- Rhodium-Catalyzed One-Pot Access to N-Polycyclic Aromatic Hydrocarbons from Aryl Ketones through Triple C-H Bond Activations
-
A Rh-catalyzed pot and step economic synthesis of aza-polycyclic aromatic hydrocarbons (N-PAHs) from readily available aryl ketones and alkynes has been disclosed. Additionally, a novel synthetic application of the well-known aminating reagent hydroxylamine-O-sulfonic acid (HOSA) has been explored as an in situ redox-neutral directing group for the formation of N-PAHs via isoquinoline. Multiple bond formation in a single operation through a cascade of triple C-H bond activations is the beauty of this protocol. The challenging annulations of two different alkynes in a regioselective fashion have been demonstrated effectively. Mechanistic studies reveal that 3,4-diphenyl-1-methylisoquinoline is an active intermediate for this one-pot transformation.
- Biswal, Pragati,Banjare, Shyam Kumar,Pati, Bedadyuti Vedvyas,Mohanty, Smruti Ranjan,Ravikumar, Ponneri Chandrababu
-
supporting information
p. 1108 - 1117
(2021/01/09)
-
- N-Tosylhydrazone as an oxidizing directing group for the redox-neutral access to isoquinolines via Cp?Co(III)-Catalyzed C–H/N–N activation
-
Herein, an efficient and economic access has been revealed for the synthesis of isoquinolines via C–H bond activation strategy by using comparatively inexpensive and versatile cobalt catalyst. A hardly investigated directing group, N-tosylhydrazone has been effectively applied as an internal oxidant for an annulation reaction with internal alkynes via C–H/N–N bond functionalization. This catalytic protocol works for the extensive variety of substrates in moderate to excellent yields under external oxidant-free conditions. Additionally, the proposed protocol has advantages such as broad substrate coverage with significant product yields, readily synthesized substrates as well as scalability up to the gram quantity which further improves the competency of the methodology.
- Deshmukh, Dewal S.,Gangwar, Neha,Bhanage, Bhalchandra M.
-
-
- Ruthenaelectro-Catalyzed Domino Three-Component Alkyne Annulation for Expedient Isoquinoline Assembly
-
The electrochemical three-component assembly of isoquinolines has been accomplished by ruthenaelectro-catalyzed C?H/N?H functionalization. The robustness of the electrocatalysis was reflected by an ample substrate scope, an efficient electrooxidation, and an operationally friendly procedure. The isolation of key intermediates and detailed mechanistic studies, including unprecedented cyclovoltammetric analysis of a seven-membered ruthenacycle, provided support for an unusual ruthenium(II/III/I) regime.
- Tan, Xuefeng,Hou, Xiaoyan,Rogge, Torben,Ackermann, Lutz
-
supporting information
p. 4619 - 4624
(2021/02/05)
-
- Rh(III)?catalyzed synthesis of isoquinolines from N-hydroxyoximes and alkynes in γ-valerolactone
-
A Rh (III)?catalyzed synthesis of isoquinoline derivatives from N-hydroxyoximes and alkynes via C–H activation/annulation process in biomass-derived γ-valerolactone (GVL) has been developed. A series of functional groups were well tolerated, affording the desired products in good to excellent yields.
- Jiang, Kuan-Chang,Wang, Liang,Chen, Qun,He, Ming-Yang,Shen, Ming-Gui,Zhang, Zhi-Hui
-
supporting information
p. 94 - 102
(2020/09/21)
-
- Hydroxylamine-O-Sulfonic Acid (HOSA) as a Redox-Neutral Directing Group: Rhodium Catalyzed, Additive Free, One-Pot Synthesis of Isoquinolines from Arylketones
-
A new application of hydroxylamine-O-sulfonic acid (HOSA) has been discovered whereby aromatic ketones react with HOSA and alkynes to form isoquinolines in the presence of a RhIII catalyst. This C–H/N–O annulation methodology gives excellent yields even without any silver additive, acid/base or metal oxidant. This is the first report wherein a directing group is simultaneously forming in situ, acting as acid additive, and also as an internal oxidant.
