Nickel-Catalyzed Direct Thiolation of C(sp³)–H Bonds in Aliphatic Amides

Abstract

Nickel-catalyzed thiolation of the inactivated methyl C(sp(3))-H bonds of aliphatic amides with disulfide is described. It is a novel strategy for the synthesis of thioethers with the ultimate goal of generating thioether carboxylic acids with various functional groups.

Theoretical study of FMO adjusted C-H cleavage and oxidative addition in nickel catalysed C-H arylation

“…2a), and the calculated free energy profile for the formation of active catalytic species 6 is shown in Fig. 3 Based on previous theoretical studies 33,[53][54][55] , oxidative addition is generally considered to occur after C-H bond cleavage in the majority of Ni(II)-catalysed C-H bond functionalization reactions. With this in mind, we initially calculated the free energy profile for pathway A as shown in Fig.…”

A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

“…Since 2015 several groups (Shi, 509 Zhang, 510 Shi 511 as well as Qiu, Xu and Yin 512 ) investigated the Ni-catalysed sulfenylation of aliphatic chains using generally disulfides or thiol derivatives ( Scheme 84A–D ). These protocols were complementary using either aromatic disulfides and even thiols ( Scheme 84A and B ) or both aromatic and aliphatic ones ( Scheme 84C and D ).…”

Photocatalytic/Cu‐Promoted C−H Activations: Visible‐light‐Induced ortho‐Selective Perfluoroalkylation of Benzamides

“…Cu‐,– Pd‐, Ni‐, Co‐,– and Fe‐catalyzed or ‐mediated chelation‐assisted C−H bond activations to construct C−C and C−X bonds (X=S, O, N, F) [Eq. (1)] with the aid of an 8‐aminoquinoline directing group have been developed by the groups of Daugulis, Hirano, and Miura,– Ge, Kuninobu and Kanai,, Stahl, Chatani,,– and others ––. Ours and other groups also independently developed the selective ortho ‐sulfonylation and nitration of benzamides bearing the 8‐aminoquinoline group .…”