- Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
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The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
- Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
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p. 10422 - 10428
(2021/07/26)
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- Rh(III)-Catalyzed C-H Cyanation of 2 H-Indazole with N-Cyano- N-phenyl- p-toluenesulfonamide
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A Rh(III)-catalyzed direct cyanation of 2H-indazoles with N-cyano-N-phenyl-p-toluenesulfonamide has been realized via a chelation-assisted strategy. The methodology enables regioselective access to various ortho-cyanated phenylindazoles in good yields with a broad substrate scope and good functional group compatibility. The obtained cyanated indazoles could further be converted into other value-added chemicals. Importantly, the current protocol is featured with several characteristics, including a novel cyanating agent, good regioselectivity, and operational convenience.
- Li, Jing,Shi, Linlin,Zhang, Shu-Ping,Wang, Xu-Yan,Zhu, Xinju,Hao, Xin-Qi,Song, Mao-Ping
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p. 10835 - 10845
(2020/09/18)
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- PYRAZOLYL COMPOUNDS AND METHODS OF USE THEREOF
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Compounds having activity as chemotherapeutic agents are provided. The compounds have the following structure (I): or a pharmaceutically acceptable salt, stereoisomer, isotopic form or prodrug thereof, wherein R1a, R1b, R1c, R1d, L, and are as defined herein. Methods associated with preparation and use of such compounds, pharmaceutical compositions comprising such compounds and methods for treating cancer (e.g., hematological cancers) are also provided.
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Paragraph 0312-0317
(2020/05/14)
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- Methyl-α-d-glucopyranoside as Green Ligand for Selective Copper-Catalyzed N-Arylation
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In the selective N-arylation of amines or azoles with aryl halidesa-, methyl-α-d-glucopyranoside (MG) was found to function as a green ligand of copper powder. In addition, nitrogen heterocyclic amine compounds can also undergo the N-arylation coupling with heterocyclic aryl chlorides. This process allows access to a variety of aromatic amines and aryl azoles under mild reaction conditions, has good tolerance, and proceeds in moderate to high yield.
- Chen, Fengyang,Chen, Guoliang,Chen, Yuanguang,Du, Fangyu,Zhou, Qifan
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p. 4590 - 4600
(2019/12/11)
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- Rhodium(iii)-catalyzed aromatic C-H cyanation with dimethylmalononitrile as a cyanating agent
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A rhodium-catalyzed aromatic C-H bond direct cyanation with safe, bench-stable, and commercially available dimethylmalononitrile as the cyanating agent has been successfully developed by using copper oxide as a promotor. Pyridine, quinoline, pyrimidine and pyrazole were used as the directing group in this type of C-H bond direct cyanation reaction.
- Li, He,Zhang, Sheng,Yu, Xiaoqiang,Feng, Xiujuan,Yamamoto, Yoshinori,Bao, Ming
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supporting information
p. 1209 - 1212
(2019/01/30)
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- Cu(II)-catalyzed C-N coupling of (hetero)aryl halides and N-Nucleophiles promoted by α-benzoin oxime
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We first reported the new application of a translate metal chelating ligand α-benzoin oxime for improving Cu-catalyzed C-N coupling reactions. The system could catalyse coupling reactions of (hetero)aryl halides with a wide of nucleophiles (e.g., azoles, piperidine, pyrrolidine and amino acids) in moderate to excellent yields. The protocol allows rapid access to the most common scaαolds found in FDA-approved pharmaceuticals.
- Yuan, Chunling,Zhang, Lei,Zhao, Yingdai
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- L -(-) -Quebrachitol as a Ligand for Selective Copper(0)-Catalyzed N-Arylation of Nitrogen-Containing Heterocycles
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l-(-)-Quebrachitol (QCT) has been found as a ligand of copper powder for selective N-arylation of nitrogen-containing heterocycles with aryl halides. Furthermore, another potential catalytic system (copper powder/QCT/t-BuOK) was successfully adapted to unactivated aryl chlorides.
- Zhou, Qifan,Du, Fangyu,Chen, Yuanguang,Fu, Yang,Sun, Wenjiao,Wu, Ying,Chen, Guoliang
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p. 8160 - 8167
(2019/06/28)
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- α-d-Galacturonic Acid as Natural Ligand for Selective Copper-Catalyzed N-Arylation of N-Containing Heterocycles
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The first application of α-d-galacturonic acid hydrate (GalA) is reported here, as a potential O-donor ligand. The C-N couplings of N-heterocycles with aryl halides or arylboronic acids could be readily conducted and exhibited good functional group tolerance with characters of selectivity. These N-Arylazoles allow rapid access to several pharmaceutical intermediates and can be easily transformed into a variety of other interesting scaffolds as well.