- Biswal, Pragati,Pati, Bedadyuti Vedvyas,Chebolu, Rajesh,Ghosh, Asit,Ravikumar
-
supporting information
p. 1006 - 1014
(2020/02/15)
-
- Rh(III)-catalyzed synthesis of isoquinolines using the N-Cl bond of N-chloroimines as an internal oxidant
-
The Rh(III)-catalyzed coupling of N-chloroimines with alkynes for the efficient synthesis of isoquinolines is reported. This represents the first use of the N-Cl bond of N-chloroimines as an internal oxidant for construction of the isoquinoline skeleton. The synthesis features atom and step economy, a green solvent (EtOH), mild reaction conditions, and a broad substrate scope.
- Chu, Benfa,Fang, Lili,Guo, Shan,Qi, Bing,Shi, Pengfei,Wang, Qi,Zhu, Jin
-
-
- Eco-friendly synthesis method of 3, 4-disubstituted isoquinoline derivative promoted by room-temperature illumination
-
The invention discloses an eco-friendly synthesis method of a 3, 4-disubstituted isoquinoline derivative promoted by room-temperature illumination. The method comprises the following steps: by using water and polyethylene glycol 400 as a mixed solvent and a phenyl oxime compound and non-terminal alkyne as raw materials, synthesizing the 3, 4-disubstituted isoquinoline derivative at a room temperature under illumination. The method is a C-H coupling reaction catalyzed by a transition metal, and eco-friendly synthesis of the isoquinoline derivative can be simply and efficiently carried out. Compared with a traditional method, the method is safer, more economical and environmentally friendly, the functional group tolerance is good, the yield is high, extra photocatalysts and oxidizing agentsare not needed, the cost is reduced, the byproduct is H2O, the generation of a large amount of wastes is avoided, the atom utilization rate is improved, the substrate does not need to be pre-activatedand the reaction is carried out at room temperature, and the operation difficulty is reduced. According to the invention, a derivative molecular library of an isoquinoline ring with biological activity can be simply and rapidly supplemented, so that screening and discovery of new drug candidate molecules are facilitated.
- -
-
Paragraph 0011
(2020/05/02)
-
- Ruthenium-Catalyzed Annulation of N -Cbz Hydrazones via C-H/N-N Bond Activation for the Rapid Synthesis of Isoquinolines
-
In this work, N -Cbz hydrazone has been employed as a rarely explored directing group for the synthesis of isoquinolines by annulation with internal alkynes via C-H/N-N activation using Ru catalyst. Additive as well as external oxidant-free rapid protocol
- Bhanage, Bhalchandra M.,Deshmukh, Dewal S.
-
p. 2506 - 2514
(2019/06/08)
-
- Cp*Co(III) catalyzed annulation of N-Cbz hydrazones for the redox-neutral synthesis of isoquinolines via C–H/N–N bond activation
-
A new cascade oxidative cyclization reaction of N-Cbz hydrazones with internal alkynes has been explored for the preparation of isoquinoline derivatives using Cp*CoIII-catalyst through C–H and N–N bond functionalization. N-Cbz hydrazones are ra
- Subhedar, Dnyaneshwar D.,Deshmukh, Dewal S.,Bhanage, Bhalchandra M.
-
p. 3121 - 3130
(2019/08/30)
-
- Cp?-Free Cobalt-Catalyzed C-H Activation/Annulations by Traceless N, O-Bidentate Directing Group: Access to Isoquinolines
-
N,O-Bidentate directing-enabled, traceless heterocycle synthesis is described via Cp?-free cobalt-catalyzed C-H activation/annulation. The weakly coordinating nature of the carboxylic acid was employed for the preparation of isoquinolines. Meanwhile, the N-O bond of the α-imino-oxy acid can serve as an internal oxidant. Terminal as well as internal alkynes can be efficiently applied to the catalytic system. This operationally simple approach shows a broad substrate scope with the products obtained in good to excellent yields.
- Li, Xiao-Cai,Du, Cong,Zhang, He,Niu, Jun-Long,Song, Mao-Ping
-
p. 2863 - 2866
(2019/04/17)
-
- Easy access to synthesize isoquinolines from aryl ketoximes and internal alkynes via Iridium (III)-catalyzed C[sbnd]H/N[sbnd]O bond activation
-
A highly efficient approach to synthesize isoquinoline derivatives through Iridium(III)-catalyzed cyclization of aryl ketoximes and internal alkynes without oxidant is reported. A broad range isoquinolines are obtained in good to excellent yields and various functional groups are well tolerated.
