- N-amino-7-azaindole as the N, N′-Bidentate directing group: Ruthenium-catalyzed oxidative annulation of N-(7-Azaindole)benzamides with alkynes via C-H bond activation
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We report a new application of N-amino-7-azaindole as a new bidentate-directing group for [Ru(p-cymene)Cl2]2-catalyzed C(sp2)-H alkenylation/annulation of N-(1H-pyrrolo[2,3-b]pyridin-1-yl)benzamides with internal alkynes to afford N-isoquinolono-7-azaindole via the formation of C-C and C-N bonds. The reaction shows a wide range of substrate scope with different symmetrical and unsymmetrical alkynes, affording the desired product in good to excellent yields. In the case of unsymmetrical alkynes, a highly regioselective product was obtained, which was confirmed by single-crystal X-ray crystallography. A new ruthenium-4-methyl-N-(1H-pyrrolo[2,3-b]pyridin-1-yl)benzamide complex was isolated, and its structure was confirmed by single-crystal X-ray crystallography.
- Sagara, Prateep Singh,Siril, Prem Felix,Ravikumar, Ponneri Chandrababu
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- Rhodium(iii)-catalyzed oxidative annulation of isoquinolones with allyl alcohols: synthesis of isoindolo[2,1-b]isoquinolin-5(7H)-ones
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An efficient rhodium(iii)-catalyzed direct C–H oxidative annulation of isoquinolones with allyl alcohols as C1 synthons has been successfully developed. This protocol enables the straightforward synthesis of structurally diverse isoindolo[2,1-b]isoquinolin-5(7H)-ones with high atom economy, tolerates a broad spectrum of functionalities, and is applicable to one-pot operation from readily available N-methoxybenzamides.
- Jiang, Jinyuan,Liu, Jidan,Liu, Zhao-Qing,Tian, Xin,Yang, Zhenke,Zheng, Jieying,Zheng, Liyao
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supporting information
p. 339 - 344
(2022/01/20)
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- Rh(III)-Catalyzed Diverse C—H Functionalization of Iminopyridinium Ylides
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Divergent synthesis of useful skeletons has been realized via rhodium(III)-catalyzed C—H activation of iminopyridinium ylides and coupling with various unsaturated coupling reagents. Isocoumarins and isoquinolones were obtained via cleavage of the C—N or
- Dong, Zhenzhen,Li, Pengfei,Li, Xingwei,Liu, Bingxian
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supporting information
p. 2489 - 2494
(2021/07/26)
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- Weakly Coordinated Cobaltacycles: Trapping Catalytically Competent Intermediates in Cp*CoIII Catalysis
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Herein, we disclose the synthesis of metallacyclic Cp*CoIII complexes containing weakly chelating functional groups. We have employed these compounds not only as an exceptional platform for accessing some of the most widely invoked transient intermediates in C?H functionalization processes but also as competent catalysts in different Cp*Co-catalyzed transformations, including a benchmark coupling reaction.
- Barranco, Sergio,Benet-Buchholz, Jordi,Martínez de Salinas, Sara,Odena, Carlota,Pérez-Temprano, Mónica H.,Sanjosé-Orduna, Jesús
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supporting information
p. 6239 - 6243
(2020/02/27)
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- Development of a Traceless Directing Group: Cp*-Free Cobalt-Catalyzed C-H Activation/Annulations to Access Isoquinolinones
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A new traceless directing group, 2-(hydroxymethyl)pyridine, has been reported for the Cp*-free cobalt-catalyzed C-H activation/annulation reaction to synthesize isoquinolinones. The reaction exhibits good functional group tolerance, affording products in good to excellent isolated yields under mild conditions. Notably, the directing group can be removed directly in situ along the catalytic process.
- Liu, Minghui,Niu, Jun-Long,Yang, Dandan,Song, Mao-Ping
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supporting information
p. 4067 - 4078
(2020/04/09)
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- Synthesis of isoquinolone via rhodium(III)-catalyzed C-H activation with 1,4,2-dioxazol-5-ones as oxidizing directing group
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An efficient rhodium-catalyzed direct C-H activation for the synthesis of isoquinolone with 1,4,2-dioxazol-5-ones as oxidizing directing groups have been developed, which featured mild reaction conditions, short reaction time and satisfactory yield.
