- Aryne Multicomponent Reactions by Directed C?H Activation
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Arylation via ortho C?H activation by the aid of directing groups has been explored recently by many researchers. Herein, a palladium-catalyzed C?H arylation using 8-aminoquinoline as a bidentate directing group has been developed. The reaction furnishes only C?H arylation, unlike previous methods where cyclization to corresponding isoquinolones is observed. More interestingly, sequential C?H functionalization was observed when methylacrylate and acrylonitrile was added; this led to C?H olefination with the aryl group, which was installed from the aryne precursor.
- Sunnam, Sunil Kumar,Belani, Jitendra D.
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p. 8846 - 8850
(2021/05/31)
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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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- Ni-Catalyzed C(sp2)-H alkylation ofN-quinolylbenzamides using alkylsilyl peroxides as structurally diverse alkyl sources
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A Ni-catalyzed direct C-H alkylation ofN-quinolylbenzamides using alkylsilyl peroxides as alkyl-radical precursors is described. The reaction forms a new C(sp3)-C(sp2) bondviathe selective cleavage of both C(sp3)-C(sp3) and C(sp2)-H bonds. This transformation shows a high functional-group tolerance and, due to the structural diversity of alkylsilyl peroxides, a wide range of alkyl chains including functional groups and complex structures can be introduced at theortho-position of readily availableN-quinolylbenzamide derivatives. Mechanistic studies suggest that the reaction involves a radical mechanism.
- Kano, Taichi,Maruoka, Keiji,Matsumoto, Akira,Sakurai, Shunya,Tsuzuki, Saori
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supporting information
p. 7942 - 7945
(2021/08/17)
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- Regioselective remote C5 cyanoalkoxylation and cyanoalkylation of 8-aminoquinolines with azobisisobutyronitrile
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The efficient regioselective C-H cyanoalkoxylation and cyanoalkylation of 8-aminoquinoline derivatives at the C5 position have been achieved under O2 and N2 atmospheres, respectively. Using 2,2′-azobisisobutyronitrile (AIBN) as a radical precursor, the pr
- Wen, Chunxia,Zhong, Ronglin,Qin, Zengxin,Zhao, Mengfei,Li, Jizhen
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supporting information
p. 9529 - 9532
(2020/09/03)
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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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- Synthesis of diaryl sulfides through C–H bond functionalization of arylamides with cobalt salt and elemental sulfur
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A cobalt(II)-mediated, highly chemoselective thioarylation reaction of arylamides with elemental sulfur was reported. This reaction led to the formation of various symmetric diaryl sulfides in yields of up to 65% under mild reaction conditions. A cobalt-sulfur radical process was proposed based on preliminary results and mechanistic studies.
- Li, Jian-Ye,Huang, Jun,Zhang, Shi-Jin,Yao, Chunna,Sun, Wen-Wu,Liu, Bin,Zhou, Yingbi,Wu, Bin
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supporting information
p. 895 - 899
(2019/02/26)
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- Iron(III)-catalyzed highly regioselective halogenation of 8-amidoquinolines in water
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A simple protocol of iron(III)-catalyzed halogenation of 8-amidoquinolines in water under mild conditions was developed, affording the 5-halogenlated products in good to excellent yields up to 98%. The reaction mechanism most likely involves a single-elec
- Long, Yang,Pan, Lei,Zhou, Xiangge
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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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- Palladium-Catalyzed H/D Exchange Reaction with 8-Aminoquinoline as the Directing Group: Access to ortho-Selective Deuterated Aromatic Acids and β-Selective Deuterated Aliphatic Acids
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We develop a palladium-catalyzed H/D exchange reaction with 8-aminoquinoline as the directing group as well as D2O as the source of deuterium atom and solvent. This reaction achieves selectively H/D exchange at the ortho-C-H of aromatic amides and the β-C-H of aliphatic amide. Ortho-deuterated aromatic acids and β-deuterated aliphatic acids are obtained by removal of the directing group. And a possible mechanism is also proposed.