- Lin, Wei,Hu, Xiu-Xiu,Zhuang, Cang-Wei,Wang, Ya-Zhen
-
p. 3015 - 3023
(2019/04/30)
-
- Redox-Neutral [4 + 2] Annulation of N-Methoxybenzamides with Alkynes Enabled by an Osmium(II)/HOAc Catalytic System
-
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
-
supporting information
p. 9904 - 9908
(2019/12/24)
-
- Rapid and Atom Economic Synthesis of Isoquinolines and Isoquinolinones by C–H/N–N Activation Using a Homogeneous Recyclable Ruthenium Catalyst in PEG Media
-
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.
-
p. 2919 - 2927
(2019/05/10)
-
- Cp*Co(iii)-catalyzed annulation of azines by C-H/N-N bond activation for the synthesis of isoquinolines
-
Herein, an efficient, atom economic and external oxidant free approach has been disclosed for the synthesis of isoquinolines. Azines were employed for annulation reactions with alkynes via sequential C-H/N-N bond activation using an air-stable cobalt catalyst. The method takes advantage of the incorporation of both the nitrogen atoms of azines into the desired isoquinoline products, offering the highest atom economy. In addition, the developed protocol works under external oxidant as well as silver salt free conditions. Furthermore, the established methodology features a relatively broad substrate scope with high product yields and scalability up to the gram level.
- Deshmukh, Dewal S.,Yadav, Prashant A.,Bhanage, Bhalchandra M.
-
p. 3489 - 3496
(2019/04/14)
-
- N-Tosylhydrazone directed annulation via C-H/N-N bond activation in Ru(ii)/PEG-400 as homogeneous recyclable catalytic system: a green synthesis of isoquinolines
-
A green and sustainable methodology for the synthesis of isoquinolines using Ru(ii)/PEG-400 as a homogeneous recyclable catalytic system has been demonstrated. N-Tosylhydrazone, a rarely explored directing group, has been successfully employed for an annu
- Deshmukh, Dewal S.,Bhanage, Bhalchandra M.
-
p. 4864 - 4873
(2018/07/15)
-
- Base-Promoted [3+2]-Annulation of Oxime Esters and Aldehydes for Rapid Isoxazoline Formation
-
A base-promoted [3+2]-annulation of ketoxime esters and aldehydes is disclosed for the facile and rapid synthesis of 3,5-disubstituted and 3,4,5-trisubstituted isoxazolines. The key to our success is the pivalate leaving group of the oxime substrates, combined with cesium carbonate as promoter. This chemistry allows the assembly of a vast array of isoxazoline derivatives under simple base conditions in a method complementary to the classic isoxazoline formation via [3+2]-dipolar cycloaddition of nitrile oxides and olefins. It also represents a new reaction pattern involving electrophilic amination/N–O bond substitution. (Figure presented.).
- Huang, Huawen,Li, Feifei,Xu, Zhenhua,Cai, Jinhui,Ji, Xiaochen,Deng, Guo-Jun
-
p. 3102 - 3107
(2017/09/13)
-
- Cobalt-Catalyzed Selective Synthesis of Isoquinolines Using Picolinamide as a Traceless Directing Group
-
Picolinamide has first been employed as a traceless directing group for the cobalt-catalyzed oxidative annulation of benzylamides with alkynes to synthesize isoquinolines through C-H/N-H bonds activation. Oxygen is used as a terminal oxidant. This protocol exhibits good functional group tolerance and excellent regioselectivity. Both terminal and internal alkynes can be efficiently applied to this catalytic system as substrates.
