Palladium/Copper‐Cocatalyzed Oxidative Amidobrominations of Alkenes

Abstract

In the presence of LiBr, a palladium/copper combination catalyzes dehydrogenative amidobrominations of acrylates with NH-sulfoximines, leading to N-vinylated products by dual NH/CH coupling, followed by oxidative enamide bromination. Mechanistically, the domino process is proposed to involve palladium(II) species as key intermediates. First synthetic applications of the products have been demonstrated.

Palladium/Copper‐Mediated Switchable Approaches towards (Chloro)ethenylphosphorylamides by Phosphorylamides and Alkenes

“…in the Pd‐catalysis. Similar aminobromination and amidobromination reactions have been achieved separately by Jiang and Bolm's group, giving the products that possessed brominated unsaturated C=C bonds under oxidative conditions (Scheme ). Meanwhile, it was noteworthy that aminochlorination and/or amindochlorination reactions were also severely sought for in the palladium‐catalysis, however, low efficiency was observed using LiCl as the chlorination reagent.…”

“…It was hypothesized that '“Cl + ” species which was generated Cl – /Cu 2+ /O 2 system played a key role in the chlorination step. Based on the results and the extensive literature explorations,[12b], it was proposed that the reaction proceed in the cross‐coupling and chlorination consequence: Pd‐olefin coordination (a Wacker‐type process) and successive electrophilic chlorination by Cl + , which was formed by the Cu 2+ /O 2 system from in situ generation of CuCl 2 or CuBr under the oxidative environment, played significant roles in the whole procedure (Scheme ).…”

Regio‐ and Stereoselective Chloro Sulfoximidations of Terminal Aryl Alkynes Enabled by Copper Catalysis and Visible Light

“…In both cases, 5 a served as representative starting material. Applying Suzuki‐type cross‐coupling conditions with phenyl boronic acid as reagent and a palladium(II)/Xphos combination led to arylated product 7 in 81% yield [17] . The formation of thioether 8 was achieved by treatment of 5 a with a mixture of thiophenol and sodium methoxide in methanol, which provided 8 in 85% yield.…”

Stereoselective Chlorination and Bromination of Enamides and Enamines via an Electrostatic Attraction Effect Using (1,1-Diacetoxyiodo)benzene and a Halide Source

“…11,31,37 The first method is limited to the production of furan skeletons, the next two produces a mixture of the two isomers and the palladium-catalyzed coupling reaction produces primary amine-substituted or sulfoximine-substituted olefins. This method is stereoselective, convenient and complementary to the known methods.…”