Nickel-Catalyzed Efficient and Practical Suzuki−Miyaura Coupling of Alkenyl and Aryl Carbamates with Aryl Boroxines

Abstract

Suzuki-Miyaura coupling of unactivated alkenyl carbamates is described to construct polysubstituted olefins. The developed process is also suitable for heteroaromatic and even electron-rich aromatic carbamates.

Palladium-catalysed cross-coupling reaction of ultra-stabilised 2-aryl-1,3-dihydro-1H-benzo[d]1,3,2-diazaborole compounds with aryl bromides: A direct protocol for the preparation of unsymmetrical biaryls

“…The sterically hindered ortho- substituted boronate 11 generally afforded lower yields when compared to other boronate derivatives (Table 2, entries 5 and 6). This was attributed to incomplete conversion of the starting materials possibly due to a steric effect around the boron atom which is consistent with the literature [6,18–19]. The cross-coupling of an electron-rich aromatic system (4-bromoanisole) was generally less efficient compared to bromobenzene (Table 2, entries 2 and 6).…”

State‐of‐the‐Art in Metal‐Catalyzed Cross‐Coupling Reactions of Organoboron Compounds with Organic Electrophiles

“…Thus, under these optimized conditions with NiCl 2 (PCy 3 ) 2 and PCy 3 HBF 4 as the catalyst system, the Snieckus group found that a wide range of biaryl products could be assembled through cross-coupling reactions. The importance of a trace amount of H 2 O was also observed by Shi and coworkers [71] shortly after these two reports (Eq. (17), Scheme 2.19).…”

Well-defined nickel and palladium precatalysts for cross-coupling

“…Along with traditional aryl halides, it can also couple heteroaryl halides 99 , as well as aryl mesylates 99 , carbamates 99–103 , carbonates 100 , sulfamates 99,101 , phosphates 104 , nitriles 105 , twisted amides 106 and pivalates 99,100,107 with boronic acids, boroxines or mixtures of both nucleophiles. In a particularly elegant demonstration of this chemistry, Garg and co-workers 100 synthesized the anti-inflammatory drug flurbiprofen by directed prefunctionalization of an aryl sulfamate before using the functionalized sulfamate as the electrophile in cross-coupling.…”