- Delivering 2-Aryl Benzoxazoles through Metal-Free and Redox-Neutral De-CF3Process
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An unexpected cleavage of the Csp3-CF3 bond of CF3-hydrobenzoxazoles has been disclosed, affording a range of 2-aryl benzoxazoles under metal-free and redox-neutral conditions. This transformation has demonstrated broad substrate scope and good compatibility of functional groups. 2-Aryl benzothiazole and 2-aryl benzoimidazole could be smoothly assembled in the same manner. On the basis of preliminary mechanistic studies, base initiated and aromatization driven β-carbon elimination was considered to be the key step for the formation of 2. This reaction offers an alternative, facile, and sustainable route to access important 2-aryl benzoxazole motifs.
- Qiao, Xinxin,Zhao, Yong-De,Rao, Mingru,Bu, Zhan-Wei,Zhang, Guangwu,Xiong, Heng-Ying
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p. 13548 - 13558
(2021/10/01)
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- One-pot multicomponent reaction of catechols, ammonium acetate, and aldehydes for the synthesis of benzoxazole derivatives using the fe(iii)-salen complex
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The Fe(III)-salen complex has been applied successfully as a catalyst for the novel, simple, efficient, and one-pot multicomponent synthesis of benzoxazole derivatives from catechols, ammonium acetate as the nitrogen source, and aldehydes (nontoxic and cheap alternatives of amines) for the first time. Using this procedure, a wide range of benzoxazoles was successfully synthesized in the presence of a catalyst in EtOH under mild conditions, and all products were obtained in excellent yields. To the best of our knowledge, this method is the first example of the multicomponent synthesis of benzoxazole derivatives using these starting materials. The notable features such as the use of air that is considered as a benign oxidant and EtOH as a green solvent, ease of product separation, readily available and inexpensive aldehydes, and mild conditions make our procedure more efficient and practical for organic synthesis. Moreover, the current protocol is successfully applied to synthesize desirable products on a large scale.
- Sharghi, Hashem,Aboonajmi, Jasem,Aberi, Mahdi
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p. 6567 - 6577
(2020/06/08)
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- Amino Acids: Nontoxic and Cheap Alternatives for Amines for the Synthesis of Benzoxazoles through the Oxidative Functionalization of Catechols
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The nano magnetic Fe3O4 (NM?Fe3O4) was applied for the synthesis of benzoxazoles via a C(aryl)?OH functionalization of catechol derivatives and amines in ethanol at room temperature. In the next step, amino acids have been applied as nontoxic and cheap alternatives for amines. The obtained products were similar with the regular amines case. This is the first report about the application of amino acids as alternatives for primary amines in organic synthesis. Furthermore, the presented method was successfully applied toward the synthesis of desired products in large scales. (Figure presented.).
- Aberi, Mahdi,Aboonajmi, Jasem,Sharghi, Hashem,Shekouhy, Mohsen
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p. 1064 - 1083
(2020/01/24)
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- Iron(0)-Catalyzed Transfer Hydrogenative Condensation of Nitroarenes with Alcohols: A Straightforward Approach to Benzoxazoles, Benzothiazoles, and Benzimidazoles
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The iron-catalyzed hydrogen transfer strategy has been applied to the redox condensation of o-hydroxynitrobenzene with alcohol, leading to the formation of benzoxazole derivatives. A wide range of 2-substituted benzoxazoles were synthesized in good to excellent yields without the addition of an external redox agent. A series of control experiments provided a plausible mechanism. Furthermore, the reaction system was successfully extended to the synthesis of benzothiazoles and benzimidazoles.