- Zhu, Huajian,Zhuang, Rangxiao,Zheng, Wenya,Fu, Liping,Zhao, Yuanke,Tu, Luping,Chai, Yitao,Zeng, Linghui,Zhang, Chong,Zhang, Jiankang
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p. 3108 - 3112
(2019/05/08)
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- Rapid and Atom Economic Synthesis of Isoquinolines and Isoquinolinones by C–H/N–N Activation Using a Homogeneous Recyclable Ruthenium Catalyst in PEG Media
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Herein, we report an atom-efficient, rapid, green, and sustainable approach to synthesize isoquinolines and isoquinolinones using a homogeneous recyclable ruthenium catalyst in PEG Media assisted by microwave energy. Dibenzoylhydrazine was used for C–H/N–N activation reactions for the first time in combination with ketazine as oxidizing directing groups for annulation reactions with internal alkynes. The developed protocol is environmentally benign due to significantly shortened times with an easy extraction method, higher atom economy, external oxidant and silver or antimony salt free conditions, applicability to a gram scale synthesis, use of biodegradable solvent and wide substrate scope with higher product yields. Moreover, it is worth noting that the established methodology allowed reuse of the catalytic system for up to five successive runs with minimal loss in activity.
- Deshmukh, Dewal S.,Gangwar, Neha,Bhanage, Bhalchandra M.
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supporting information
p. 2919 - 2927
(2019/05/10)
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- Redox-Neutral [4 + 2] Annulation of N-Methoxybenzamides with Alkynes Enabled by an Osmium(II)/HOAc Catalytic System
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By making use of a direct C-H activation strategy, an efficient osmium(II)-catalyzed redox-neutral [4 + 2] annulation of N-methoxybenzamides with alkynes has been accomplished. Computational and experimental studies revealed that such transformation leading to the synthesis of the isoquinolone core might follow an Os(II)-Os(IV)-Os(II) catalytic pathway, in which an unusual HOAc-assisted oxidative addition of osmium(II) into the N-O bond to generate the osmium(IV) species was involved as one of the key transition states. Further exploration of divergent C-H activation reaction modes enabled by the osmium(II) catalyst has also been exemplified for one-pot assembly of other either linear or cyclic products.
- Yang, Jian,Wu, Liexin,Xu, Huiying,Gao, Hui,Zhou, Zhi,Yi, Wei
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supporting information
p. 9904 - 9908
(2019/12/24)
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- Three-Component Synthesis of Isoquinoline Derivatives by a Relay Catalysis with a Single Rhodium(III) Catalyst
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A rhodium(III)-catalyzed one-pot three-component reaction of N-methoxybenzamide, α-diazoester, and alkyne was developed, providing an alternative way to synthesize isoquinoline derivatives. Mechanistically, it is a relay catalysis, and the reaction occurred via successive O-alkylation and C-H activation processes, both of which were promoted by the same catalyst.
- Zhou, Chao,Jiang, Jijun,Wang, Jun
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supporting information
p. 4971 - 4975
(2019/09/03)
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- Palladium-Catalyzed Inert C?H Bond Activation and Cyclocarbonylation of Isoquinolones with Carbon Dioxide Leading to Isoindolo[2,1-b]isoquinoline-5,7-Diones
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A palladium-catalyzed inert C?H bond activation and cyclocarbonylation of isoquinolones leading to isoindolo[2,1-b]isoquinoline-5,7-diones under 1 atm of carbon dioxide has been developed. This transformation features high regio- and chemo-selectivity, step-economy, and good functional group tolerance. Most of the corresponding products were obtained in moderate to good yields. It offers an alternative approach for the synthesis of useful diverse isoindolo[2,1-b]isoquinoline-5,7-dione derivatives. (Figure presented.).
- Yan, Kelu,Jin, Junbin,Kong, Yong,Li, Bin,Wang, Baiquan
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supporting information
p. 3080 - 3085
(2019/05/21)
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- Formal Lossen Rearrangement/[3+2] Annulation Cascade Catalyzed by a Modified Cyclopentadienyl RhIII Complex
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It has been established that a cyclopentadienyl RhIII complex with two phenyl groups and a pendant amide moiety catalyzes the formal Lossen rearrangement/[3+2] annulation cascade of N-pivaloyl benzamides and acrylamides with alkynes leading to substituted indoles and pyrroles. Mechanistic studies revealed that this cascade reaction proceeds via not the Lossen rearrangement to form anilides or enamides but C?H bond cleavage, alkyne insertion, and the formal Lossen rearrangement.