- Kuai, Changsheng,Wang, Lianhui,Li, Bobin,Yang, Zhenhui,Cui, Xiuling
-
supporting information
p. 2102 - 2105
(2017/04/27)
-
- Novel polysubstitution isoquinoline derivative and synthesis method thereof
-
The invention provides a novel polysubstitution isoquinoline derivative shown as a formula (I) and a synthesis method thereof. The formula I is shown in the specification. A C-H activation/cyclization method is used; ketoxime and diphenylacetypene are used as raw material; pentamethyl cyclopentadiene iridochloride is used as a catalyst for synthesizing the isoquinoline derivative. The preparation method is simple; the catalyst consumption is low; the reaction conditions are mild; the reaction steps are few; the reaction time is short; the yield is high. The isoquinoline derivative provided by the invention belongs to a kind of alkaloid compounds with important medicine activity, and can be widely applied to the study in aspects of fields of medicine and agriculture.
- -
-
Paragraph 0020; 0021
(2018/03/01)
-
- Bidentate Directing-Enabled, Traceless Heterocycle Synthesis: Cobalt-Catalyzed Access to Isoquinolines
-
Traceless heterocycle synthesis based on transition-metal-catalyzed C-H functionalization is synthetically appealing but has been realized only in monodentate directing systems. Bidentate directing systems allow for the achievement of high catalytic reactivity without the need for a high-cost privileged ligand. The first bidentate directing-enabled, traceless heterocycle synthesis is demonstrated in the cobalt-catalyzed synthesis of isoquinolines via 2-hydrazinylpyridine-directed C-H coupling/cyclization with alkynes. Convenient directing group installation through a ubiquitously present ketone group allows synthetic elaboration for complex molecules.
- Zhou, Shuguang,Wang, Mingyang,Wang, Lili,Chen, Kehao,Wang, Jinhu,Song, Chao,Zhu, Jin
-
supporting information
p. 5632 - 5635
(2016/11/17)
-
- A kind of high-efficient synthetic indole and isoquinoline derivatives (by machine translation)
-
The invention discloses a substituted indole and isoquinoline preparation method, which belongs to the technical field of organic chemical synthesis. This method adopts the oxygen as the oxidizing agent, various substituents substituted alkyne starting material of the aromatic amine or [...] , by transition metal-catalyzed, get containing indole or isoquinoline compound of the structure. The reaction raw material, oxidizing agent and cheap and easily obtained catalyst, synthesis technique is simple, which greatly reduces the cost of synthesizing; mild reaction conditions, high yield, easy industrialization; reaction raw materials and catalyst cleaning non-toxic, small pollution to the environment. Such compounds and their derivatives as an important fine chemicals, in the medical, agricultural chemicals, perfume and widely used photoelectric and other industries. (by machine translation)
- -
-
Paragraph 0060; 0061
(2016/10/07)
-
- Palladium-catalyzed enolate arylation as a key C-C bond-forming reaction for the synthesis of isoquinolines
-
The palladium-catalyzed coupling of an enolate with an ortho-functionalized aryl halide (an α-arylation) furnishes a protected 1,5-dicarbonyl moiety that can be cyclized to an isoquinoline with a source of ammonia. This fully regioselective synthetic route tolerates a wide range of substituents, including those that give rise to the traditionally difficult to access electron-deficient isoquinoline skeletons. These two synthetic operations can be combined to give a three-component, one-pot isoquinoline synthesis. Alternatively, cyclization of the intermediates with hydroxylamine hydrochloride engenders direct access to isoquinoline N-oxides; and cyclization with methylamine, gives isoquinolinium salts. Significant diversity is available in the substituents at the C4 position in four-component, one-pot couplings, by either trapping the in situ intermediate after α-arylation with carbon or heteroatom-based electrophiles, or by performing an α,α-heterodiarylation to install aryl groups at this position. The α-arylation of nitrile and ester enolates gives access to 3-amino and 3-hydroxyisoquinolines and the α-arylation of tert-butyl cyanoacetate followed by electrophile trapping, decarboxylation and cyclization, C4-functionalized 3-aminoisoquinolines. An oxime directing group can be used to direct a C-H functionalization/bromination, which allows monofunctionalized rather than difunctionalized aryl precursors to be brought through this synthetic route.
- Pilgrim, Ben S.,Gatland, Alice E.,Esteves, Carlos H. A.,McTernan, Charlie T.,Jones, Geraint R.,Tatton, Matthew R.,Procopiou, Panayiotis A.,Donohoe, Timothy J.
