- Rhodium(III)-catalyzed chemodivergent annulations between phenyloxazoles and diazos via C–H activation
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Acid-controlled, chemodivergent and redox-neutral annulations for the synthesis of isocoumarins and isoquinolinones have been realized via Rh(III)-catalyzed C[sbnd]H activation. Diazo compounds act as a carbene precursor, and coupling occurs in one-pot process, where adipic acid and trimethylacetic acid promote chemodivergent cyclizations.
- Zhang, Xueguo,Wang, Peigen,Zhu, Liangwei,Chen, Baohua
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supporting information
p. 695 - 699
(2020/06/28)
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- Lewis-acid-promoted cyclization reaction: Synthesis of N3-chloroethyl and N3-thiocyanatoethyl quinazolinones
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A Lewis-acid-promoted cyclization reaction of benzoyl chlorides with 2-(4,5-dihydrooxazol-2-yl)anilines, which can offer a series of N3-chloroethyl quinazolinones, is disclosed. The reaction is compatible with the functional groups of the substrates; environment-friendly AlCl3 is probably the chloride source. Moreover, the addition of NH4SCN can also produce a range of N3-thiocyanatoethyl quinazolinones in moderate-to-good yields.
- Hu, Fang-Peng,Zhang, Ming-Ming,Huang, Guo-Sheng
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supporting information
p. 9315 - 9319
(2021/06/14)
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- Base-promoted Lewis acid catalyzed synthesis of quinazoline derivatives
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A one-pot protocol has been developed for the synthesis of quinazolinones from amide-oxazolines with TsCl via a cyclic 1,3-azaoxonium intermediate and 6π electron cyclization in the presence of a Lewis acid and base. The process is operationally simple and has a broad substrate scope. This method provides a unique strategy for the construction of quinazolinones.
- Cui, Xin-Feng,Hu, Fang-Peng,Huang, Guo-Sheng,Lu, Guo-Qiang
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p. 4376 - 4380
(2020/10/20)
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- Synthesis of quinazoin-4-ones through an acid ion exchange resin mediated cascade reaction
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An interesting cascade reaction of N-(2-(4,5-dihydrooxazol-2-yl)phenyl)benzamide in the presence of an acid ion exchange resin is described. In this reaction, a range of substrates bearing various substituent groups are well compatible. This work provides a green and atom-economical alternative approach for the synthesis of quinazolin-4-ones in good yields.
- He, Lei,Li, Wanmei,Xu, Jun,Yang, Huiyong,Zhang, Pengfei,Zhang, Yilan
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supporting information
p. 4406 - 4414
(2020/10/20)
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- Cu-Catalyzed C-H Alkenylation of Benzoic Acid and Acrylic Acid Derivatives with Vinyl Boronates
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An efficient Cu-catalyzed C-H alkenylation with acyclic and cyclic vinyl boronates was realized for the first time under mild conditions. The scope of the vinyl borons and the compatibility with functional groups including heterocycles are superior than Pd-catalyzed C-H coupling with vinyl borons, providing a reliable access to multisubstituted alkenes and dienes. Subsequent hydrogenation of the product from the internal vinyl borons will lead to installation of secondary alkyls.
- Li, Jian-Jun,Wang, Cheng-Gang,Yu, Jin-Feng,Wang, Peng,Wang, Peng,Yu, Jin-Quan
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supporting information
p. 4692 - 4696
(2020/06/25)
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- Copper mediated C(sp2)-H amination and hydroxylation of phosphinamides
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Copper mediated C(sp2)-H amination and hydroxylation of arylphosphinic acid are accomplished by adopting phosphinamide as the directing group. This method is distinguished by its wide substrate scope and excellent functional group tolerance, th
- Sun, Shang-Zheng,Shang, Ming,Xu, Hui,Cheng, Tai-Jin,Li, Ming-Hong,Dai, Hui-Xiong
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supporting information
p. 1444 - 1447
(2020/02/11)
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- Cu-Mediated C-H Thioetherification of Arenes at Room Temperature
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Cu-mediated C-H thioetherification of arenes with ethylene sulfide has been developed using a readily removable directing group. The reaction proceeded at room temperature, and a variety of sensitive functional groups including chloro, bromo, and vinyl were well tolerated. The thiolated products could be converted to the seven-membered benzoxathiepinones derivatives by a sequence of hydrolysis-lactonization reactions.
