4953-10-0Relevant articles and documents
Magnetically recoverable copper nanorods and their catalytic activity in Ullmann cross-coupling reaction
Rajabzadeh, Maryam,Eshghi, Hossein,Khalifeh, Reza,Bakavoli, Mehdi
, (2017)
A novel polydentate ligand supported on Fe3O4@SiO2 was designed and demonstrated for the synthesis of Cu nanorods. The Fe3O4@SiO2/EP.EN.EG@Cu was characterized using X-ray diffraction, ther
Mechanistic investigations on C-H activated dealkylating cyclo-amination reactions of substituted triazenes, formamidines and amidines
Preusser, Silvio,Kalden, Diana,Wendler, Felix,Sch?nherr, Paul R. W.,G?rls, Helmar,Westerhausen, Matthias,Imhof, Wolfgang
, p. 651 - 664 (2020/07/27)
Catalytic dealkylating cycloamination reactions of N 1-methylated-N 1,N 3-diarylated triazenes proceed via two subsequent oxidative addition reactions, regioselectivity producing benzotriazoles by C-H and C-Br activation steps. Whereas palladium-based catalysis in the presence of dealkylating reagents and directing phosphane ligands leads to high yields, the homologous metals nickel and platinum as well as other 3d transition metals show only poor catalytic activity in similar procedures. Starting compounds have been widely varied to introduce potentially competing reaction sites and to investigate the reaction mechanism of the catalytic cyclization reactions. Yields of the benzotriazole synthesis strongly depend on the electronic and steric properties of the directing phosphane ligands, the nature of the dealkylating bases and the substitution pattern in 2- A nd 4-position of the aryl groups of the starting triazenes. In order to clarify the role of the catalyst, palladium-based intermediates were identified. Finally, formamidines and bulky amidines were tested in related C-H activated dealkylating cycloamination reactions.
Regioselective Ortho Amination of an Aromatic C-H Bond by Trifluoroacetic Acid via Electrochemistry
Wang, Jing-Hao,Lei, Tao,Nan, Xiao-Lei,Wu, Hao-Lin,Li, Xu-Bing,Chen, Bin,Tung, Chen-Ho,Wu, Li-Zhu
supporting information, p. 5581 - 5585 (2019/08/01)
A trifluoroacetic acid-facilitated ortho amination of alkoxyl arene has been established via anodic oxidation in an undivided cell. In the absence of any additional metal or oxidant reagents, a series of aromatic and heteroaromatic amine derivatives have
Cu-catalyzed arylation of 1-acyl-1H-1,2,3-Benzotriazoles via C–N activation
Zhang, Wenying,Wang, Yangyang,Jia, Xiangru,Du, Zhengyin,Fu, Ying
, p. 64 - 67 (2019/06/10)
An efficient copper-catalyzed arylation reaction of 1-acyl-1H-1,2,3-benzotriazoles with diaryliodonium salts via C–N activation is explored. The reaction is conducted regioselectively to form 1-aryl-1H-1,2,3-benzotriazoles in MeCN at 80 °C in the presence of cesium carbonate. 29 examples are given with the product yield of up to 84%. The probable reaction mechanism is proposed.
The Disappearing Director: The Case of Directed N-Arylation via a Removable Hydroxyl Group
Andrzejewska, Magdalena R.,Vuram, Prasanna K.,Pottabathini, Narender,Gurram, Venkateshwarlu,Relangi, Siva Subrahmanyam,Korvinson, Kirill A.,Doddipalla, Raju,Stahl, Lothar,Neary, Michelle C.,Pradhan, Padmanava,Sharma, Somesh,Lakshman, Mahesh K.
