- Transition metal free oxygenation of 8-aminoquinoline amides in water
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The oxygenation of 8-aminoquinoline amides by benzoyl peroxide at the C5 position in water is developed in the absence of a transition metal catalyst, affording the desired products in moderate to good yields of up to 88%. Mechanism studies reveal that the reaction would involve a radical process.
- Yao, Xinghui,Weng, Xin,Wang, Kaixuan,Xiang, Haifeng,Zhou, Xiangge
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- Nickel-mediated C(sp2)-H amidation in synthesis of secondary sulfonamides via sulfonyl azides as amino source
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In this paper, Ni(II)- Catalyzed ortho-amidation of C(sp2)-H bond with sulfonyl azides directed by (quinolin-8-yl) amine (AQ-amine) is described. The method provides a straightforward method for the synthesis of sulfonamides from available sulfonyl azides via the transition-metal-catalyzed C(sp2)-N bond forming reaction. The amidation reactions exhibit high functional group compatibility, which might proceed a Ni(III)/Ni(I) catalytic cycle. We also applied sulfonamide compound in OLEDs, which exhibits the certain application potential in OLEDs field.
- Xu, Peng,Ding, Peng-Fei,Zhang, Mei-Qi,Xia, Yu-Shi,Xie, Ting
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- Transition Metal-Free Regioselective Remote C?H Bond 2,2,2-Trifluoroethoxylation of 8-Aminoquinoline Derivatives at the C5 Position
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The regioselective 2,2,2-trifluoroethoxylation at the C5 position of amides derived from the 8-aminoquinoline has been developed. In the presence of PIDA, an unprecedented and undirected transition metal-free transformation was achieved using the readily available and appealing 2,2,2-trifluoroethanol as the fluorinated source. The selective distal 2,2,2-trifluoroethoxylation of an array of amides was achieved in moderate to good yields (12 examples, up to 61 % yield). This approach provided efficient access to high-value added fluorinated quinoline derivatives, key building blocks for bulk and fine chemical industry.
- Ruyet, Louise,Poisson, Thomas,Besset, Tatiana
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supporting information
p. 3407 - 3410
(2021/06/28)
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- Highly regioselective and stereoselective synthesis of C-Aryl glycosidesvianickel-catalyzedortho-C-H glycosylation of 8-aminoquinoline benzamides
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C-Aryl glycosides are of high value as drug candidates. Here a novel and cost-effective nickel catalyzedortho-CAr-H glycosylation reaction with high regioselectivity and excellent α-selectivity is described. This method shows great functional group compatibility with various glycosides, showing its synthetic potential. Mechanistic studies indicate that C-H activation could be the rate-determining step.
- Chen, Xi,Ding, Ya-Nan,Gou, Xue-Ya,Liang, Yong-Min,Luan, Yu-Yong,Niu, Zhi-Jie,Shi, Wei-Yu,Zhang, Zhe,Zheng, Nian
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p. 8945 - 8948
(2021/09/10)
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- C-5 selective chlorination of 8-aminoquinoline amides using dichloromethane
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An oxidant-free electrochemical regioselective chlorination of 8-aminoquinoline amides at ambient temperature in batch and continuous-flow was achieved. Inert DCM was used as the chlorinating reagent. Owing to the continuous-flow setup, the reaction scale
- Lin, Xinxin,Zeng, Cuilian,Liu, Chengkou,Fang, Zheng,Guo, Kai
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supporting information
p. 1352 - 1357
(2021/02/26)
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- Visible-Light-Triggered Decarboxylative Alkylation of 8-Acylaminoquinoline with N -Hydroxyphthalimide Ester
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A facile protocol for visible-light-induced decarboxylative radical coupling of NHP esters with 8-aminoquinoline amides is reported, affording a highly efficient approach to synthesize a variety of 2-alkylated or 2,4-dialkylated 8-aminoquinoline derivativ
- Aisha, Aertuke,Jin, Can,Li, Deyu,Sun, Bin,Zhu, Rui,Zhuang, Xiaohui
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supporting information
p. 677 - 682
(2020/04/08)
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- Metal-Free Electrochemical Oxidative Dihalogenation of Quinolines on the C5 and C7 Positions Using N-Halosuccinimides