-
p. 1065 - 1090
(2016/01/15)
-
- Easy Access to 1-Amino and 1-Carbon Substituted Isoquinolines via Cobalt-Catalyzed C - H/N - O Bond Activation
-
A green atom-economical method for the synthesis of highly functionalized 1-amino and 1-carbon substituted isoquinolines from the reaction of N′-hydroxybenzimidamides and aryl ketoximes, respectively, with alkynes via pentamethylcyclopentadienylcobalt(III)-catalyzed C - H/N - O bond activation is described. The external oxidant-free annulation reaction uses the =NOH moiety in N′-hydroxybenzimidamides or N-aromatic ketone oximes as the directing group and internal oxidant. This first row transition metal-catalyzed annulation serves as an efficient alternative for the synthesis of isoquinolines, as water is the only by-product and expensive noble metals such as rhodium(III), iridium(III), palladium(II), and ruthenium(II) are not required. The reaction proceeds via C - H activation, alkyne insertion, reductive elimination, and N - O activation.
- Muralirajan, Krishnamoorthy,Kuppusamy, Ramajayam,Prakash, Sekar,Cheng, Chien-Hong
-
p. 774 - 783
(2016/03/09)
-
- Cobalt(III)-Catalyzed C-H/N-O Functionalizations: Isohypsic Access to Isoquinolines
-
C-H/N-O functionalizations by cobalt(III) catalysis allowed the expedient synthesis of a broad range of isoquinolines. Thus, internal and challenging terminal alkynes proved to be viable substrates for an isohypsic annulation, which was shown to proceed by a facile C-H cobaltation.
- Wang, Hui,Koeller, Julian,Liu, Weiping,Ackermann, Lutz
-
supporting information
p. 15525 - 15528
(2015/11/03)
-
- Cobalt(III)-Catalyzed Dehydrative [4+2] Annulation of Oxime with Alkyne by C-H and N-OH Activation
-
Efficient, scalable cobalt-catalyzed redox-neutral [4+2] annulation of readily available oximes and alkyne is reported. The developed synthetic methodology is widely applicable and tolerates various functional groups including heterocycles. A stable CpCoIII neutral complex is employed as the catalyst for this redox-neutral [4+2] annulation reaction, which progresses smoothly by way of a reversible cyclometallation without any external oxidizing agent, and produces only water as the side product.
- Sen, Malay,Kalsi, Deepti,Sundararaju, Basker
-
supporting information
p. 15529 - 15533
(2015/11/03)
-
- Rhodium(III)-catalyzed one-pot access to isoquinolines and heterocycle-fused pyridines in aqueous medium through C-H cleavage
-
An efficient RhIII-catalyzed ortho-C-H bond activation for the synthesis of substituted isoquinolines and heterocycle-fused pyridines in aqueous medium has been developed. This method involves the in situ generation of ketimines from ketones an
- Zhang, Jitan,Qian, Hongsheng,Liu, Zhanxiang,Xiong, Chunhua,Zhang, Yuhong
-
p. 8110 - 8118
(2015/02/02)
-
- C-H activation guided by aromatic N-H ketimines: Synthesis of functionalized isoquinolines using benzyl azides and alkynes
-
Aromatic N-H ketimines were in situ generated from various benzylic azides by ruthenium catalysis for the subsequent Rh-catalyzed annulation reaction with alkynes to give the corresponding isoquinolines. In contrast to conventional synthetic methods for aromatic N-H ketimines, our protocol works under mild and neutral conditions, which enabled the synthesis of isoquinolines having various functionalities such as carbonyl, ester, alkenyl, and ether groups. In addition, the imidates generated from α-azido ethers were successfully used for the synthesis of 1-alkoxyisoquinolines.
- Gupta, Sreya,Han, Junghoon,Kim, Yongjin,Lee, Soon W.,Rhee, Young Ho,Park, Jaiwook
-
p. 9094 - 9103
(2014/12/11)
-
- Rh-catalyzed sequential oxidative C-H and N-N bond activation: Conversion of azines into isoquinolines with air at room temperature
-
A rhodium-catalyzed sequential oxidative C-H annulation reaction between ketazines and internal alkynes has been developed via C-H and N-N bond activation with air as an external oxidant, which led to an efficient approach toward isoquinolines with high atom efficiency at rt. Utilizing the distinctive reactivity of this catalysis, both N-atoms of the azines could be efficiently incorporated to the desired isoquinolines under very robust and mild reaction conditions.