- Wang, Xing,Yi, Xing,Xu, Hui,Dai, Hui-Xiong
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supporting information
p. 5981 - 5985
(2019/08/26)
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- Palladium-Catalyzed Electrochemical C-H Bromination Using NH4Br as the Brominating Reagent
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The palladium-catalyzed electrochemical C-H bromination of benzamide derivatives under divided cells is developed, in which NH4Br serves as a brominating reagent and electrolyte. The protocol avoids the use of chemical oxidants and provides an alternative method for the synthesis of aryl bromides.
- Yang, Qi-Liang,Wang, Xiang-Yang,Wang, Tong-Lin,Yang, Xiang,Liu, Dong,Tong, Xiaofeng,Wu, Xin-Yan,Mei, Tian-Sheng
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supporting information
p. 2645 - 2649
(2019/04/17)
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- Synthesis of quinazolin-4(1 H)-ones via amination and annulation of amidines and benzamides
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Quinazolinones have broad applications in the biological, pharmaceutical and material fields. Studies on the synthesis of these compounds are therefore widely conducted. Herein, a novel and highly efficient copper-mediated tandem C(sp2)-H amination and annulation of benzamides and amidines for the synthesis of quinazolin-4(1H)-ones is proposed. This synthetic route can be useful for the construction of quinazolin-4(1H)-one frameworks.
- Hu, Fangpeng,Cui, Xinfeng,Ban, Zihui,Lu, Guoqiang,Luo, Nan,Huang, Guosheng
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supporting information
p. 2356 - 2360
(2019/03/06)
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- Amide-Oxazoline Directed ortho-C–H Nitration Mediated by CuII
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A CuII-mediated ortho-C–H nitration using amide-oxazoline as the directing group has been developed. The reactions utilize sodium nitrite as the source of the nitro group under O2 atmosphere and proceed smoothly. The desired products can be obtained in yields of 26–94 %.
- Gao, Tian-Hong,Wang, Chun-Meng,Tang, Kai-Xiang,Xu, Yun-Gen,Sun, Li-Ping
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p. 3005 - 3011
(2019/05/15)
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- Copper-Mediated Amination of Aryl C-H Bonds with the Direct Use of Aqueous Ammonia via a Disproportionation Pathway
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The direct amination of C-H bonds with ammonia is a challenge in synthetic chemistry. Herein, we present a copper-mediated approach that enables a chelation-assisted aromatic C-H bond amination using aqueous ammonia. A key strategy was to use soft low-valent Cu(I) species to avoid the strong coordination of ammonia. Mechanistic investigations suggest that the catalysis is initiated by a facile deprotonation of bound ammonia, and the C-N coupling is achieved by subsequent reductive elimination of the resultant copper-amido intermediate from a Cu(III) intermediate that is readily generated by disproportionation of low-valent copper analogues. This mechanistic postulate was supported by a preliminary kinetic isotope effect study and computations. This new chelation-assisted, copper-mediated C-H bond amination with aqueous ammonia was successfully applied to a broad range of substrates to deliver primary anilines. Moreover, the mild conditions required for this transformation allowed the reaction to operate even under substoichiometric conditions to enable a late-stage application for the preparation of pharmaceutical agents.