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An efficient and convenient method for electrochemically oxidative dichlorination or dibromination of 8-aminoquinolines on C5 and C7 positions using N-halosuccinimides (NCS and NBS) as the halogen source was described. Substrates with various functional g
- Hou, Jiahao,Wang, Kai,Zhang, Changjun,Wei, Tingting,Bai, Renren,Xie, Yuanyuan
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supporting information
p. 6382 - 6386
(2020/10/19)
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- Catalyst- And oxidant-free electrochemical: para -selective hydroxylation of N -arylamides in batch and continuous-flow
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Hydroxyl compounds serve as key building blocks in the preparation of biologically active natural products and drugs. Traditionally, hydroxylation of the aromatic ring is achieved using stoichiometric amounts of oxidants, which leads to low atom-economy, undesired by-products, potential explosion risk and environmental pollution. Recently, electrosynthesis has attracted increasing attention as it employs clean electrical energy to promote redox reactions avoiding the use of oxidants. However, due to the poor mass and heat transfers of batch cells, low productivity and selectivity limit its further application. Herein, we develop a catalyst-, oxidant-, acidic solvent- and quaternary ammonium salt-free electrochemical para-selective hydroxylation of N-arylamides at room temperature in batch and continuous-flow. This proposal features excellent position control and water, air and functional group tolerance. Also, it is easy to scale up with higher productivity and selectivity using a flow electrolysis cell.
- Chen, Meng-Yi,Fang, Zheng,Guo, Kai,Lin, Xin-Xin,Liu, Cheng-Kou
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supporting information
p. 6437 - 6443
(2020/11/09)
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- Method for preparing phenanthridone compound by copper compound induction
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The invention belongs to the fields of organic synthesis and metal catalysis, and discloses a method for preparing a phenanthridone compound by copper compound induction. The method comprises the following steps: adding a benzamide derivative, an O-bromob
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Paragraph 0150; 0159
(2019/02/25)
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- Copper-mediated synthesis of quinazolin-4(3: H)-ones from N-(quinolin-8-yl)benzamide and amidine hydrochlorides
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An efficient copper-mediated tandem C(sp2)-H amination to provide quinazolinones from N-(quinolin-8-yl)benzamide and amidine hydrochlorides has been developed. It can afford rather complex products in a single step synthesis from easily availab
- Ban, Zihui,Cui, Xinfeng,Hu, Fangpeng,Lu, Guoqiang,Luo, Nan,Huang, Guosheng
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supporting information
p. 12963 - 12966
(2019/08/28)
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- CoIII-Catalyzed Isonitrile Insertion/Acyl Group Migration Between C?H and N?H bonds of Arylamides
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A general efficient and site-selective cobalt-catalyzed insertion of isonitrile into C?H and N?H bonds of arylamides through C?H bond activation and alcohol assisted intramolecular trans-amidation is demonstrated. This straightforward approach overcomes the limitation by the presence of strongly chelating groups. Isolation of CoIII-isonitrile complex B has been achieved for the first time to understand the reaction mechanism.
- Kalsi, Deepti,Barsu, Nagaraju,Sundararaju, Basker
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p. 2360 - 2364
(2018/02/22)
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- Synthesis of phthalic acid derivatives: Via Pd-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates
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A Pd(ii)-catalyzed alkoxycarbonylation of aromatic C-H bonds with alkyl chloroformates has been developed. A broad range of benzamides and alkyl chloroformates are compatible with this protocol. The reaction is operationally simple and scalable. The direct group could be readily removed to access substituted phthalic acid esters (PAEs), 1,2-dibenzyl alcohols and phthalamides. Besides alkoxycarbonylation of benzamide β-C-H bonds, γ-alkoxycarbonylation of 2-phenylacetamide is also feasible.