- Yamada, Takayuki,Shibata, Yu,Kawauchi, Susumu,Yoshizaki, Soichi,Tanaka, Ken
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supporting information
p. 5723 - 5727
(2018/04/11)
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- Palladium-Catalyzed Oxidative Cyclocarbonylation of Isoquinolones with CO via C?H/N?H Bond Cleavage: Easy Access to Isoindolo[2,1-b]isoquinoline-5,7-dione Derivatives
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An efficient and practical synthesis of isoindolo[2,1-b]isoquinoline-5,7-diones through Pd-catalyzed C?H activation/carbonylative annulation of isoquinolones with CO (1 atm) is presented. Deuterium-labeling experiments revealed that the aryl C(sp2)?H bond activation might be the rate-determining step. More interestingly, the title compounds could also be prepared directly from the cascade reaction of N-methoxy benzamides and internal alkynes, as the precursors of isoquinolones, under an atmospheric pressure of carbon monoxide through a Rh/Pd relay catalysis in a user-friendly manner. (Figure presented.).
- Guo, Shenghai,Wang, Fang,Sun, Lincong,Zhang, Xinying,Fan, Xuesen
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p. 2537 - 2545
(2018/05/16)
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- Iridium(III)-Catalyzed Regiocontrolled Direct Amidation of Isoquinolones and Pyridones
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Iridium(III)-catalyzed highly regiocontrolled C3/C8 amidation of isoquinolones and C6 amidation of 2-pyridones has been successfully accomplished with various azides. The optimized method is operationally simple with a broad substrate scope. The protocol has been found to be scalable. (Figure presented.).
- Das, Debapratim,Samanta, Rajarshi
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supporting information
p. 379 - 384
(2017/12/26)
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- Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes
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Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.
- Mei, Ruhuai,Sauermann, Nicolas,Oliveira, Jo?o C. A.,Ackermann, Lutz
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supporting information
p. 7913 - 7921
(2018/06/08)
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- Palladium-Nanoparticles-Catalyzed Oxidative Annulation of Benzamides with Alkynes for the Synthesis of Isoquinolones
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A novel method to synthesize isoquinolones via oxidative annulation of N-alkoxy benzamides and alkynes using binaphthyl-stabilized palladium nanoparticles (Pd-BNP) as catalyst has been developed. This methodology affords various isoquinolone derivatives in good to excellent yields with high regioselectivities in the presence of air as oxidant. N-Methoxybenzothioamide was also found to undergo oxidative annulation with alkyne successfully and provided a sulfur analogue of isoquinolones in moderate yields. The Pd-BNP catalyst was easily recovered and reused up to four times without any apparent agglomeration. (Figure presented.).
- Sharma, Nidhi,Saha, Rajib,Parveen, Naziya,Sekar, Govindasamy
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p. 1947 - 1958
(2017/06/09)
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- 2-(1-Methylhydrazinyl)pyridine as a reductively removable directing group in a cobalt-catalyzed C(sp2)-H bond alkenylation/annulation cascade
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We describe a new application of 2-(1-methylhydrazinyl)pyridine as a bidentate directing group to directing cobalt-catalyzed C(sp2)-H alkenylation/annulation of the corresponding benzoic hydrazides to form an isoquinoline backbone, via reacting
- Zhai, Shengxian,Qiu, Shuxian,Chen, Xiaoming,Wu, Jiang,Zhao, Hua,Tao, Cheng,Li, Yun,Cheng, Bin,Wang, Huifei,Zhai, Hongbin
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supporting information
p. 98 - 101
(2017/12/27)
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- Direct access to cobaltacycles via C-H activation: N-chloroamide- enabled room-temperature synthesis of heterocycles
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Cobaltacycle synthesis via C-H activation has been achieved for the first time, providing key mechanistic insight into cobalt catalytic chemistry. NChloroamides are used as a directing synthon for cobalt-catalyzed roomtemperature C-H activation and construction of heterocycles. Alkynes as coupling partners allow convenient access to isoquinolones, a class of synthetically and pharmaceutically important compounds. The broad substrate scope enables a diverse range of substitution patterns to be incorporated into the heterocyclic scaffold.