- Kim, Hyunwoo,Heo, Joon,Kim, Junho,Baik, Mu-Hyun,Chang, Sukbok
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supporting information
p. 14350 - 14356
(2018/11/06)
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- A 2 - substituted oxazoline or 2 - substituted piperazine synthetic method (by machine translation)
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The invention discloses a method for synthesizing 2 - substituted oxazoline or 2 - substituted oxazine new method, by nitrile and amino ethanol or 3 - amino - 1 - propanol as raw material, in the absence of solvent, can be used for the recycling of the sulfur to induce synthesis of 2 - substituted oxazoline and 2 - substituted piperazine. The method of the invention has low cost, simple reaction process, mild reaction conditions, the reaction time is short, the yield and the like, is suitable for the industrial generation. (by machine translation)
- -
-
Paragraph 0021; 0034
(2017/08/25)
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- A Novel Synthesis of 1,2,3-Benzotriazinones from 2-(o -Aminophenyl)oxazolines
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1,2,3-Benzotriazinones were synthesized in excellent yields by the reaction of 2-(o-aminophenyl)oxazolines and isoamyl nitrite in methanol. The crystal structure of the acetyl derivative of one of the 1,2,3-benzotriazinones provided additional support for
- Rocha-Alonzo, Fernando,Chávez, Daniel,Ochoa-Terán, Adrián,Morales-Morales, David,Velázquez-Contreras, Enrique F.,Parra-Hake, Miguel
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- Nickel-Catalyzed Regioselective C–H Bond Mono- and Bis-Nitration of Aryloxazolines with tert-Butyl Nitrite as Nitro Source
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An efficient and regioselective nickel-catalyzed remote C–H nitration of 2-aryloxazoline amides using the non-corrosive tert-butyl nitrite (TBN) as nitro source has been developed. The protocol makes use of inexpensive nickel salts as catalysts and delivers the corresponding products in excellent yields. Notably, bis-nitration products were obtained by simply increasing the amount of tert-butyl nitrite. This reaction proceeds in air and features excellent functional group compatibility, broad substrate scope and is suitable for gram-scale synthesis. (Figure presented.).
- Wan, Li,Qiao, Kai,Yuan, Xin,Zheng, Ming-Wei,Fan, Bing-Bing,Di, Zhe Chen,Zhang, Dong,Fang, Zheng,Guo, Kai
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supporting information
p. 2596 - 2604
(2017/08/16)
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- Highly efficient synthesis of β-nitrate ester carboxamides through the ring-opening of 2-oxazolines
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A novel method for the synthesis of β-nitrate ester carboxamides using non-corrosive tert-butyl nitrite (TBN) as the nitro source and easily available oxygen as the oxidant has been developed. Variously substituted 2-oxazolines were efficiently ring-opened to deliver the corresponding products in excellent yields. Notably, this reaction provides fast access to pharmaceuticals such as nicorandil.
- Qiao, Kai,Yuan, Xin,Wan, Li,Zheng, Ming-Wei,Zhang, Dong,Fan, Bing-Bing,Di, Zhe-Chen,Fang, Zheng,Guo, Kai
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supporting information
p. 5789 - 5793
(2017/12/26)
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- Supramolecular ensemble of PBI derivative and copper nanoparticles: A light harvesting antenna for photocatalytic C(sp2)-H functionalization
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Supramolecular aggregates of triazole-appended perylene bisimide (PBI) derivative 3 served as reactors for the generation of copper nanoparticles (CuNPs). During the reduction process, these aggregates were oxidized to triazole N-oxide species 4. Interestingly, the in situ generated CuNPs, in combination with oxidized species 4 (supramolecular ensemble 4:CuNPs), exhibited excellent photocatalytic efficiency in C(sp2)-H alkynylation and amination reactions of arenes under mild and eco-friendly conditions (inexpensive catalyst, room temperature, mixed aqueous media, aerial conditions and visible light irradiation).