- Liao, Gang,Chen, Hao-Ming,Shi, Bing-Feng
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p. 10859 - 10862
(2018/10/02)
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- Ruthenium-Catalyzed Difluoroalkylation of 8-Aminoquinoline Amides at the C5-Position
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A ruthenium-catalyzed highly selective difluoromethylation of 8-aminoquinoline amides at the C5 position has been developed. It tolerates a broad range of functional groups, providing the corresponding difluoromethylated products in moderate to good yields. Preliminary experimental results indicate that the tricoordinate ruthenium intermediate is the key factor in achieving the C5-position selectivity.
- Chen, Changpeng,Zeng, Runsheng,Zhang, Jingyu,Zhao, Yingsheng
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p. 6947 - 6950
(2017/12/26)
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- Copper-Catalyzed Selective ortho-C-H/N-H Annulation of Benzamides with Arynes: Synthesis of Phenanthridinone Alkaloids
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An efficient and convenient copper-catalyzed method has been developed to achieve direct ortho-C-H/N-H annulation to synthesize phenanthridinones with arynes. This method highlights an emerging strategy to transform inert C-H bonds into versatile functional groups in organic synthesis and provides a new way to synthesize phenanthridinone alkaloids efficiently.
- Zhang, Ting-Yu,Lin, Jun-Bing,Li, Quan-Zhe,Kang, Jun-Chen,Pan, Jin-Long,Hou, Si-Hua,Chen, Chao,Zhang, Shu-Yu
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supporting information
p. 1764 - 1767
(2017/04/11)
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- Copper-Mediated Remote Highly Site-Selective C–H Bond Bromination and Chlorination of Quinolines at the C5 Position that is Geometrically Difficult to Access
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A concise, simple, and efficient method for remote C–H bond halogenation (Br and Cl) of 8-aminoquinoline scaffolds at the geometrically difficult-to-access C5 position was explored with diverse substrate combinations in DMF. This protocol made use of inex
- Rao, Naidu Sambasiva,Reddy, Ganapam Manohar,Sridhar,Sarma, Maheswaran Harihara
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supporting information
p. 438 - 442
(2017/02/05)
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- Iron(iii)-catalyzed chelation assisted remote C-H bond oxygenation of 8-amidoquinolines
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Iron catalyzed site selective and chelation assisted C-H functionalization in 8-amidoquinolines is achieved. The remote C5-benzoxylation with benzoyl peroxide produced a variety of potentially bioactive 8-arylcarboxamido-5-benzoyloxy quinoline derivatives. The efficiency of the reaction reflects from the wide substrate scope with electronic differentiation on carboxamide and acyl peroxide in addition to tolerance of halo-substitutions on either of the aryls. The reaction is additive, silver free and proceeds without the exclusion of air or moisture.
- Vinayak, Botla,Navyasree, Pilli,Chandrasekharam, Malapaka
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p. 9200 - 9208
(2017/11/14)
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- One-Pot Approach to N-Quinolyl 3′/4′-Biaryl Carboxamides by Microwave-Assisted Suzuki-Miyaura Coupling and N-Boc Deprotection
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N-Quinolyl biaryl carboxamides have received tremendous attention for their notable biological properties. Here we have described a general protocol for the preparation of N-quinolyl 3′/4′-biaryl carboxamides by microwave-assisted Suzuki-Miyaura cross-coupling reaction and N-Boc deprotection in one pot. This method, which did not require acids, was used to produce a series of N-quinolyl 3′/4′-biaryl carboxamides with excellent functional group tolerance and high yields (70% to 95%).
- Huang, Zhi-You,Yang, Jing-Fang,Song, Ke,Chen, Qian,Zhou, Shao-Lin,Hao, Ge-Fei,Yang, Guang-Fu
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p. 9647 - 9657
(2016/11/02)
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- Ligand-enabled, copper-promoted regio- and chemoselective hydroxylation of arenes, aryl halides, and aryl methyl ethers
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We report here a practical method for the ortho C-H hydroxylation of benzamides with inexpensive copper(II) acetate monohydrate and a pyridine ligand. An intra- and intermolecular ligand combination was explored to achieve regio- and chemoselective hydroxylation. Interestingly, typical regiochemical scrambling associated with the C-H activation was further resolved by introducing a ligand-directed ortho hydroxylation of haloarenes and aryl methyl ethers.