- Putta, Ramachandra Reddy,Chun, Simin,Choi, Seung Hyun,Lee, Seok Beom,Oh, Dong-Chan,Hong, Suckchang
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p. 15396 - 15405
(2020/12/02)
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- Synthesis of benzoxazoles via the copper-catalyzed hydroamination of alkynones with 2-aminophenols
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We describe herein the synthetic method to benzoxazole derivatives via the copper-catalyzed hydroamination of alkynones with 2-aminophenols. The method produced a wide variety of functionalized benzoxazole derivatives in good yields. Preliminary mechanistic experiments revealed that the reaction would proceed through the copper-catalyzed hydroamination of alkynones and the sequential intramolecular cyclization of β-iminoketones/elimination of acetophenone promoted by the copper catalyst.
- Oshimoto, Kohei,Tsuji, Hiroaki,Kawatsura, Motoi
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p. 4225 - 4229
(2019/05/10)
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- Cesium Fluoride and Copper-Catalyzed One-Pot Synthesis of Benzoxazoles via a Site-Selective Amide C?N Bond Cleavage
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We report herein a two-step one-pot strategy for the synthesis of benzoxazoles from amides by using cesium fluoride/copper as catalysts. This approach involves the in situ generation of acyl fluorides from the corresponding amides, and the acyl fluorides undergo transamidation and cyclization to give benzoxazoles in good yields. In this work, the amide C?N bonds are activated by CsF to form the acyl fluoride intermediates, which further react with o-bromoanilines to efficiently yield benzoxazoles. Notably, this methodology demonstrates a broad substrate scope, as primary/secondary benzamides are well tolerated, and this process might facilitate the development of one-pot transformations of amides. (Figure presented.).
- Luo, Zhongfeng,Wu, Hongxiang,Li, Yue,Chen, Yuwen,Nie, Jingyi,Lu, Siqi,Zhu, Yulin,Zeng, Zhuo
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p. 4117 - 4125
(2019/08/01)
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- Iodine Promoted One-Pot Synthesis of 2-Aryl Benzoxazoles from Amidoximes via Oxidative Cyclization and Ring Contraction
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A molecular I2-promoted one-pot synthesis of 2-aryl benzoxazoles has been developed by using amidoximes rather than the limited 2-aminophenols or 2-haloamides as substrates. The amidoxime substrates provided unique and efficient strategies for converting readily available aniline and benzaldehyde precursors into valuable chemicals. This transformation proceeded smoothly under transition-metal-free conditions through a sequential oxidative cyclization and ring contraction, and provided a potential route for introducing certain groups at any site of the scaffold.
- Zhang, Yong,Ji, Min
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supporting information
p. 7506 - 7510
(2019/11/28)
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- OMS-2/H2O2/Dimethyl Carbonate: An Environmentally-Friendly Heterogeneous Catalytic System for the Oxidative Synthesis of Benzoxazoles at Room Temperature
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A manganese octahedral molecular sieve (OMS-2) was found to be an efficient and recyclable heterogeneous catalyst for the oxidative synthesis of benzoxazoles in the gram-scale from phenolic imines at room temperature. H2O2 and biobased reagent dimethyl carbonate (DMC) were successfully employed as the environmentally friendly oxidant and solvent, respectively, in an OMS-2-catalysted redox reaction for the first time. Benzoxazoles could also be obtained from N-substituted 2-aminophenols via Cu(OH)x/OMS-2-catalyzed sequential oxidative transformation at elevated temperatures.
- Meng, Xu,Wang, Yuanguang,Chen, Baohua,Chen, Gexin,Jing, Zhenqiang,Zhao, Peiqing
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p. 2018 - 2024
(2017/12/26)
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- Nickel-catalyzed C?H arylation of benzoxazoles and oxazoles: Benchmarking the influence of electronic, steric and leaving group variations in phenolic electrophiles
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Electronic, steric and leaving group effects for Ni-catalyzed direct arylations using C?O electrophiles were benchmarked. The scope of arylations with pivalates was general with respect to both the electronics on the electrophile and the azoles. Furthermore, the arylation of azoles with tosylates, mesylates and carbamates with varying electronics was explored, and showed electronic trends similar to those of the pivalate reactions. Finally, the relative rate of arylation of 5-methyl benzoxazole with two electronically-similar electrophiles bearing different leaving groups was established. The results from these studies implicate the following order of relative reactivity: mesylates>pivalates>carbamates.