- Yu, Xiaolong,Chen, Kehao,Guo, Shan,Shi, Pengfei,Song, Chao,Zhu, Jin
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p. 5348 - 5351
(2017/11/07)
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- Nickel-catalyzed C-H/N-H annulation of aromatic amides with alkynes in the absence of a specific chelation system
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The Ni-catalyzed reaction of aromatic amides with alkynes in the presence of KOBut involves C-H/N-H oxidative annulation to give 1(2H)-isoquinolinones. A key to the success of the reaction is the use of a catalytic amount of strong base, such a
- Obata, Atsushi,Ano, Yusuke,Chatani, Naoto
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p. 6650 - 6655
(2017/08/29)
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- N-Sulfonylcarboxamide as an Oxidizing Directing Group for Ruthenium-Catalyzed C–H Activation/Annulation
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N-Sulfonylcarboxamides can act as both a directing group for C–H activation and an internal oxidant in the Ru-catalyzed annulation reaction with alkynes to give isoquinolones. Of all of the N-sulfonylcarboxamides that were studied, the N-(2,6-difluorophenyl)sulfonamide derivatives were found to be the most efficient and led to the formation of an unstable sulfinate byproduct that decomposed into 1,3-difluorobenzene under the reaction conditions. The described isoquinolone synthesis provides an alternative to the currently known traceless annulations of hydroxamic acid and sulfoximine derivatives.
- Petrova, Elina,Rasina, Dace,Jirgensons, Aigars
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p. 1773 - 1779
(2017/04/13)
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- Preparation method of pharmaceutical intermediate isoquinoline compound
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The invention relates to a preparation method of pharmaceutical intermediate isoquinoline compound, comprising the steps of in the presence of a catalyst and a base, allowing a substituted benzamide compound to react with a substituted alkyne compound to
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Paragraph 0025; 0026; 0027; 0040; 0041; 0042; 0043-0045
(2017/08/29)
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- Ru(II)/PEG-400 as a highly efficient and recyclable catalytic media for annulation and olefination reactions: Via C-H bond activation
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In this report synthesis of isoquinolinones, isocoumarins, and N-methyl isoquinolinones and olefination of the Weinreb amides by C-H bond activation using Ru(ii)/PEG-400 as green and recyclable media are documented. This developed methodology is capable o
- Yedage, Subhash L.,Bhanage, Bhalchandra M.
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p. 5635 - 5642
(2016/10/21)
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- Cobalt-Catalyzed Cyclization of N-Methoxy Benzamides with Alkynes using an Internal Oxidant through C-H/N-O Bond Activation
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The cyclization of substituted N-methoxy benzamides with alkynes in the presence of an easily affordable cobalt complex and NaOAc provides isoquinolone derivatives in good to excellent yields. The cyclization reaction is compatible with a range of functio
- Sivakumar, Ganesan,Vijeta, Arjun,Jeganmohan, Masilamani
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supporting information
p. 5899 - 5903
(2016/04/26)
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- Rhodium-catalyzed C-H activation of hydrazines leads to isoquinolones with tunable aggregation-induced emission properties
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Using an internally oxidizing directing group (DG) strategy, we report a RhIII-catalyzed synthesis of isoquinolones via C-H activation/annulation of benzoylhydrazines and alkynes. Tunable double cascade cyclization of benzoylhydrazines with two equivalents of alkynes led to tetracyclic amides. These N-heterocycles demonstrated adjustable AIE properties.
- Yu, Bole,Chen, Ying,Hong, Mei,Duan, Pingping,Gan, Shifeng,Chao, Hui,Zhao, Zujin,Zhao, Jing
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p. 14365 - 14368
(2015/09/21)
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- Diversity-Oriented Synthesis through Rh-Catalyzed Selective Transformations of a Novel Multirole Directing Group
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In the context of transition-metal-catalyzed C-H functionalization, directing-group strategy was developed for the improvement of chemical reactivity and selectivity. Recently, to avoid the inherent limitations of traditional mono-role directing groups, a dual-role oxidizing-directing-group strategy was developed, in which the directing group acts both as directing group and oxidant. Herein, we report a multirole directing group, which possesses multiple reactive sites, exhibits unique reactivity and selectivity, and leads to four different types of products from a single starting material through rhodium-catalyzed C-H activation/alkyne annulation reactions. The excellent product diversity and regio- and redox selectivity were well controlled by the tuning of solvents and oxidants. Chemical multitasking: A novel N-N bond containing a multirole directing group is developed, which enables the synthesis of four different products selectively from the same starting material through RhIII catalysis. Key features include ready availability, multiple reactive sites, high redox selectivity and controllability, and multifarious transformations toward important scaffolds and structural diversification. Phth=phthaloyl; DCE=1,2-dichloroethane.