- Singh, Bijaya Kumar,Jana, Ranjan
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p. 831 - 841
(2016/02/18)
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- Cobalt-Catalyzed sp2-C?H Activation: Intermolecular Heterocyclization with Allenes at Room Temperature
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The reactivity of allenes in transition-metal-catalyzed C?H activation chemistry is governed by the formation of either alkenyl–metal (M–alkenyl) or metal–π-allyl intermediates. Although either protonation or a β-hydride elimination is feasible with a M–alkenyl intermediate, cyclization has remained unexplored to date. Furthermore, due to the increased steric hindrance, the regioselectivity for the intramolecular cyclization of the metal–π-allyl intermediate was hampered towards the more substituted side. To address these issues, a unified approach to synthesize a diverse array of biologically and pharmaceutically relevant heterocyclic moieties by cobalt-catalyzed directed C?H functionalization was envisioned. Upon successful implementation, the present strategy led to the regioselective formation of dihydroisoquinolin-1(2H)-ones, isoquinolin-1(2H)-ones, dihydropyridones, and pyridones.
- Thrimurtulu, Neetipalli,Dey, Arnab,Maiti, Debabrata,Volla, Chandra M. R.
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supporting information
p. 12361 - 12365
(2016/10/13)
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- Diastereoselective [3+2] Annulation of Aromatic/Vinylic Amides with Bicyclic Alkenes through Cobalt-Catalyzed C-H Activation and Intramolecular Nucleophilic Addition
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A highly diastereoselective method for the synthesis of dihydroepoxybenzofluorenone derivatives from aromatic/vinylic amides and bicyclic alkenes is described. This new transformation proceeds through cobalt-catalyzed C-H activation and intramolecular nucleophilic addition to the amide functional group. Transition-metal-catalyzed C-H activation reactions of secondary amides with alkenes usually lead to [4+2] or [4+1] annulation; to the best of our knowledge, this is the first time that a [3+2] cycloaddition is described in this context. The reaction proceeds under mild conditions and tolerates a wide range of functional groups. Mechanistic studies imply that the C-H bond cleavage may be the rate-limiting step. [3+2] instead of [4+2] or [4+1]: The diastereoselective [3+2] annulation of secondary amides with alkenes proceeds by cobalt-catalyzed C-H activation and intramolecular nucleophilic addition to the amide functional group under mild conditions. Mechanistic studies suggest that the C-H bond cleavage is the rate-limiting step.
- Gandeepan, Parthasarathy,Rajamalli, Pachaiyappan,Cheng, Chien-Hong
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p. 4308 - 4311
(2016/04/01)
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- Nickel(II)-Mediated Regioselective C H Monoiodination of Arenes and Heteroarenes by using Molecular Iodine
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The 8-aminoquinoline-directed, nickel(II)-mediated ortho-iodination of benzamides using molecular iodine has been developed. The process is highly regioselective and furnishes only monoiodinated products. A broad range of arenes and heteroarenes with diverse functional groups provided monoiodinated products in good to excellent yields. (Figure presented.) .
- Khan, Bhuttu,Kant, Ruchir,Koley, Dipankar
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supporting information
p. 2352 - 2358
(2016/07/28)
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- Directing Group-Assisted Copper(II)-Catalyzed ortho-Carbonylation to Benzamide using 2,2′-Azobisisobutyronitrile (AIBN)
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An efficient copper-catalyzed regioselective C—H bond carbonylation of benzamides has been developed using 2,2′-azobisisobutyronitrile (AIBN) as traceless cyanating agent. The non-toxic and readily available AIBN was used for the carbonylative cyclization
- Khan, Bhuttu,Khan, Afsar Ali,Kant, Ruchir,Koley, Dipankar
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supporting information
p. 3753 - 3758
(2016/12/16)
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- Access to different isomeric dibenzoxazepinones through copper-catalyzed C-H etherification and C-N bond construction with controllable smiles rearrangement
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An efficient new way to access two regio-isomeric dibenzoxazepinones is reported from 8-aminoquinoline benzamides and 2-bromophenols. Through choice of conditions, the reaction proceeds either through a sequential C-H etherification and subsequent Goldberg reaction, both controlled by the aminoquinoline group and Cu(I), or via a C-H etherification and subsequent Smiles rearrangement promoted by Cu(II) and t-BuOK. The 8-aminoquinoline moiety, e.g., 8-amino-5-methoxyquinoline, is readily removable from the structures of dibenzoxazepinones under moderate conditions.
