1198575-42-6Relevant articles and documents
N-Tosylhydrazone as an oxidizing directing group for the redox-neutral access to isoquinolines via Cp?Co(III)-Catalyzed C–H/N–N activation
Deshmukh, Dewal S.,Gangwar, Neha,Bhanage, Bhalchandra M.
, (2021/06/28)
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.
Ruthenaelectro-Catalyzed Domino Three-Component Alkyne Annulation for Expedient Isoquinoline Assembly
Tan, Xuefeng,Hou, Xiaoyan,Rogge, Torben,Ackermann, Lutz
supporting information, p. 4619 - 4624 (2021/02/05)
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.
Rh(III)?catalyzed synthesis of isoquinolines from N-hydroxyoximes and alkynes in γ-valerolactone
Jiang, Kuan-Chang,Wang, Liang,Chen, Qun,He, Ming-Yang,Shen, Ming-Gui,Zhang, Zhi-Hui
supporting information, p. 94 - 102 (2020/09/21)
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.
Rh(III)-catalyzed synthesis of isoquinolines using the N-Cl bond of N-chloroimines as an internal oxidant
Chu, Benfa,Fang, Lili,Guo, Shan,Qi, Bing,Shi, Pengfei,Wang, Qi,Zhu, Jin
supporting information, (2020/03/10)
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.
Hydroxylamine-O-Sulfonic Acid (HOSA) as a Redox-Neutral Directing Group: Rhodium Catalyzed, Additive Free, One-Pot Synthesis of Isoquinolines from Arylketones
Biswal, Pragati,Pati, Bedadyuti Vedvyas,Chebolu, Rajesh,Ghosh, Asit,Ravikumar
, p. 1006 - 1014 (2020/02/15)
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.
Eco-friendly synthesis method of 3, 4-disubstituted isoquinoline derivative promoted by room-temperature illumination
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Paragraph 0013, (2020/05/02)
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.
Rhodium(iii)-catalysed carboxylate-directed C-H functionalizations of isoxazoles with alkynes
Yugandar, Somaraju,Nakamura, Hiroyuki
, p. 8382 - 8385 (2019/07/22)
An efficient oxidative [4+2] annulation of isoxazolyl-4-carboxylic acids with internal alkynes proceeded in the presence of the [Cp?RhCl2]2 catalyst. Oxidants controlled the formation of pyranoisoxazolones and isoquinolines. A decarb
Cp?-Free Cobalt-Catalyzed C-H Activation/Annulations by Traceless N, O-Bidentate Directing Group: Access to Isoquinolines
Li, Xiao-Cai,Du, Cong,Zhang, He,Niu, Jun-Long,Song, Mao-Ping
, p. 2863 - 2866 (2019/04/17)
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.
Rapid and Atom Economic Synthesis of Isoquinolines and Isoquinolinones by C–H/N–N Activation Using a Homogeneous Recyclable Ruthenium Catalyst in PEG Media
Deshmukh, Dewal S.,Gangwar, Neha,Bhanage, Bhalchandra M.
, p. 2919 - 2927 (2019/05/10)
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.
Cp*Co(iii)-catalyzed annulation of azines by C-H/N-N bond activation for the synthesis of isoquinolines
Deshmukh, Dewal S.,Yadav, Prashant A.,Bhanage, Bhalchandra M.
, p. 3489 - 3496 (2019/04/14)
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.
