1805-90-9Relevant academic research and scientific papers
Synthesis of Biaryls by Decarboxylative Hiyama Coupling
Katayev, Dmitry,Exner, Benjamin,Goossen, Lukas J.
, p. 2028 - 2032 (2015)
A trimetallic palladium/copper/silver system has been developed that allows the decarboxylative Hiyama coupling of ortho-substituted aryl carboxylates with trialkoxyarylsilanes to give the corresponding biaryls. The cross-coupling is catalyzed by a Pd/N-heterocyclic carbene complex with silver carbonate aiding its reoxidation. Copper(II) fluoride acts as decarboxylation catalyst, stoichiometric oxidant, and fluoride source. The scope of the protocol is demonstrated by 22 examples, among them aryl halides suitable for further coupling, and the synthetic utility of the products is illustrated by their conversion into carbazoles and 1H-indazoles.
Modular and Selective Arylation of Aryl Germanes (C?GeEt3) over C?Bpin, C?SiR3 and Halogens Enabled by Light-Activated Gold Catalysis
Dahiya, Amit,Fricke, Christoph,Funes-Ardoiz, Ignacio,Gevondian, Avetik G.,Schoenebeck, Franziska,Sherborne, Grant J.
supporting information, p. 15543 - 15548 (2020/06/22)
Selective C (Formula presented.) –C (Formula presented.) couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe3, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings.
Palladium Catalyzed Arylation and Benzylation of Nitroarenes Using Aryl Sulfonates and Benzyl Acetates
Yi, Zubaoyi,Aschenaki, Yodit,Daley, Ryan,Davick, Stephen,Schnaith, Abigail,Wander, Rylee,Kalyani, Dipannita
, p. 6946 - 6957 (2017/07/13)
Pd-catalyzed arylation or benzylation of nitroazoles using aryl sulfonates or benzyl acetates is described. Electronically varied aryl tosylates and mesylates, as well as benzyl acetates, afford the arylated and benzylated products. Arylation of nitrobenz
Synthesis of nitrodienes, nitrostyrenes, and nitrobiaryls through palladium-catalyzed couplings of β-nitrovinyl and o-nitroaryl thioethers
Creech, Gardner S.,Kwon, Ohyun
, p. 2670 - 2674 (2013/07/11)
A highly efficient, base-free, mild protocol for the palladium-catalyzed, copper-activated desulfitative couplings of vinyl and aryl β- nitrothioethers generates a wide variety of conjugated nitroorganics. Orthogonality to traditional Suzuki-Miyaura coupling is demonstrated, as well as synthetic utility, through reductive Cadogan cyclization, for the formation of indoles, carbazoles, and pyrroles.