, p. 2503 - 2510 (2018/05/08)
A facile and broadly applicable method for the regiospecific N-arylation of benzotriazoles is reported. Copper-mediated reactions of diverse 1-hydroxy-1H-benzotriazoles with aryl boronic acids lead to 1-aryl-1H-benzotriazole 3-oxides. A N1-OH→N3 prototropy in the 1-hydroxy-1H-benzotriazoles is plausibly the underlying basis, where the tautomer is captured by the boronic acid, leading to C?N (not C?O) bond formation. Because the N?O bond in amine N-oxides and 1-hydroxy-1H-benzotriazoles can be easily reduced by diboron reagents such as (pinB)2 and B2(OH)4, exposure of the 1-aryl-1H-benzotriazole 3-oxides to B2(OH)4 then leads to facile reduction of the N?O bond resulting in diverse, regiospecifically-arylated benzotriazoles. Thus, the N-hydroxyl group in 1-hydroxy-1H-benzotriazoles acts as a disposable arylation director. (Figure presented.).
Selective Synthesis of 3-Arylbenzo-1,2,3-triazin-4(3H)-ones and 1-Aryl-(1H)-benzo-1,2,3-triazoles from 1,3-Diaryltriazenes through Pd(0) Catalyzed Annulation Reactions
Chandrasekhar, Attoor,Sankararaman, Sethuraman
, p. 11487 - 11493 (2017/11/10)
Pd(0) catalyzed carbonylative annulation reaction of 1-(2-iodophenyl)-3-aryltriaz-1-enes in the presence of DABCO and 1 atm of carbon monoxide in toluene at 80 °C gave the corresponding 3-arylbenzo-1,2,3-triazin-4(3H)-ones with high selectivity and in exc
Photochemical C–H Activation: Generation of Indole and Carbazole Libraries, and First Total Synthesis of Clausenawalline D
Alimi, Isak,Remy, Richard,Bochet, Christian G.
, p. 3197 - 3210 (2017/06/21)
The photolysis of N-aryltriazoles and N-arylbenzotriazoles leads to indoles and carbazoles, respectively. Because libraries of triazoles can be accessed rapidly, for example by the copper-catalyzed [3+2] cycloaddition reaction between alkynes and azides, this reaction allows the preparation of indoles in a single operation, by the simultaneous photolysis of the precursor library. As an example of such a synthesis of carbazoles, we prepared for the first time clausenawalline D, an antimalarial alkaloid that was recently isolated.
A aryne synthetic method (by machine translation)
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Paragraph 0062-0065, (2017/08/25)
The invention discloses a method for synthesizing aryne new method, which belongs to the technical field of chemical industry. The method firstly to sulfuryl fluoride with 2 - trialkyl (or aryl) silicon phthalimidephenol as the starting material for synthesizing new aryne precursor, then make it with alkali is produced aryne (active intermediates). The active intermediate in situ chemical reaction with other compounds. The method substrate fluorine atom content is low, with high atom economy, and effectively reduce the reaction and post-processing in the process cause pollution to the environment and luminescent harm to human body; at the same time cheap and easy to obtain, synthesis technique is simple, mild reaction conditions, post-processing process is simple, the productive rate is high, and is favorable for industrial production. (by machine translation)
Oxidation-induced C-H amination leads to a new avenue to build C-N bonds
Yi, Hong,Tang, Zilu,Bian, Changliang,Chen, Hong,Qi, Xiaotian,Yue, Xiaoyu,Lan, Yu,Lee, Jyh-Fu,Lei, Aiwen
supporting information, p. 8984 - 8987 (2017/08/15)
In this work, we develop an oxidation-induced C-H functionalization strategy, which not only leads to a new avenue to build C-N bonds, but also leads to different site-selectivity compared with "classic directing-groups". The high selectivity of our new catalytic system originates from the heterogeneous electron-density distribution of the radical cation species which are induced by single electron transfer between the aromatics and oxidant-Cu(ii) species.
Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles
Das, Somnath,Natarajan, Palani,K?nig, Burkhard
supporting information, p. 18161 - 18165 (2017/12/28)
The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.