- Su, Bo,Wei, Jiang-Bo,Wu, Wen-Lian,Shi, Zhang-Jie
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p. 2986 - 2990
(2015/09/22)
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- Metal-free iodine(III)-promoted synthesis of isoquinolones
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A metal-free oxidative cycloaddition reaction of substituted benzamides and alkynes has been developed for the synthesis of isoquinolones by using bis(trifluoracetoxy)iodobenzene (PIFA) and trifluoroacetic acid (TFA). Under mild conditions, a wide variety of isoquinolones were conveniently prepared via oxidative annulation of simple N-methoxybenzamide and diarylacetylene or aryl/alkyl acetylene derivatives in yields up to 87%.
- Chen, Zhi-Wei,Zhu, Yi-Zhou,Ou, Jin-Wang,Wang, Ya-Ping,Zheng, Jian-Yu
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p. 10988 - 10998
(2015/01/08)
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- Organocatalytic oxidative annulation of benzamide derivatives with alkynes
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Organocatalytic annulation by functionalization of benzamide derivatives with alkynes has been developed. We report a new approach of cycloaddition under mild reaction conditions using simple catalysts, such as iodobenzene and peracetic acid, as oxidant. Those novel, mild reaction conditions provided a straightforward synthesis of isoquinolones with fast reaction rate. Notable selectivity in annulation of unsymmetrically disubstituted alkynes was demonstrated.
- Manna, Srimanta,Antonchick, Andrey P.
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p. 7324 - 7327
(2014/07/21)
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- Ruthenium(ii)-catalyzed C-H activation/C-N bond formation via in situ generated iminophosphorane as the directing group: Construction of annulated pyridin-2(1H)-ones
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We describe an efficient and straightforward synthesis of annulated pyridin-2(1H)-ones following condensation of acyl azides with internal alkynes via the ruthenium-catalyzed ortho C-H bond activation. The reaction in DCE proceeds via in situ generation of iminophosphoranes as directing group-coordination of Ru with N-atom-ortho cyclometallation-insertion of an alkyne into the Ru-C bond-protonation-reductive elimination in a domino sequence. The role and stability of in situ generated iminophosphorane and ruling out the possibility for the benzamide involvement was established using 1H and 31P NMR experiments. This journal is
- Arigela, Rajesh K.,Kumar, Ravi,Joshi, Trapti,Mahar, Rohit,Kundu, Bijoy
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p. 57749 - 57753
(2015/01/08)
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- Dehydrative C-H/N-OH functionalizations in H2O by ruthenium(II) catalysis: Subtle effect of carboxylate ligands and mechanistic insight
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(Chemical Equation Presented) A ruthenium(II) complex derived from the electron-deficient aromatic carboxylic acid 3-(F3C)C6H4CO2H proved to be a highly efficient catalyst for dehydrative alkyne annulation by NH-free hydroxamic acids in water. The C-H/N-OH functionalization occurred with excellent positional selectivity as well as ample substrate scope, setting the stage for effective intermolecular alkenylations of hydroxamic acids. Detailed mechanistic studies were suggestive of a kinetically relevant C-H metalation by carboxylate assistance along with subsequent migratory alkyne insertion, reductive elimination, and intramolecular oxidative addition.
- Yang, Fanzhi,Ackermann, Lutz
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p. 12070 - 12082
(2015/02/19)
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- A practical one-pot procedure for the synthesis of N-H isoquinolones
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A practical one-pot procedure for the preparation of N-H isoquinolones has been developed. This 2-step process via C-H activation of N-alkoxyl benzamides and NaH-mediated dealkoxylation reaction has been demonstrated to be a high yielding alternative meth
- Lu, Shaonan,Lin, Yingfu,Zhong, Hongban,Zhao, Kang,Huang, Jianhui
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p. 2001 - 2005
(2013/04/23)
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- Synthesis of functionalized isoquinolin-1(2H)-ones by copper-catalyzed α-arylation of ketones with 2-halobenzamides
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Copper is key: A concise route to isoquinolin-1(2H)-ones from simple and readily available starting materials is provided by an efficient copper-catalyzed annulation of ketones with 2-halobenzamides. The method is applicable to a wide range of ketones con
- Shi, Yan,Zhu, Xuebin,Mao, Haibin,Hu, Hongwen,Zhu, Chengjian,Cheng, Yixiang
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supporting information
p. 11553 - 11557
(2013/09/12)
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- Ruthenium-catalyzed aerobic oxidative cyclization of aromatic and heteroaromatic nitriles with alkynes: A new route to isoquinolones
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The oxidative cyclization of aromatic and heteroaromatic nitriles with alkynes in the presence of a catalytic amount of [{RuCl2(p-cymene)} 2], Cu(OAc)2·H2O and KPF6 in acetic acid under air gave isoquinolones in good to excellent yields.