- Yuan, Chunling,Zhao, Yingdai,Zheng, Li
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p. 2173 - 2180
(2019/11/25)
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- Rhodium-Catalyzed Direct C-H Bond Cyanation in Ionic Liquids
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A Cp?Rh(III)/IL-based direct C-H bond cyanation system was developed for the first time. The system is a mild, efficient, and recyclable method for the synthesis of aryl nitriles. Many different directing groups can be used in this cyanation, and the reaction tolerates a variety of functional groups.
- Lv, Songyang,Li, Yaling,Yao, Tian,Yu, Xinling,Zhang, Chen,Hai, Li,Wu, Yong
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supporting information
p. 4994 - 4997
(2018/08/24)
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- α-Iminonitrile: A new cyanating agent for the palladium catalyzed C-H cyanation of arenes
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An efficient palladium-catalyzed C-H cyanation reaction of arenes using α-iminonitrile as a new cyanating reagent has been developed. With high regioselectivity and broad substrate scope, this reaction offers monocyanated products in moderate to excellent
- Chen, Zhen-Bang,Zhang, Fang-Ling,Yuan, Qing,Chen, Hai-Fang,Zhu, Yong-Ming,Shen, Jing-Kang
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p. 64234 - 64238
(2016/07/23)
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- N-Picolinamides as ligands for Ullmann-type C-N coupling reactions
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The use of N-phenyl-2-pyridincarboxamide-1-oxide as a ligand with Cu2O in Ullmann type C-N bond formations between aryl halides and N-heteroaryls in common solvents, such as MeCN, DMF, and DMSO at 82-120 °C has been successfully demonstrated. The ligand is effective when only 4% equiv is used relative to the substrate. The reaction provided the corresponding products in coupling of electron-rich, electron poor, and ortho-substituted aryl halides, including ortho aryl-chlorides, in good to very good yields. N-arylation is selectively preferred at the benzyl position when ortho-halide benzyl bromide is reacted with one equivalent of pyrazole. However, di-N-arylation is achieved in very high yields when 2.5 equiv of pyrazole is used, providing a stoichiometric control over the coupling reaction.
- Damkaci, Fehmi,Alawaed, Abdulkhaliq,Vik, Erik
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supporting information
p. 2197 - 2200
(2016/05/02)
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- Synthesis of quinazolinimines and quinazolinamines from 2-fluorobenzonitriles under catalyst-free conditions
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A convenient procedure for the synthesis of quinazolinimines and quinazolinamines from 2-fluorobenzonitriles has been developed. By using KOtBu as the promotor with 2-aminopyridines or amidines as the reaction partner, the desired heterocycles
- Feng, Jian-Bo,Wu, Xiao-Feng
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supporting information
p. 10656 - 10662
(2015/11/17)
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- Cobalt-catalyzed C-H cyanation of (Hetero)arenes and 6-Arylpurines with N -cyanosuccinimide as a new cyanating agent
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A cobalt-catalyzed C-H cyanation reaction of arenes has been developed using N-cyanosuccinimide as a new electrophilic cyanating agent. The reaction proceeds with high selectivity to afford monocyanated products with excellent functional group tolerance. Substrate scope was found to be broad enough to include a wide range of heterocycles including 6-arylpurines.
- Pawar, Amit B.,Chang, Sukbok
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supporting information
p. 660 - 663
(2015/03/04)
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- Cobalt-catalyzed C-H cyanation of arenes and heteroarenes
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Carboxylate assistance proved to be the key for the success of efficient cobalt(III)-catalyzed C-H cyanations. Thus, an in situ generated cationic cobalt complex was identified as a versatile catalyst for the site-selective synthesis of various aromatic a
- Li, Jie,Ackermann, Lutz
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supporting information
p. 3635 - 3638
(2015/03/18)
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- Co(III)-catalyzed C-H activation/formal SN-type reactions: Selective and efficient cyanation, halogenation, and allylation
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The first cobalt-catalyzed cyanation, halogenation, and allylation via C-H activation have been realized. These formal SN-type reactions generate valuable (hetero)aryl/alkenyl nitriles, iodides, and bromides as well as allylated indoles using a bench-stable Co(III) catalyst. High regio- and mono-selectivity were achieved for these reactions. Additionally, allylation proceeded efficiently with a turnover number of 2200 at room temperature, which is unprecedented for this Co(III) catalyst. Alkenyl substrates and amides have been successfully utilized in CpCo(III)-catalyzed C-H activation for the first time.
