4971-80-6Relevant academic research and scientific papers
Controlled Relay Process to Access N-Centered Radicals for Catalyst-free Amidation of Aldehydes under Visible Light
Chang, Sukbok,Jeon, Hyun Ji,Jung, Hoimin,Kim, Dongwook,Lee, Wongyu,Seo, Sangwon
supporting information, p. 495 - 508 (2021/01/28)
Nitrogen-centered radicals have attracted increasing attention as a versatile reactive intermediate for diverse C–N bond constructions. Despite the significant advances achieved in this realm, the controllable formation of such species under catalyst-free conditions remains highly challenging. Here, we report a new relay process involving the slow in situ generation of a photoactive N-chloro species via C–N bond formation, which subsequently enables mild and selective access to N-centered radicals under visible light conditions. The utility of this approach is demonstrated by the conversion of aldehydes to amides, employing N-chloro-N-sodio carbamates as a practical amidating source. This synthetic operation obviates the need for catalysts, external oxidants, and coupling reagents that are typically required in related processes, consequently allowing high functional group tolerance and excellent applicability for late-stage functionalization. Amides are an important class of structural motifs prevalently found in bioactive compounds and synthetic materials of great significance. Amidation of aldehydes has been established as an atom-efficient strategy for amide synthesis; however, current methods lack in applicability mainly due to the requirement of troublesome reagents. In this article, we describe an unconventional relay process to convert aldehydes to amides under catalyst-, oxidant-, and coupling-reagent-free conditions, which is enabled by the development of a new mechanistic platform that gives efficient and controllable access to N-centered radicals under visible light. A wide range of (hetero)aromatic and aliphatic aldehydes can be employed, including those derived from biologically relevant complex molecules. We anticipate that the accomplished methodological advances, combined with the unique mechanistic features, will lead to the widespread application of the present strategy in broad research fields. A catalyst-free approach for controlled access to N-centered radicals is described, which enables the conversion of aldehydes to amides via an unconventional relay process harnessing visible light. The key tactic relies on the use of photostable N-chloro-N-sodio-carbamate amidating reagent that leads to slow incorporations of a photoactive radical source via C–N formation and other involved intermediates thereafter. This methodology displays excellent applicability and sustainable chemistry credentials and, thus, holds a promise for finding broad applications.
NOVEL AMIDATION METHOD
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Paragraph 0104-0110; 0120-0121, (2021/09/21)
The present invention relates to a novel amidation process. To the present invention, an active N -center radical activated by light irradiation can be utilized to provide a selective amidation method. In addition, the present invention can provide an amide compound derived from an aldehyde having a functional group of various aspects, and is expected to be applicable to various technical fields.
Pd-Catalyzed Carbonylation of Acyl Azides
Chang, Wenxu,Fu, Bin,Huang, Baoliang,Jiao, Lei,Li, Zongyang,Wang, Peng,Xu, Shiyang,Yuan, Chenhui,Zhang, Zhenhua
, p. 9497 - 9508 (2019/08/26)
Pd-catalyzed reactions of azides with CO to access an isocynate intermediate have been developed extensively in recent years. However, the catalytic carbonylation of sensitive acyl azides has not been reported. Herein, we report a simple Pd-catalyzed carbonylation reaction of acyl azides with broad substrate scope, high efficiency, and simple operation under mild conditions, which provides facile access to acyl ureas. In addition, a mechanistic study was carried out by both experiment and DFT calculation. Control experiments and kinetic study revealed that the real active palladium species were Pd(0). The result of kinetic study suggested that palladium catalyst, azide, and CO were all involved in the turnover-limiting step except for amine. Further DFT study suggested that an unprecedented five-membered palladacycle intermediate was the key intermediate in the carbonylation reaction. ?
Metal-free synthesis of imido derivatives by direct oxidation of α-amido sulfones
Martinelli, Fabio,Palmieri, Alessandro,Petrini, Marino
experimental part, p. 5085 - 5089 (2010/10/21)
Oxidation of α-amidoaryl sulfones with m-chloroperoxybenzoic acid under mild conditions readily provides the corresponding imides in satisfactory yields. The overall processprobably involves formation of an N-acyliminium ion intermediate, which by attack
Reaction of C-alkylated heterocyclic ketene aminals with diethyl azodicarboxylate: Synthesis of polyfunctionalized quaternary carbon derivatives and their thermal fragmentation
Zhao, Mei-Xin,Wang, Zhe-Ming,Wang, Mei-Xiang,Yan, Chun-Hua,Huang, Zhi-Tang
, p. 7791 - 7796 (2007/10/03)
Five-membered ring C-alkylated heterocyclic ketene aminals react with diethyl azodicarboxylate to give the quaternary carbon-containing adducts in moderate to excellent yields while the six-membered analogs afford imidazo[1,5-a]pyrimidin-6-one derivatives
The contribution made by triphenylphosphane in the putative catalysis by ruthenium species in conjugate additions of β-dicarbonyl compounds
Lumbierres, Maria,Marchi, Caroline,Moreno-Manas, Marcial,Sebastian, Rosa M.,Vallribera, Adelina,Lago, Elena,Molins, Elies
, p. 2321 - 2328 (2007/10/03)
Triphenylphosphane catalyzes conjugate additions of β-di-carbonyl compounds to φ-acceptor olefins and dialkyl azodicarboxylates. Formation of quaternary centers at the nucleophiles has been achieved. The catalytic action of tris(triphenylphosphane)rutheni
Ozonolysis of 5-Bromo- and 5-Ethoxy-2-phenyloxazoles. The Products and the Reaction Mechanism
Kashima, Choji,Arao, Hideki
, p. 805 - 807 (2007/10/02)
The ozonolysis of 2-phenyloxazoles having the good leaving group as an anion at C-5 position gave mainly N-benzoylisocyanate (2) with the formation of carbon dioxide.
ADDITION OF PYRIDINE AND ISOQUINOLINE TO BENZOYLCARBONITRILE OXIDE
Caramella, P.,Bandiera, T.,Albini, F. Marinone,Gamba, A.,Corsaro, A.,Perrini, G.
, p. 4917 - 4926 (2007/10/02)
Addition of pyridine to benzoylcarbonitrile oxide affords a fragile zwitterionic adduct, which slowly reverts to the addends, leading ultimately to benzoyl isocyanate and products deriving from it.A moderately stable cycloadduct is obtained in the reaction with isoquinoline.