- Reddy, Mallu Chenna,Manikandan, Rajendran,Jeganmohan, Masilamani
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supporting information
p. 6060 - 6062
(2013/07/19)
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- Water as a green solvent for efficient synthesis of isocoumarins through microwave-accelerated and Rh/Cu-catalyzed C-H/O-H bond functionalization
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Green chemistry that uses water as a solvent has recently received great attention in organic synthesis. Here we report an efficient synthesis of biologically important isocoumarins through direct cleavage of C-H/O-H bonds by microwave-accelerated and Rh/
- Li, Qiu,Yan, Yunnan,Wang, Xiaowei,Gong, Binwei,Tang, Xiaobo,Shi, Jingjing,Xu, H. Eric,Yi, Wei
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p. 23402 - 23408
(2013/11/19)
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- Pd-catalysed synthesis of isoquinolinones and analogues via C-H and N-H bonds double activation
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An atom economical synthesis of isoquinolinones and analogues via ligand-free Pd-catalysed C-H and N-H double activation has been developed. A series of isoquinolinones were obtained in good to excellent yields. Good regioselectivities were also observed during the activation reactions with unsymmetrical alkynes. A practical one-pot procedure for the preparation of N-H isoquinolinones is also described. The Royal Society of Chemistry 2012.
- Zhong, Hongban,Yang, Dan,Wang, Songqing,Huang, Jianhui
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supporting information; experimental part
p. 3236 - 3238
(2012/04/11)
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- Ruthenium-catalyzed C-H/N-O bond functionalization: Green isoquinolone syntheses in water
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Ruthenium-catalyzed isoquinolone syntheses with ample scope were accomplished through carboxylate assistance in environmentally benign water as a reaction medium. The high chemoselectivity of the ruthenium(II) carboxylate complex also set the stage for th
- Ackermann, Lutz,Fenner, Sabine
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supporting information; experimental part
p. 6548 - 6551
(2012/02/06)
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- Ruthenium-catalyzed isoquinolone synthesis through C-H activation using an oxidizing directing group
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The oxidant directs: A mild, practical, efficient, and regioselective Ru-catalyzed isoquinolone synthesis with a broad substrate scope was reported (see scheme). In this redox neutral process, the aromatic CiH bond functionalization can be performed at room temperature without using any external oxidant. The mechanism of the reaction was probed, and it was found that CiH activation is the turnover-limiting step.
- Li, Bin,Feng, Huiliang,Xu, Shansheng,Wang, Baiquan
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supporting information; experimental part
p. 12573 - 12577
(2011/12/03)
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- Nickel-catalyzed chelation-assisted transformations involving ortho C-H bond activation: Regioselective oxidative cycloaddition of aromatic amides to alkynes
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Although the pioneering example of ortho metalation involving cleavage of C-H bonds was achieved using a nickel complex (Kleiman, J. P.; Dubeck, M. J. Am. Chem. Soc. 1963, 85, 1544), no examples of catalysis using nickel complexes have been reported. In this work, the Ni-catalyzed transformation of ortho C-H bonds utilizing chelation assistance, such as oxidative cycloaddition of aromatic amides with alkynes, has been achieved.
- Shiota, Hirotaka,Ano, Yusuke,Aihara, Yoshinori,Fukumoto, Yoshiya,Chatani, Naoto
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p. 14952 - 14955
(2011/11/05)
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- Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: Improved reactivity and mechanistic studies
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Directing groups that can act as internal oxidants have recently been shown to be beneficial in metal-catalyzed heterocycle syntheses that undergo C-H functionalization. Pursuant to the rhodium(III)-catalyzed redox-neutral isoquinolone synthesis that we recently reported, we present in this article the development of a more reactive internal oxidant/directing group that can promote the formation of a wide variety of isoquinolones at room temperature while employing low catalyst loadings (0.5 mol %). In contrast to previously reported oxidative rhodium(III)-catalyzed heterocycle syntheses, the new conditions allow for the first time the use of terminal alkynes. Also, it is shown that the use of alkenes, including ethylene, instead of alkynes leads to the room temperature formation of 3,4-dihydroisoquinolones. Mechanistic investigations of this new system point to a change in the turnover limiting step of the catalytic cycle relative to the previously reported conditions. Concerted metalation-deprotonation (CMD) is now proposed to be the turnover limiting step. In addition, DFT calculations conducted on this system agree with a stepwise C-N bond reductive elimination/N-O bond oxidative addition mechanism to afford the desired heterocycle. Concepts highlighted by the calculations were found to be consistent with experimental results.