- Zhao, Donghong,Luo, Haofan,Chen, Binhui,Chen, Wenteng,Zhang, Guolin,Yu, Yongping
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p. 7860 - 7866
(2018/07/21)
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- Rh(I)-Catalyzed Alkylation of ortho-C-H Bonds in Aromatic Amides with Maleimides
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An alkylation of C-H bonds with maleimides by a rhodium-catalyzed reaction of aromatic amides containing an 8-aminoquinoline moiety as the directing group is reported. Various N-substituents in the maleimide, including methyl, ethyl, cyclohexyl, benzyl, a
- He, Qiyuan,Yamaguchi, Takuma,Chatani, Naoto
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supporting information
p. 4544 - 4547
(2017/09/11)
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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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- 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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- Chelation-Assisted Nickel-Catalyzed Oxidative Annulation via Double C-H Activation/Alkyne Insertion Reaction
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A nickel/NHC system for regioselective oxidative annulation by double C-H bond activation and concomitant alkyne insertion is described. The catalytic reaction requires a bidentate directing group, such as an 8-aminoquinoline, embedded in the substrate. Various 5,6,7,8-tetrasubstituted-N-(quinolin-8-yl)-1-naphthamides can be prepared as well as phenanthrene and benzo[h]quinoline amide derivatives. Diarylalkynes, dialkylalkynes, and arylalkylalkynes can be used in the system. A Ni0/NiII catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two-component coupling partner and as a hydrogen acceptor. In two shakes: Oxidative annulation by a double C-H activation/alkyne insertion reaction was achieved by a nickel/NHC system. A Ni0/NiII catalytic cycle is proposed as the main catalytic cycle. The alkyne plays a double role as a two-component coupling partner and as a hydrogen acceptor.
- Misal Castro, Luis C.,Obata, Atsushi,Aihara, Yoshinori,Chatani, Naoto
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p. 1362 - 1367
(2016/01/25)
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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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- A General Method for Aminoquinoline-Directed, Copper-Catalyzed sp2 C-H Bond Amination
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An operationally simple and general method for copper-catalyzed, aminoquinoline-assisted amination of β-C(sp2)-H bonds of benzoic acid derivatives is reported. The reaction employs Cu(OAc)2 or (CuOH)2CO3 catalysts, an amine coupling partner, and oxygen from air as a terminal oxidant. Exceptionally high generality with respect to amine coupling partners is observed. Specifically, primary and secondary aliphatic and aromatic amines, heterocycles, such as indoles, pyrazole, and carbazole, sulfonamides, as well as electron-deficient aromatic and heteroaromatic amines are competent coupling components.
- Roane, James,Daugulis, Olafs
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supporting information
p. 4601 - 4607
(2016/05/09)
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- Dicumyl Peroxide as a Methylating Reagent in the Ni-Catalyzed Methylation of Ortho C-H Bonds in Aromatic Amides
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The direct methylation of ortho C-H bonds in aromatic amides with dicumyl peroxide (DCP) using a nickel complex as the catalyst is reported. The reaction shows a high functional group tolerance and is inhibited by radical scavengers. In reactions of meta-substituted aromatic amides, the reaction proceeds in a highly selective manner at the less hindered C-H bonds.
- Kubo, Teruhiko,Chatani, Naoto
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supporting information
p. 1698 - 1701
(2016/04/26)
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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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- Pd-catalyzed monoselective ortho -C-H alkylation of N -quinolyl benzamides: Evidence for stereoretentive coupling of secondary alkyl iodides
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We report a method for the monoselective alkylation of ortho-C-H bonds of N-quinolyl benzamides with both primary and secondary alkyl halides under palladium catalysis. With promotion by NaHCO3 and (BnO)2PO2H or (PhO)
- Zhang, Shu-Yu,Li, Qiong,He, Gang,Nack, William A.,Chen, Gong
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supporting information
p. 531 - 539
(2015/01/30)
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- Carboxylate Assisted Ni-Catalyzed C-H Bond Allylation of Benzamides
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A one-step synthetic method was developed for allylation of benzamides using Ni(COD)2/RCO2H and [Ni(μ-H2O)(OOCCMe3)2(HOOCCMe3)2]2 (A′) catalytic system. Efficient, well-defined, air and moisture-stable Ni-pivalate complex was isolated and employed in catalytic allylation. The influence of solvent on product selectivity was also investigated. Nickel-back: A one-step synthetic method was developed for the allylation of benzamides using in situ formed nickel carboxylate Ni(COD)2/RCO2H catalyst (see scheme). The air and moisture stable Ni-pivalate complex was isolated and employed in catalytic allylation. The influence of solvent on product selectivity is discussed.