- Han, Wenjia,Zhang, Guoying,Li, Guangxing,Huang, Hanmin
-
supporting information
p. 3532 - 3535
(2014/07/21)
-
- Manganese-catalyzed dehydrogenative [4+2] annulation of N-H imines and alkynes by C-H/N-H activation
-
Described herein is a manganese-catalyzed dehydrogenative [4+2] annulation of N-H imines and alkynes, a reaction providing highly atom-economical access to diverse isoquinolines. This transformation represents the first example of manganese-catalyzed C-H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H2 as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition-metal-catalyzed C-H activation. Mechanistic studies revealed the five-membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle.
- He, Ruoyu,Huang, Zhi-Tang,Zheng, Qi-Yu,Wang, Congyang
-
supporting information
p. 4950 - 4953
(2014/05/20)
-
- Rhodium-catalyzed synthesis of isoquinolines and indenes from benzylidenehydrazones and internal alkynes
-
A new route is presented for the selective assembly of isoquinolines and indenes by rhodium-catalyzed tandem cyclization of benzylidenehydrazones with internal alkynes. This method involves the selective cleavage of the N-N bond and the C=N bonds and is dependent on the substituents of the benzylidenehydrazone.
- Huang, Xiao-Cheng,Yang, Xu-Heng,Song, Ren-Jie,Li, Jin-Heng
-
p. 1025 - 1031
(2014/03/21)
-
- Synthesis of isoquinolines via Rh(III)-catalyzed C-H activation using hydrazone as a new oxidizing directing group
-
An efficient and mechanistically interesting method for the synthesis of highly substituted isoquinolines by a Rh(III)-catalyzed hydrazone directed ortho C-H bond activation and annulation without an external oxidant is described. This reaction is accomplished via a C-C and C-N bond formation along with N-N bond cleavage.
- Chuang, Sheng-Chieh,Gandeepan, Parthasarathy,Cheng, Chien-Hong
-
supporting information
p. 5750 - 5753
(2013/12/04)
-
- Activating group recycling in action: A rhodium-catalyzed carbothiolation route to substituted isoquinolines
-
A new rhodium(I) catalyst allows practical and efficient alkyne carbothiolation reactions to be achieved on synthetically useful ketone-bearing aryl methyl sulfides. The carbothiolation adducts, featuring a 'recycled methyl sulfide' activating group, are convenient precursors to highly substituted isoquinolines.
- Arambasic, Milan,Hooper, Joel F.,Willis, Michael C.
-
p. 5162 - 5165
(2013/11/06)
-
- Rhodium-catalyzed oxidative coupling of aryl hydrazones with internal alkynes: Efficient synthesis of multisubstituted isoquinolines
-
An efficient rhodium-catalyzed oxidative coupling reaction has been developed that gives high yields of multisubstituted isoquinolines from easily accessible aryl hydrazones and internal alkynes. Indenone hydrazone can also be synthesized in high yield from the corresponding benzaldehyde hydrazone by using this approach.
- Liu, Wenting,Hong, Xiaohu,Xu, Bin
-
p. 2137 - 2149
(2013/08/23)
-
- Isoquinoline N-oxide synthesis under Pd-Catalysed C-H activation/annulation processes
-
An oxime directed C-H activation-annulation reaction for the selective synthesis of a range of isoquinoline N-oxides has been developed. Under palladium-catalyzed acid-assisted conditions, the reaction undergoes concerted metallation deprotonation followed by carbopalladation and transmetallation to give poly substituted isoquinoline N-oxides in moderate to good yields. Georg Thieme Verlag Stuttgart, New York.
