Site‐Selective Remote Radical C−H Functionalization of Unactivated C−H Bonds in Amides Using Sulfone Reagents

Abstract

A general and practical strategy for remote site-selective functionalization of unactivated aliphatic C-H bonds in various amides by radical chemistry is introduced. C-H bond functionalization is achieved by using the readily installed N-allylsulfonyl moiety as an N-radical precursor. The in situ generated N-radical engages in intramolecular 1,5-hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C-H functionalized amides. The generality of the approach is documented by the successful remote C-N , C-Cl, C-Br, C-SCF , C-SPh, and C-C bond formation. Unactivated tertiary and secondary C-H bonds, as well as activated primary C-H bonds, can be readily functionalized by this method.

Generation and Reactivity of Amidyl Radicals: Manganese‐Mediated Atom‐Transfer Reaction

“…We first addressed remote C(sp 3 )−H chlorination of amine substrates, since alkyl chlorides are very important and versatile synthetic intermediates for organic synthesis . The groups of Studer, Leonori, and Yu have recently achieved elegant amidyl radical directed remote C(sp 3 )−H chlorinations by cleaving N−S, N−O, and N−Cl bonds with the help of LPO radical initiator and precious photoredox catalysts . Obviously, developing alternative methods that feature a cheap catalytic system and operate under mild conditions to realize site‐selective distal C(sp 3 )−H chlorination would be very fascinating.…”

Thiosulfonates as Emerging Reactants: Synthesis and Applications

“…Studer and co‐workers employed thiosulfonates ( 7 ) for the remote site‐selective functionalization of unactivated aliphatic C−H bonds in various amides 232 via radical chemistry (Scheme ) . The reaction is initiated by light‐induced dilauroylperoxide decarboxylation, which produces benzenesulfonyl radical ( 229 , PhSO 2 . )…”

Fabrication of a Flowerlike Ag Microsphere Film with Applications in Catalysis and as a SERS Substrate

“…[1] In particular, significant efforts have promoted the development of the shape-controlled synthesis of silver nanoparticles (NPs) in the past decades. [2][3][4][5][6][7] The synthesis of the Ag particles with different shapes and sizes is currently widely investigated because shape control shows a greater versatility for tuning the properties of Ag nanostructures. Hence, tremendous efforts have been made to search for a versatile method to precisely control the morphology of Ag NPs, because applications such as catalysis can be strongly affected by particle size and shape.…”

“…Hence, tremendous efforts have been made to search for a versatile method to precisely control the morphology of Ag NPs, because applications such as catalysis can be strongly affected by particle size and shape. [2,5,7,8] Recently, a class of sophisticated attractive Ag structures has been synthesized by electrochemical methods, chemical deposition, galvanic replacement, and so on. [8] For example, Nie and coworkers obtained flowerlike silver hierarchical microcrystals with high catalytic activity by reducing silver nitrate with L-ascorbic acid in nitric acid-mediated systems.…”