- Zhou, Yunfei,Zhu, Jianming,Li, Bo,Zhang, Yong,Feng, Jia,Hall, Adrian,Shi, Jiye,Zhu, Weiliang
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supporting information
p. 380 - 383
(2016/02/19)
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- Ligand-Controlled Monoselective C-Aryl Glycoside Synthesis via Palladium-Catalyzed C-H Functionalization of N-Quinolyl Benzamides with 1-Iodoglycals
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A monoselective synthesis of aryl-C-Δ1,2-glycosides from 1-iodoglycals via palladium-catalyzed ortho-C-H activation of N-quinolyl benzamides has been developed. An amino acid derivative was used as a crucial ligand to improve the yield and mono
- Liu, Minglong,Niu, Youhong,Wu, Yan-Fen,Ye, Xin-Shan
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supporting information
p. 1836 - 1839
(2016/05/19)
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- Rh-Catalyzed, Regioselective, C-H Bond Functionalization: Access to Quinoline-Branched Amines and Dimers
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Rh-catalyzed, chelation-induced, C-5 regioselective C-H functionalization of 8-amidoquinolines with a range of N-Boc aminals is reported for the first time. The addition of in situ generated imines to C(sp2)-H bonds afforded branched amines in
- Reddy, M. Damoder,Fronczek, Frank R.,Watkins, E. Blake
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supporting information
p. 5620 - 5623
(2016/11/17)
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- Cobalt-promoted dimerization of aminoquinoline benzamides
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A method for aminoquinoline-directed, cobalt-promoted dimerization of benzamides has been developed. Reactions proceed in ethanol solvent in the presence of Mn(OAc)2 cocatalyst and Na2CO3 base and use oxygen as a terminal oxidant. Bromo, iodo, nitro, ether, and ester moieties are compatible with the reaction conditions. Cross-coupling of electronically dissimilar aminoquinoline benzamides proceeds with modest yields and selectivities.
- Grigorjeva, Liene,Daugulis, Olafs
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supporting information
p. 1204 - 1207
(2015/05/20)
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- Cobalt-catalyzed, aminoquinoline-directed C(sp2)-H bond alkenylation by alkynes
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A method for cobalt-catalyzed, aminoquinoline- and picolinamide-directed C(sp2)-H bond alkenylation by alkynes was developed. The method shows excellent functional-group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2·4 H2O catalyst, Mn(OAc)2 co-catalyst, and oxygen (from air) as a terminal oxidant.
- Grigorjeva, Liene,Daugulis, Olafs
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supporting information
p. 10209 - 10212
(2015/03/31)
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- Copper-mediated ortho-nitration of (hetero)arenecarboxylates
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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.