- Li, Bingyao,Jiao, Pingxuan,Zhong, Hongban,Huang, Jianhui
-
supporting information
p. 2431 - 2436
(2013/11/06)
-
- Cationic ruthenium catalysts for alkyne annulations with oximes by C-H/N-O functionalizations
-
Cationic ruthenium(II) complexes enabled efficient redox-neutral annulations of alkynes with readily available oximes. The catalytic dehydrative C-H/N-O bond functionalization proved to be broadly applicable and was shown to proceed through a reversible cyclometalation.
- Kornhaass, Christoph,Li, Jie,Ackermann, Lutz
-
p. 9190 - 9198,9
(2012/12/11)
-
- Synthesis of substituted isoquinolines utilizing palladium-catalyzed α-arylation of ketones
-
The utilization of sequential palladium-catalyzed α-arylation and cyclization reactions provides a general approach to an array of isoquinolines and their corresponding N-oxides. This methodology allows the convergent combination of readily available precursors in a regioselective manner and in excellent overall yields. This powerful route to polysubstituted isoquinolines, which is not limited to electron rich moieties, also allows rapid access to analogues of biologically active compounds.
- Donohoe, Timothy J.,Pilgrim, Ben S.,Jones, Geraint R.,Bassuto, Jose A.
-
p. 11605 - 11608
(2012/09/07)
-
- Synthesis of isoquinolines and heterocycle-fused pyridines via three-component cascade reaction of aryl ketones, hydroxylamine, and alkynes
-
An efficient one-pot synthesis of isoquinolines and heterocycle-fused pyridines by three-component reaction of aryl ketones, hydroxylamine, and alkynes is developed. The reaction involves condensation of aryl ketones and hydroxylamine, rhodium(III)-cataly
- Zheng, Liyao,Ju, Jia,Bin, Yunhui,Hua, Ruimao
-
experimental part
p. 5794 - 5800
(2012/07/30)
-
- Synthesis of polysubstituted isoquinolines through cross-coupling reactions with α-alkoxytosylhydrazones
-
A Pd-catalyzed cross-coupling reaction of α-alkoxytosylhydrazones with sulfonates derived from salicyl aldehydes gives rise to protected 1,5-dicarbonyl compounds. Treatment with ammonium hydroxide readily transforms these alkenes into isoquinolines with d
- Florentino, Lucia,Aznar, Fernando,Valdes, Carlos
-
supporting information; experimental part
p. 2323 - 2325
(2012/06/18)
-
- Nickel-catalyzed cyclization of ortho-iodoketoximes and ortho-iodoketimines with alkynes: Synthesis of highly substituted isoquinolines and isoquinolinium salts
-
A convenient method for the synthesis of highly substituted isoquinolines and isoquinolinium salts by the nickel-catalyzed cyclization of ortho-haloketoximes and -ketimines, respectively, with alkynes is described. The reaction of ortho-haloketoximes and various alkynes in the presence of [Ni(PPh3)2Br2] and zinc powder in a mixture of acetonitrile and tetrahydrofuran at 80 °C for 15 hours gave 1,3,4-trisubstituted isoquinoline products in moderate to excellent yields and high regioselectivity. The corresponding isoquinoline N-oxide was found to be the intermediate in the cyclization reaction pathway. In contrast, the reaction of ortho-haloketimines and alkynes under similar catalytic conditions in tetrahydrofuran at 70 °C for two hours gave 1,2,3,4-tetrasubstituted isoquinolinium salts in good to excellent yields. In the nickel of time: ortho-Haloketoximes and -ketimines undergo [4+2] cyclization reactions with alkynes, catalyzed by nickel complexes to give highly substituted isoquinolines and isoquinolinium salts, respectively, in good to excellent yields (see scheme).