- Steinberg, Deborah F.,Turk, Morgan C.,Kalyani, Dipannita
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supporting information
p. 2196 - 2209
(2017/03/24)
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- Transition-metal free 2-arylbenzoxazole formation from aryl amides and cyclohexanones
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A transition-metal-free method for the synthesis of 2-arylbenzoxazoles from readily available cyclohexanones and benzamides is described. The combined use of KI, p-TsOH and DMSO significantly improved the reaction yields. Non-aromatic cyclohexanones were smoothly dehydrogenated and acted as the aryl source using oxygen as the oxidant.
- Cao, Xiangxiang,Cheng, Xiufang,Bai, Yang,Liu, Saiwen,Deng, Guo-Jun
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supporting information
p. 4644 - 4648
(2015/02/19)
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- Mechanistic exploration of the palladium-catalyzed process for the synthesis of benzoxazoles and benzothiazoles
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A convenient one-pot palladium-catalyzed cascade process for the preparation of both benzoxazoles and benzothiazoles has been developed. While these reactions proceed to give similar compounds the mechanisms governing the processes are different as are the experimental conditions employed.
- Bochatay, Valentin N.,Boissarie, Patrick J.,Murphy, John A.,Suckling, Colin J.,Lang, Stuart
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p. 1471 - 1477
(2013/03/28)
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- Palladium-catalyzed direct arylation of benzoxazoles with unactivated simple arenes
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Using CuBr2 as an additive, the Pd-catalyzed intermolecular C-H-C-H cross-coupling between benzoxazoles and unactivated simple arenes has been developed. This protocol provides a straightforward approach for the biological activity of 2-arylbenzoxazole derivatives.
- Wu, Ge,Zhou, Jun,Zhang, Min,Hu, Peng,Su, Weiping
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supporting information
p. 8964 - 8966
(2012/11/14)
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- Iron-catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols
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The iron-catalyzed 2-arylbenzoxazole formation from o-nitrophenols and benzylic alcohols using hydrogen transfer is described. Various 2-arylbenzoxazoles were selectively obtained in good to excellent yields. The reaction tolerated a wide range of functionalities. The alcohol oxidation, nitro reduction, condensation, and dehydrogenation were realized in a cascade without external reducing reagent and oxidant.
- Wu, Mingyue,Hu, Xiong,Liu, Juan,Liao, Yunfeng,Deng, Guo-Jun
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supporting information; experimental part
p. 2722 - 2725
(2012/07/28)
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- A powerful palladium-catalyzed multicomponent process for the preparation of oxazolines and benzoxazoles
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Efficient and convenient three-component couplings of an aryl halide, isocyanide, and an amino alcohol under palladium catalysis provide a range of oxazolines and benzoxazoles in excellent yield.
- Boissarie, Patrick J.,Hamilton, Zoe E.,Lang, Stuart,Murphy, John A.,Suckling, Colin J.
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supporting information; experimental part
p. 6256 - 6259
(2012/01/06)
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- Oxidative conversion of amines into benzoxazoles using hydrogen transfer catalysis
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Benzoxazoles are synthesised directly by oxidative condensation of primary and secondary amines with o-aminophenols under hydrogen transfer catalysis. The optimal system utilises 1 mol % of the Shvo catalyst, with dimethoxybenzoquinone as the hydrogen-acc
- Blacker, A. John,Farah, Mohamed M.,Marsden, Stephen P.,Saidi, Ourida,Williams, Jonathan M.J.