- Barsu, Nagaraju,Kalsi, Deepti,Sundararaju, Basker
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p. 9364 - 9368
(2015/06/30)
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- Iron-Catalyzed Directed C(sp2)-H and C(sp3)-H Functionalization with Trimethylaluminum
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Conversion of a C(sp2)-H or C(sp3)-H bond to the corresponding C-Me bond can be achieved by using AlMe3 or its air-stable diamine complex in the presence of catalytic amounts of an inorganic iron(III) salt and a diphosphine along with 2,3-dichlorobutane as a stoichiometric oxidant. The reaction is applicable to a variety of amide substrates bearing a picolinoyl or 8-aminoquinolyl directing group, enabling methylation of a variety of (hetero)aryl, alkenyl, and alkyl amides. The use of the mild aluminum reagent prevents undesired reduction of iron and allows the reaction to proceed with catalyst turnover numbers as high as 6500.
- Shang, Rui,Ilies, Laurean,Nakamura, Eiichi
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supporting information
p. 7660 - 7663
(2015/06/30)
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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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- 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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- Iron-catalyzed C(sp2)-H bond functionalization with organoboron compounds
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We report here that an iron-catalyzed directed C-H functionalization reaction allows the coupling of a variety of aromatic, heteroaromatic, and olefinic substrates with alkenyl and aryl boron compounds under mild oxidative conditions. We rationalize these results by the involvement of an organoiron(III) reactive intermediate that is responsible for the C-H bond-activation process. A zinc salt is crucial to promote the transfer of the organic group from the boron atom to the iron(III) atom.
- Shang, Rui,Ilies, Laurean,Asako, Sobi,Nakamura, Eiichi
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supporting information
p. 14349 - 14352
(2014/12/11)
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- Nickel-catalyzed direct alkylation of C-H bonds in benzamides and acrylamides with functionalized alkyl halides via bidentate-chelation assistance
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The alkylation of the ortho C-H bonds in benzamides and acrylamides containing an 8-aminoquinoline moiety as a bidentate directing group with unactivated alkyl halides using nickel complexes as catalysts is described. The reaction shows high functional group compatibility. In reactions of meta-substituted aromatic amides, the reaction proceeds in a highly selective manner at the less hindered C-H bond.
- Aihara, Yoshinori,Chatani, Naoto
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p. 5308 - 5311
(2013/05/21)
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- Directed amination of non-acidic arene C-H bonds by a copper-silver catalytic system
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Amine meets arene: A method for direct amination of β-C(sp 2)-H bonds of benzoic acid derivatives and γ-C(sp 2)-H bonds of benzylamine derivatives has been developed. The reaction is catalyzed by Cu(OAc)2 and a Ag2/s
- Tran, Ly Dieu,Roane, James,Daugulis, Olafs
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supporting information
p. 6043 - 6046
(2013/06/27)
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- Palladium-catalyzed direct ortho -alkynylation of aromatic carboxylic acid derivatives
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The palladium-catalyzed direct alkynylation of C-H bonds in aromatic carboxylic acid derivatives is described. The use of 8-aminoquinoline as a directing group facilitates the alkynylation of an electronically diverse range of C(sp2)-H bonds.
- Ano, Yusuke,Tobisu, Mamoru,Chatani, Naoto
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p. 354 - 357
(2012/03/09)
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- Copper-promoted sulfenylation of sp2 C-H bonds
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An auxiliary-assisted, copper catalyzed or promoted sulfenylation of benzoic acid derivative β-C-H bonds and benzylamine derivative γ-C-H bonds has been developed. The method employs disulfide reagents, copper(II) acetate, and DMSO solvent at 90-130 °C. Application of this methodology to the direct trifluoromethylsulfenylation of C-H bonds was demonstrated.
- Tran, Ly Dieu,Popov, Ilya,Daugulis, Olafs
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supporting information
p. 18237 - 18240,4
(2020/10/15)
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