production. (by machine translation)
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Paragraph 0040; 0042; 0050; 0051
(2019/02/10)
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- Imidazolium chloride-catalyzed synthesis of benzimidazoles and 2-substituted benzimidazoles from o-phenylenediamines and DMF derivatives
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A facile, general, and economical synthesis of diversely functionalized benzimidazoles and 2-substituted benzimidazoles has been realized via the imidazolium chloride-catalyzed cyclization of o-phenylenediamines with DMF derivatives. This protocol shows a broad substrate scope for aliphatic, aromatic, and heteroaromatic amides. A series of benzimidazoles and 2-substituted benzimidazoles have been obtained in moderate to excellent yields.
- Gan, Zongjie,Tian, Qingqiang,Shang, Suqin,Luo, Wen,Dai, Zeshu,Wang, Huajun,Li, Dan,Wang, Xuetong,Yuan, Jianyong
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p. 7450 - 7456
(2018/11/27)
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- Novel pyrrolo-imidazole derivatives and preparation method and application thereof
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The invention discloses novel pyrrolo-imidazole derivatives and a preparation method and application thereof, and relates to the field of organic synthesis and medical chemistry. The derivatives referto benzimidazo-pyrrole compounds and medicinal salts, enantiomers, diastereoisomers or racemes; a synthetic method of the novel pyrrolo-imidazole derivatives is simple and high in yield; the derivatives are of good antibacterial activity against various fungi and have a promising application prospect in antibacterial anti-cancer activity application.
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Paragraph 0041; 0042; 0044-0051
(2018/09/12)
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- Atmospheric CO2 promoted synthesis of N-containing heterocycles over B(C6F5)3 catalyst
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B(C6F5)3 combined with atmospheric CO2 was found to be highly effective for the cyclization of ortho-substituted aniline derivatives with N,N-dimethylformamide (DMF), and a series of N-containing heterocycles including benzothiazoles, benzimidazoles, quinazolinone and benzoxazole were obtained in good to excellent yields.
- Gao, Xiang,Yu, Bo,Mei, Qingqing,Yang, Zhenzhen,Zhao, Yanfei,Zhang, Hongye,Hao, Leiduan,Liu, Zhimin
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p. 8282 - 8287
(2016/10/11)
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- Deprotection of N-benzylbenzimidazoles and N-benzylimidazoles with triethylsilane and Pd/C
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The benzyl group is a protecting group for benzimidazoles and imidazoles that can survive acidic, basic, oxidizing, and reducing conditions. Deprotection, however, can require vigorous and potentially non-chemoselective methods. The triethylsilane–Pd/C reduction system is an exceptionally mild, convenient, and efficient method for deprotecting N-benzylbenzimidazoles that are unsubstituted at the 2- and 4-positions as well as suitably substituted N-benzylimidazoles.
- Graham, Thomas H.
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supporting information
p. 2688 - 2690
(2017/11/14)
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- A simple and convenient two-step, one-pot synthesis of hetero-imidazoles from nitroaminoaryls catalyzed by Ytterbium triflate
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A mild two-step one-pot procedure for the conversion of ortho-nitroamino aromatic heterocycles into corresponding benzo and heteroaromatic fused imidazoles is described. The procedure utilizes iron powder, acetic acid, triethylorthoformate, and a catalytic amount of Ytterbium triflate at 75 C for the nitro group reduction and cyclization reaction. The optimum stoichiometry of each component is highlighted and the broad utility is demonstrated with high compatibility to numerous functional groups.
- Wang, Fen,Tran-Dubé, Michelle,Scales, Stephanie,Johnson, Sarah,McAlpine, Indrawan,Ninkovic, Sacha
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p. 4054 - 4057
(2013/07/25)
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- Cyclization of o-phenylenediamines by CO2 in the presence of H2 for the synthesis of benzimidazoles
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The cyclization of o-phenylenediamines by CO2 in the presence of H2 was presented to directly synthesize benzimidazoles, and a series of benzimidazoles were obtained in excellent yields using RuCl 2(dppe)2 as the catalyst.
- Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Chen, Sha,Xu, Jilei,Huang, Changliang,Liu, Zhimin
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supporting information
p. 95 - 99
(2013/02/25)
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- A facile one-pot synthesis of benzimidazoles from 2-nitroanilines by reductive cyclization
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A facile one-pot process to prepare benzimidazole derivatives is described. Reductive cyclization of a serial of 2-nitroanilines with orthoesters in the presence of Pd/C in methanol at room temperature, which is promoted by a catalytic amount of acetic acid, affords the corresponding benzimidazole derivatives in high yields.
- Liu, Zheng,Li, Haihong,Zhao, Qingjie,Shen, Jingshan
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scheme or table
p. 1907 - 1911
(2009/04/06)
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- Rapid one-pot preparation of 2-substituted benzimidazoles from 2-nitroanilines using microwave conditions
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A high yielding one-pot procedure for the generation of 2-substituted benzimidazoles directly from 2-nitroanilines by in situ reduction and cyclization using a microwave procedure is described.
- VanVliet, David S.,Gillespie, Paul,Scicinski, Jan J.
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p. 6741 - 6743
(2007/10/03)
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- Pyrimidine derivatives as IL-8 receptor antagonists
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Compounds containing the pyrimidine nucleus and their use to treat diseases and conditions related to inappropriate Interleukin-8 receptor activity are disclosed. The compounds are of the formula I In these compounds, Q is preferably unsubstituted and substituted heterocyclyl; U is usually hydrogen or fluorine; and V is preferably hydrogen, halogen, alkyl, —O—alkyl or —S-alkyl. A representative example is:
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- (2S)-2-((PYRIMIDIN-4-YL)AMINO)-4-METHYLPENTANOIC ACID AMINOETHYLAMID DERIVATIVES AS IL-8 RECEPTOR MODULATORS FOR THE TREATMENT OF ATHEROSCLEROSIS AND RHEUMATOID ARTHRITIS
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The invention relates to compounds of the formula: (I); wherein R1 is a basic moiety having the structure -NH(CH2)2NR5R6, (Formula II) or (Formula II); wherein R5, R6 and R7 are independently selected from H, (1-6C)alkyl, (2-6C)alken
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- Benzimidazole derivatives for the treatment of viral infections
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According to a first aspect of the invention there is provided compounds of formula (I): wherein: R1is hydroxy; O-acetyl; or a halo atom; R2is hydroxy; O-acetyl; or a halo atom; R3is hydrogen; a halo atom; azido; C2-6alkenyl; C2-6alkynyl; C6-14aryl C2-6alkenyl; C6-14arylC2-6alkynyl —NR8R9(where R8and R9may be the same or different and are hydrogen, C1-8alkyl, cyanoC1-8alkyl, hydroxyC1-8alkyl, haloC1-8alkyl, C3-7cycloalkyl, C1-8alkylC3-7cycloalkyl, C2-6alkenyl, C3-7cycloalkylC1-8alkyl, C2-6alkynyl, C6-14aryl, C6-14arylC1-8alkyl, heterocycleC1-8alkyl, C1-8alkylcarbonyl, C6-14arylsulfonyl, C1-8alkysulfonyl, or R8R9together with the N atom to which they are attached form a 3,4,5 or 6 membered heterocyclic ring); —OR10(where R10is hydrogen, C1-8alkyl, C6-14aryl, or C6-14arylC1-8alkyl, C2-6alkenyl, C2-6alkynyl, C6-14aryl C2-6alkenyl or C6-14arylC2-6alkynyl); or —SR11(where R11is hydrogen, C1-8alkyl, C6-14aryl, or C6-14arylC1-8alkyl).
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- Photochemical Perfluoroalkylation of Imidazoles
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Imidazole and its derivatives undergo facile trifluoromethylation or perfluoroalkylation, in methanol solution at ambient temperature, following radical dissociation of RFI by γ or UV irradiation.In the case of imidazole, attack occurs preferen
- Kimoto, Hiroshi,Fujii, Shozo,Cohen, Louis A.
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p. 2867 - 2872
(2007/10/02)
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