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p. 9902 - 9905
(2014/08/18)
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- Copper-catalyzed phosphorylation of sp2 C-H bonds
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The phosphorylation of the ortho C-H bonds in benzamides containing an 8-aminoquinoline moiety as a bidentate directing group with H-phosphonates using copper as a catalyst under mild temperature conditions is described. This method shows high functional group compatibility and selectively gives mono-substituted products. This journal is
- Wang, Shan,Guo, Rui,Wang, Gao,Chen, Shan-Yong,Yu, Xiao-Qi
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p. 12718 - 12721
(2015/05/20)
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- Cobalt-catalyzed direct carbonylation of aminoquinoline benzamides
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A method for direct carbonylation of aminoquinoline benzamides has been developed. Reactions proceed at room temperature in trifluoroethanol solvent, use oxygen from air as an oxidant, and require Mn(OAc)3 as a cocatalyst. Benzoic and acrylic a
- Grigorjeva, Liene,Daugulis, Olafs
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supporting information
p. 4688 - 4690
(2015/01/08)
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- Cobalt-catalyzed, aminoquinoline-directed coupling of sp2 C-H bonds with alkenes
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A method for cobalt-catalyzed, aminoquinoline-directed ortho-functionalization of sp2 C-H bonds with alkenes has been developed. Reactions proceed at room temperature in trifluoroethanol solvent, use oxygen from air as an oxidant, and require Mn(OAc)3 as a cocatalyst. Benzoic, heteroaromatic, and acrylic acid aminoquinoline amides react with ethylene as well as mono- and disubstituted alkenes affording products in good yields. Excellent functional group tolerance is observed; halogen, nitro, ether, and unprotected alcohol functionalities are compatible with the reaction conditions.
- Grigorjeva, Liene,Daugulis, Olafs
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supporting information
p. 4684 - 4687
(2015/01/08)
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- Copper-mediated C-H(sp2)/C-H(sp3) coupling of benzoic acid derivatives with ethyl cyanoacetate: An expedient route to an isoquinolinone scaffold
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A facile, copper-mediated, direct C-H(sp2)/C-H(sp3) bond coupling of benzoic acid derivatives with ethyl cyanoacetate by the deployment of an 8-aminoquinoline moiety as a bidentate directing group is disclosed. Such a unique transfor
- Zhu, Wei,Zhang, Dengyou,Yang, Nan,Liu, Hong
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supporting information
p. 10634 - 10636
(2014/10/15)
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- Directed arene/alkyne annulation reactions via aerobic copper catalysis
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We describe a straightforward protocol for a smooth dehydrogenative annulation reaction between various arenes and terminal alkynes using a catalytic amount of CuBr2 and molecular oxygen. 3-Methyleneisoindoline derivatives are prepared in high
- Zhang, Yi,Wang, Qian,Yu, Huidong,Huang, Yong
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p. 8844 - 8850
(2015/02/19)
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- SUBSTITUTED 4-AMINOBENZAMIDES AS KCNQ2/3 MODULATORS
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The invention relates to substituted 4-aminobenzamides, to pharmaceutical compositions containing these compounds and also to these compounds for use in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Page/Page column 158-159
(2013/11/05)
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- SUBSTITUTED 4-AMINOBENZAMIDES AS KCNQ2/3 MODULATORS
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Substituted 4-aminobenzamides, pharmaceutical compositions containing these compounds and also methods of using these compounds in the treatment and/or prophylaxis of pain and further diseases and/or disorders.
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Paragraph 0754
(2013/11/05)
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- Auxiliary-assisted palladium-catalyzed arylation and alkylation of sp 2 and sp3 carbon-hydrogen bonds
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We have developed a method for auxiliary-directed, palladium-catalyzed β-arylation and alkylation of sp3 and sp2 C-H bonds in carboxylic acid derivatives. The method employs a carboxylic acid 2-methylthioaniline- or 8-aminoquinoline amide substrate, aryl or alkyl iodide coupling partner, palladium acetate catalyst, and an inorganic base. By employing 2-methylthioaniline auxiliary, selective monoarylation of primary sp3 C-H bonds can be achieved. If arylation of secondary sp 3 C-H bonds is desired, 8-aminoquinoline auxiliary may be used. For alkylation of sp3 and sp2 C-H bonds, 8-aminoquinoline auxiliary affords the best results. Some functional group tolerance is observed and amino- and hydroxy-acid derivatives can be functionalized. Preliminary mechanistic studies have been performed. A palladacycle intermediate has been isolated, characterized by X-ray crystallography, and its reactions have been studied.
- Shabashov, Dmitry,Daugulis, Olafs
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supporting information; experimental part
p. 3965 - 3972
(2010/05/15)
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