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experimental part
p. 6106 - 6109
(2009/12/26)
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- Indium-mediated one-pot synthesis of benzoxazoles or oxazoles from 2-nitrophenols or 1-aryl-2-nitroethanones
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One-pot reduction-triggered heterocyclizations from 2-nitrophenols to benzoxazoles and from 1-aryl-2-nitroethanones to oxazoles were investigated. In the presence of indium/AcOH in benzene at reflux, 2-nitrophenols and R-C(OMe)3 (R=H, Me, Ph) produced excellent yields of corresponding benzoxazoles within an hour. Similarly, 1-aryl-2-nitroethanones and Ph-C(OMe)3 in the presence of indium/AcOH in acetonitrile transformed into the corresponding oxazoles with good yields.
- Lee, Jung June,Kim, Jihye,Jun, Young Moo,Lee, Byung Min,Kim, Byeong Hyo
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experimental part
p. 8821 - 8831
(2009/12/26)
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- Copper-catalyzed synthesis of benzoxazoles via a regioselective C-H functionalization/C-O bond formation under an air atmosphere
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(Chemical Equation Presented) An efficient method for the synthesis of functionalized benzoxazoles is described that involves a copper(II)-catalyzed regioselective C-H functionalization/C-O bond formation protocol. The use of dichlorobenzene as a solvent at 160°C allows the use of air as the terminal oxidant in the catalytic synthesis of benzoxazoles in a process that has high functional group tolerance. The presence of a directing group at the meta position markedly improves the reaction efficacy and a variety of 7-substituted benzoxazoles are selectively produced under mild reaction conditions. The mechanism of the reaction is also discussed in this report.
- Ueda, Satoshi,Nagasawa, Hideko
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supporting information; experimental part
p. 4272 - 4277
(2009/09/08)
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- Synthesis of 2-arylbenzoxazoles by copper-catalyzed intramolecular oxidative C-O coupling of benzanilides
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(Chemical Equation Presented) No need for additives: A wide variety of functionalized 2-arylbenzoxazoles can be prepared with high functional-group tolerance and regioselectivity by a copper-catalyzed intramolecular oxidative C-O coupling of benzanilides. The catalytic cycle is completed by the regeneration of the copper catalyst using molecular oxygen as a terminal oxidant without the need for additives.
- Ueda, Satoshi,Nagasawa, Hideko
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supporting information; experimental part
p. 6411 - 6413
(2009/03/11)
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- Parallel synthesis of benzoxazoles via microwave-assisted dielectric heating
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A facile route to benzoxazoles has been developed using microwave-assisted dielectric heating. The ease of synthesis and workup allowed the parallel synthesis of a 48-membered library of benzoxazoles quickly and efficiently.
- Pottorf, Richard S.,Chadha, Naresh K.,Katkevics, Martins,Ozola, Vita,Suna, Edgars,Ghane, Hadi,Regberg, Tor,Player, Mark R.
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p. 175 - 178
(2007/10/03)
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- Investigation of the Synthesis of Benzoxazole via Aryne Reaction
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The reaction of o- and m-halobenzamides under aryne-forming conditions yielded the corresponding o-hydroxyphenyl amidines instead of the expected benzoxazole derivatives.The amidines, however, were converted to the corresponding benzoxazole either by sublimation or acidic hydrolysis.Evidence is presented that benzoxazoles are initially formed in these reactions but are readily aminated to the corresponding hydroxyphenyl amidines under the highly basic reaction conditions used in these aryne-forming reactions.
- El-Sheikh, Mustafa I.,Marks, Alan,Biehl, Edward R.
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p. 3256 - 3259
(2007/10/02)
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- Zur Kinetik des Ringschlusses von 2-Hydroxybenzaniliden zu Benzoxazolen
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The reaction rates of cyclization of 2-hydroxybenzanilides to benzoxazoles have been measured in N-methyl-2-pyrrolidone at different temperatures.The reactions follow second-order kinetics.
- Seha, Zdenek
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p. 916 - 917
(2007/10/02)
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