- Kaur, Sandeep,Kumar, Manoj,Bhalla, Vandana
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p. 5870 - 5883
(2016/11/06)
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- Oxazolines as Dual-Function Traceless Chromophores and Chiral Auxiliaries: Enantioselective Photoassisted Synthesis of Polyheterocyclic Ketones
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2-(o-Amidophenyl)oxa- and -thiazolines undergo excited-state intramolecular proton transfer (ESIPT), generating aza-o-xylylenes capable of intramolecular [4+2] and [4+4] cycloadditions with tethered unsaturated pendants. Facile hydrolysis of the primary p
- Mukhina, Olga A.,Kutateladze, Andrei G.
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supporting information
p. 2110 - 2113
(2016/03/05)
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- Design, Synthesis, Fungicidal Activity, and Unexpected Docking Model of the First Chiral Boscalid Analogues Containing Oxazolines
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Chirality greatly influences the biological and pharmacological properties of a pesticide and will contribute to unnecessary environmental loading and undesired ecological impact. No structure and activity relationship (SAR) of enantiopure succinate dehydrogenase inhibitors (SDHIs) was documented during the structure optimization of boscalids. On the basis of commercial SDHIs, oxazoline natural products, and versatile oxazoline ligands in organic synthesis, the first effort was devoted to explore the chiral SDHIs and the preliminary mechanism thereof. Fine-tuning furnished chiral nicotinamides 4ag as a more promising fungicidal candidate against Rhizoctonia solani, Botrytis cinerea, and Sclerotinia sclerotiorum, with EC50 values of 0.58, 0.42, and 2.10 mg/L, respectively. In vivo bioassay and molecular docking were investigated to explore the potential in practical application and plausible novelty in action mechanism, respectively. The unexpected molecular docking model showed the different chiral effects on the binding site with the amino acid residues. This chiral nicotinamide also featured easy synthesis and cost-efficacy. It will provide a powerful complement to the commercial SDHI fungicides with the introduction of chirality.
- Li, Shengkun,Li, Dangdang,Xiao, Taifeng,Zhang, Shasha,Song, Zehua,Ma, Hongyu
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p. 8927 - 8934
(2016/12/07)
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- A Mild and Regioselective Route to Functionalized Quinazolines
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A Rh-catalyzed ortho-amidation cyclocondensation sequence gave a range of 4-aminoquinazolines in high yield. The method features a remarkably mild C(sp2)-H activation step and can be exploited to rapidly access compounds with established biological activity.
- Maiden, Tracy M. M.,Swanson, Stephen,Procopiou, Panayiotis A.,Harrity, Joseph P. A.
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supporting information
p. 14342 - 14346
(2015/10/05)
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- Cu(II)-Mediated C(sp2)-H Hydroxylation
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A Cu(II)-mediated ortho-C-H hydroxylation using a removable directing group has been developed. The reaction exhibits considerable functional group tolerance. The use of O2 as an oxidant is crucial for the reactivity. Water is also found to significantly improve this reaction.
- Sun, Shang-Zheng,Shang, Ming,Wang, Hong-Li,Lin, Hai-Xia,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 8843 - 8848
(2015/09/15)
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- Cu(II)-catalyzed coupling of aromatic C-H bonds with malonates
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A new Cu(II)-catalyzed oxidative coupling of arenes with malonates has been developed using an amide-oxazoline directing group. The reaction proceeds via C(sp2)-H activation and malonate coupling, followed by intramolecular oxidative N-C bond formation. A variety of arenes bearing different substituents are shown to be compatible with this reaction.