- Yu, Da-Gang,Gensch, Tobias,De Azambuja, Francisco,Vsquez-Cspedes, Suhelen,Glorius, Frank
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supporting information
p. 17722 - 17725
(2015/02/19)
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- Rhodium-catalyzed directed C-H cyanation of arenes with N-cyano-N-phenyl-p-toluenesulfonamide
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A Rh-catalyzed directed C-H cyanation reaction was developed for the first time as a practical method for the synthesis of aromatic nitriles. N-Cyano-N-phenyl-p-toluenesulfonamide, a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this C-H cyanation process, and the reaction tolerates a variety of synthetically important functional groups.
- Gong, Tian-Jun,Xiao, Bin,Cheng, Wan-Min,Su, Wei,Xu, Jun,Liu, Zhao-Jing,Liu, Lei,Fu, Yao
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supporting information
p. 10630 - 10633
(2013/08/23)
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- Copper-catalyzed cyanation of arenes using benzyl nitrile as a cyanide anion surrogate
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The copper-catalyzed cyanation of arenes using benzyl nitrile as a cyanide anion surrogate furnishes aromatic nitriles in moderate to good yields. The cascade process involves a copper-catalyzed aerobic C-H oxidation, a retro-cyanohydrination, and a copper-catalyzed aerobic oxidative C-H functionalization. The Royal Society of Chemistry 2012.
- Jin, Jisong,Wen, Qiaodong,Lu, Ping,Wang, Yanguang
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supporting information
p. 9933 - 9935
(2012/10/29)
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- Chelation-assisted palladium-catalyzed cascade bromination/cyanation reaction of 2-arylpyridine and 1-arylpyrazole C-H bonds
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(Chemical Equation Presented) A chelation-assisted palladium-catalyzed cascade bromination/cyanation reaction of 2-arylpyridine and 1-arylpyrazole C-H bonds has been developed. Notably, the reaction employs K3[Fe(CN) 6] as a safe and
- Jia, Xiaofei,Yang, Dongpeng,Wang, Wenhui,Luo, Fang,Cheng, Jiang
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experimental part
p. 9470 - 9474
(2010/03/04)
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- DPP-IV INHIBITORS
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The invention relates to compounds of formula (I), Z-C(R1R 2)-C(R3NH2)-C(R4R5)-X-N(R 6R7), wherein Z, R1-7 and X have the meaning as cited in the description and the claims. Said compounds are useful as DPP-lV inhibitors. The invention also relates to the
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Page/Page column 53-54
(2010/02/14)
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- HIGH AFFINITY SMALL MOLECULE C5A RECEPTOR MODULATORS
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This invention relates to low molecular weight, non-peptidic, non-peptidomimetic, organic molecules that act as modulators of mammalian complement C5a receptors, preferably ones that act as high affinity C5a receptor ligands and also to such ligands that act as antagonists or inverse agonists of complement C5a receptors, preferably human C5a receptors, Preferred compounds of the invention possess one or more, and preferably two or more, three or more, four or more, or all of the following properties in that they are; 1) multi-aryl in structure (having a plurality of un-fused or fused aryl groups), 2) heteroaryl in structure, 3) orally available in vivo (such that a sub-lethal or preferably a pharmaceutically acceptable oral dose can provide a detectable in vitro effect such as a reduction of C5a-induced neutropenia) , 4) comprised of fewer than four, preferably fewer than three, or fewer than two, or no amide bonds, and 5) capable of inhibiting leukocyte chemotaxis at nanomolar concentrations and preferably at sub-nanomolar concentrations. Specifically exemplified representative compounds include, but are not limited to optionally substituted arylimidazoles, optionally substituted arylpyridyls, optionally substituted aryl-substituted cycloalkylimidazoles, optionally substituted arylpyrazoles, optionally substituted benzimidazoles, optionally substituted aryl-substituted tetrahydroisoquinolines, and optionally substituted biaryl carboxamides. This invention also relates to pharmaceutical compositions comprising such compounds. It further relates to the use of such compounds in treating a variety of inflammatory and immune system disorders. Additionally, this invention relates to the use such compounds as probes for the localization of C5a receptors.
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Page/Page column 142
(2010/02/06)
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- Solvent-free preparation of tris-pyrazolyl-1,3,5-triazines
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Tris-pyrazolyl-1,3,5-triazines have been prepared by cyclotrimerization of aromatic nitriles in solvent-free conditions. The interesting structures of these compounds make them candidates for application in coordination chemistry and crystal engineering.
- De La Hoz, Antonio,Díaz-Ortiz, Angel,Elguero, José,Martínez, Luis J.,Moreno, Andrés,Sánchez-Migallón, Ana
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p. 4397 - 4403
(2007/10/03)
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