- Guimond, Nicolas,Gorelsky, Serge I.,Fagnou, Keith
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supporting information; experimental part
p. 6449 - 6457
(2011/06/16)
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- Oxidative coupling of NH isoquinolones with olefins catalyzed by Rh(III)
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Rh(III)-catalyzed oxidative coupling reactions between isoquinolones with 3-aryl groups and activated olefins have been achieved using anhydrous Cu(OAc)2 as an oxidant to give tetracyclic products. The nitrogen atom acts as a directing group to
- Wang, Fen,Song, Guoyong,Du, Zhengyin,Li, Xingwei
-
scheme or table
p. 2926 - 2932
(2011/06/17)
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- Synthesis of highly substituted isoquinolone derivatives by nickel-catalyzed annulation of 2-halobenzamides with alkynes
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(Equation Presented). An efficient method for the synthesis of substituted 1(2H)-isoquinolone derivatives via nickel-catalyzed annulation of substituted 2-halobenzamides with alkynes is described. This protocol is successfully applied to the total synthes
- Liu, Chuan-Che,Parthasarathy, Kanniyappan,Cheng, Chien-Hong
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supporting information; experimental part
p. 3518 - 3521
(2010/10/02)
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- Rhodium(III)-catalyzed isoquinolone synthesis: The N-O bond as a handle for C-N bond formation and catalyst turnover
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An external-oxidant-free process to access the isoquinolone motif via cross-coupling/cyclization of benzhydroxamic acid with alkynes is described. The reaction features a regioselective cleavage of a C-H bond on the benzhydroxamic acid coupling partner as well as a regioselective alkyne insertion. Mechanistic studies point out the important involvement of a N-O bond as a tool for C-N bond formation and catalyst turnover.
- Guimond, Nicolas,Gouliaras, Christina,Fagnou, Keith
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supporting information; experimental part
p. 6908 - 6909
(2010/07/05)
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- SYNTHESIS OF 1-SUBSTITUTED 3,4-DIARYLISOQUINOLINE DERIVATIVES
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3,4-Diaryl-2H-isoquinolin-2-ones and corresponding 1-chloro derivatives were easily prepared in a way involving i) condensation of 2-aroylbenzyl chlorides with arylmethylamines; ii) treatment of the resulting 1-aryl-N-1-hydroxyarylmethylisoindol-3-ones wi
- Delcey, Martine Croisy,Huel, Christiane,Bisagni, Emile
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p. 1721 - 1730
(2007/10/03)
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- Photolysis of Vinyl Halides. Reaction of Photogenerated Vinyl Cations with Cyanate and Thiocyanate Ions
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The title reaction was conducted in a two-phase system of dichloromethane and water using a tetrabutylammonium halide as a phase-transfer catalyst.The reaction of the photogenerated arylvinyl cation with cyanate ion gave only isoquinolone derivatives, whereas the reaction with thiocyanate ion afforded products derived from S attack, vinyl thiocyanates, and products derived from N attack, vinyl isothiocyanates or thioisoquinolones.The ambident nature of thiocyanate ion is compared with the reaction of benzyl bromides.
- Kitamura, Tsugio,Kobayashi, Shinjiro,Taniguchi, Hiroshi
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p. 1801 - 1805
(2007/10/02)
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- REACTION OF PHOTOGENERATED VINYL CATIONS WITH AMBIDENT ANIONS
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Photolysis of vinyl bromides with cyanate anion in a two-phase system gave only isoquinolinones as the N-site attacked products.However, the photolysis with thiocyanate anion gave the N-site attacked products, isothioquinolinones or vinyl isothiocyanates, and the S.site attacked products, vinyl thiocyanates.
- Kitamura, Tsugio,Kobayashi, Shinjiro,Taniguchi, Hiroshi
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p. 1523 - 1526
(2007/10/02)
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