- Wang, Hong-Li,Shang, Ming,Sun, Shang-Zheng,Zhou, Zeng-Le,Laforteza, Brian N.,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 1228 - 1231
(2015/03/14)
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- Ruthenium(II) 8-quinolinolates: Synthesis, characterization, crystal structure and catalysis in the synthesis of 2-oxazolines
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Abstract New octahedral ruthenium(II) complexes (1-4) have been synthesized from the reaction of ruthenium(II) precursors [RuHCl(CO)(EPh3)3] (E = P or As) with the bidentate Schiff base ligands, 2-((2,6-dimethylphenylimino)methyl)quinolin-8-ol (L1) and 2-((2,6-diisopropylphenylimino)methyl)quinolin-8-ol (L2) in ethanol. These complexes have been characterized by elemental analyses, IR, UV-Vis, 1H, 13C and 31P NMR and ESI-Mass spectroscopy. The molecular structure of the complex [RuCl(CO)(PPh3)2(L2)] (2) was determined by single-crystal X-ray diffraction, which reveals a distorted octahedral geometry around ruthenium(II) ion. The catalytic activity of the new complexes was evaluated for the condensation of nitriles with ethanolamine under solvent free conditions. The processes were operative with aromatic and heteroaromatic nitriles and tolerated several substitutional groups. The studies on the effect of substitution over ligands, coligands, reaction time, temperature and catalyst loading were carried out in order to find the best catalyst in this series of complexes and favorable reaction conditions. A probable mechanism for the catalytic condensation of nitrile has also been proposed. The catalyst was recovered and recycled up to five times without significant loss of its activity.
- Anitha,Manikandan,Prakash,Pachiyappan,Viswanathamurthi,Malecki
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p. 266 - 273
(2015/06/22)
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- Cu(II)-mediated C-H amidation and amination of arenes: Exceptional compatibility with heterocycles
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A Cu(OAc)2-mediated C-H amidation and amination of arenes and heteroarenes has been developed using a readily removable directing group. A wide range of sulfonamides, amides, and anilines function as amine donors in this reaction. Heterocycles present in both reactants are tolerated, making this a broadly applicable method for the synthesis of a family of inhibitors including 2-benzamidobenzoic acids and N-phenylaminobenzoates.
- Shang, Ming,Sun, Shang-Zheng,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 3354 - 3357
(2014/03/21)
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- Living cationic ring-opening polymerization of 2-oxazolines initiated by rare-earth metal triflates
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The cationic ring-opening polymerization (CROP) of substituted 2-oxazolines using rare-earth metal triflates (RE(OTf)3) as initiator was investigated for the first time. In this work, we examined the polymerization characteristics of 2-ethyl-2-oxazoline (EtOx) initiated by Sc(OTf)3 under conventional thermal heating and microwave irradiation, and compared the respective outcomes with those obtained with the most frequently used initiator methyl tosylate (MeOTs). The results indicated that Sc(OTf)3 exhibits a higher catalytic efficiency to the EtOx polymerization than MeOTs under identical conditions. The controlled/living nature of the Sc(OTf)3-catalyzed CROP was confirmed by its linear first-order kinetics and the narrow molecular weight distribution of the resultant polymers as well as the block copolymerization of EtOx and 2-phenyl-2-oxazoline (PhOx). Based on in situ NMR spectroscopic studies and SEC analysis of PEtOx samples obtained from the control termination experiments, a possible initiating/propagating mechanism has been proposed for the living cationic ring-opening polymerization. Morever, this rare-earth catalytic system can also be applied to the ring-opening polymerization of some sterically hindered or aryl-substituted 2-oxazolines.
- Hu, Fangyu,Xie, Shoulei,Jiang, Liming,Shen, Zhiquan
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p. 59917 - 59926
(2015/02/19)
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- Cu(II)-mediated ortho C-H alkynylation of (hetero)arenes with terminal alkynes
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Cu(II)-promoted ortho alkynylation of arenes and heteroarenes with terminal alkynes has been developed to prepare aryl alkynes. A variety of arenes and terminal alkynes bearing different substituents are compatible with this reaction, thus providing an alternative disconnection to Sonogashira coupling.