- Shih, Wei-Chun,Teng, Chu-Chun,Parthasarathy, Kanniyappan,Cheng, Chien-Hong
-
p. 306 - 313
(2012/05/05)
-
- Rhodium(III)-catalyzed heterocycle synthesis using an internal oxidant: Improved reactivity and mechanistic studies
-
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
-
supporting information; experimental part
p. 6449 - 6457
(2011/06/16)
-
- Synthesis of isoquinolines via rhodium(III)-catalyzed dehydrative C-C and C-N coupling between oximines and alkynes
-
Isoquinolines have been synthesized from the redox-neutral dehydrative C-N and C-C cross-coupling between oximines and alkynes using a catalytic amount of (pentamethylcyclopentadiene)rhodium dichloride dimer {[RhCp*Cl 2]2} and cesium
- Zhang, Xingping,Chen, Dan,Zhao, Miao,Zhao, Jing,Jia, Aiqun,Li, Xingwei
-
p. 719 - 723
(2011/05/08)
-
- Rhodium(III)-catalyzed synthesis of isoquinolines from aryl ketone o -acyloxime derivatives and internal alkynes
-
A synthetic method of isoquinolines from aryl ketone O-acyloxime derivatives and internal alkynes has been developed using [Cp*RhCl 2]2 - NaOAc as the potential catalyst system. The present transformation is carried out by a redox-neutral sequence of C - H vinylation via ortho-rhodation and C - N bond formation of the putative vinyl rhodium intermediate on the oxime nitrogen, where the N - O bond of oxime derivatives could work as an internal oxidant to maintain the catalytic cycle.
- Too, Pei Chui,Wang, Yi-Feng,Chiba, Shunsuke
-
p. 5688 - 5691
(2011/03/23)
-
- Easy access to isoquinolines and tetrahydroquinolines from ketoximes and alkynes via rhodium-catalyzed C-H bond activation
-
(Chemical Equation Presented) Described herein is a convenient and highly regioselective synthesis of substituted isoquinoline derivatives from various aromatic ketoximes and alkynes via a one-pot, rhodium-catalyzed C-H bond activation. In addition, tetra
- Parthasarathy, Kanniyappan,Cheng, Chien-Hong
-
supporting information; experimental part
p. 9359 - 9364
(2010/03/04)
-
- Rhodium-catalyzed one-pot synthesis of substituted pyridine derivatives from α,β-unsaturated ketoximes and alkynes
-
(Chemical Equation Presented) A rhodium-catalyzed chelation-assisted C-H activation of α,β-unsaturated ketoximes and the reaction with alkynes to afford highly substituted pyridine derivatives is described.
- Parthasarathy, Kanniyappan,Jeganmohan, Masilamani,Cheng, Chien-Hong
-
p. 325 - 328
(2008/09/19)
-
- Rh(I)-catalyzed direct ortho-alkenylation of aromatic ketimines with alkynes and its application to the synthesis of isoquinoline derivatives
-
Novel synthetic methods of both ortho-alkenylated aromatic ketones and isoquinoline derivatives have been developed through the Rh(I)-catalyzed direct ortho-alkenylation of common aromatic ketimines with alkynes. Furthermore, a highly efficient one-pot sy
- Lim, Sung-Gon,Lee, Jun Hee,Moon, Choong Woon,Hong, Jun-Bae,Jun, Chul-Ho
-
p. 2759 - 2761
(2007/10/03)
-
- Synthesis of Isoquinolines by Cycloaddition of Arynes to 1,2,4-Triazines
-
Benzyne has been generated from benzenediazonium-2-carboxylate in the presence of several 1,2,4-triazines 1 and isoquinolines 2 have been isolated in moderate yield. 1-Aminobenzotriazole was also used as the source of benzyne and isoquinolines were again isolated in moderate yield from these reactions. 4-Methylbenzyne, which was generated from 5-methylanthranilic acid, reacted unselectively with the triazines to give mixtures of 6- and 7-methylisoquinolines 3 and 4.On the other hand reactions of 3-methylbenzyne with the triazines 1d and 1e proceeded with high regioselectivity, giving only the 5-methylisoquinoline 5a and the 8-methylisoquinoline 6b, respectively.
- Gonsalves, Antonio M. d'A. Rocha,Melo, Teresa M. V. D. Pinho e
-
p. 6821 - 6826
(2007/10/02)
-
- ISOQUINOLINE DERIVATIVES FROM THE RITTER-TYPE REACTION OF VINYL CATIONS
-
Both silver-assisted reaction of β-arylvinyl bromides and the photolysis in nitriles gave isoquinoline derivatives, indicating that the Ritter reaction involving a vinyl cation took place.
- Kitamura, Tsugio,Kobayashi, Shinjiro,Taniguchi, Hiroshi
-
p. 1351 - 1354
(2007/10/02)
-