- Shang, Ming,Wang, Hong-Li,Sun, Shang-Zheng,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 11590 - 11593
(2014/10/15)
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- S-Co(II) cascade catalysis: Cyclocondensation of aromatic nitriles with alkamine
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A solvent-free S/Co(NO3)2 cascade catalyzed cyclocondensation reaction of aromatic nitriles with 3-amino-1-propanol or 2-aminoethanol has been successfully developed under thermal and microwave conditions. By this two-component protocol, mono- and bis-oxazines and oxazolines were selectively synthesized both in good to excellent yields and short reaction times. This catalytic system exhibits excellent chemoselectivity, and can be reused at least seven times without significant loss of activity in subsequent reactions.
- Ge, Haixia,Liu, Ping,Li, Xiangnan,Sun, Wei,Li, Jianli,Yang, Bingqin,Shi, Zhen
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p. 6591 - 6597
(2013/07/26)
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- Solvent-free tandem synthesis of 2-thiazolines and 2-oxazolines catalyzed by a copper catalyst
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Tandem reactions of nitriles with 2-aminoethanethiol hydrochloride or amino alcohols in the presence of a catalytic amount of cupric methacrylate (Cu II2L4, L = methacrylate) were employed to prepare 2-thiazolines and 2-ox
- Li, Xiangnan,Zhou, Baoyue,Zhang, Jin,She, Mengyao,An, Shujuan,Ge, Haixia,Li, Cong,Yin, Bing,Li, Jianli,Shi, Zhen
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experimental part
p. 1626 - 1632
(2012/05/04)
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- Cooperative thiourea-Bronsted acid organocatalysis: Enantioselective cyanosilylation of aldehydes with TMSCN
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We report a new thiourea - Bronsted acid cooperative catalytic system for the enantioselective cyanosilylation of aldehydes with yields up to 90% and enantioselectivities up to 88%. The addition of an achiral acid was found to be crucial for high asymmetric induction. Mechanistic investigations using a combination of NMR, ESI-MS, and density functional theory computations (including solvent corrections) at the M06/6-31G(d,p) level of theory suggest that the key catalytic species results from the cooperative interaction of bifunctional thioureas and an achiral acid that form well-defined chiral hydrogen-bonding environments.
- Zhang, Zhiguo,Lippert, Katharina M.,Hausmann, Heike,Kotke, Mike,Schreiner, Peter R.
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experimental part
p. 9764 - 9776
(2012/01/03)
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- Oxazoline chemistry part III. Synthesis and characterisation of [2-(2′-anilinyl)-2-oxazolines] and some related compounds
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The syntheses and characterisation of a series of chiral and achiral 2-(aminophenyl)-2-oxazolines and some related compounds is reported. All of the derivatives have been produced by a one-step procedure involving the treatment of isatoic anhydride (i.e.
- Button, Karen M.,Gossage, Robert A.
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p. 513 - 517
(2007/10/03)
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- Reaction of isatoic anhydride with bifunctional reagents: Synthesis of some new quinazolone fused heterocycles, 2-substituted anilinoheterocyclic derivatives and other related compounds
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A new synthesis of quinazolone fused heterocycles (2, 5, 8), anilinoheterocycles (4, 7, 10, 12, 14) and substituted 2-aminoquinoline (15, 16) based on the reaction of isatoic anhydride (1) with different active bifunctional compounds in presence of glacial acetic acid and freshly fused sodium acetate is described. Structures of the newly prepared compounds are established by chemical and spectral data.
- Fadda,Refat,Zaki,Monir
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p. 3537 - 3545
(2007/10/03)
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- Clay catalyzed conversion of isatoic anhydride to 2-(o-aminophenyl)oxazolines
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A simple and environmentally safe procedure for the preparation of 2-(o-aminophenyl)oxazolines from isatoic anhydride is presented. A series of chiral derivatives of the title compound is prepared in moderate yield via natural kaolinitic clay catalyzed re
- Gajare, Anil S.,Shaikh, Nadim S.,Jnaneshwara, Gowda K.,Deshpande, Vishnu H.,Ravindranathan, Thottappilli,Bedekar, Ashutosh V.
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p. 999 - 1001
(2007/10/03)
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