Ag–Cu copromoted direct C2–H bond thiolation of azoles with Bunte salts as sulfur sources

Abstract

A direct C2–H thiolation of azoles with Bunte salts was achieved under the combined action of copper and silver salts. This protocol could furnish various substituted 2-thioazoles in moderate to...

Ru‐catalyzed Formation of Thiosilanes and Selenosilanes using Dichalcogenides as a User‐Friendly Alternative to Thiols and Selenols

“…To our delight, a nucleophilic aromatic substitution proceeded under the above conditions to generate 2‐thiophenyl benzothiazole 9a (Scheme 5). Notably, arylbenzothiazoles (including thio‐derivatives) [42–46] have emerged in recent years as important pharmacophores and building blocks [47–49] …”

“…To our delight, a nucleophilic aromatic substitution proceeded under the above conditions to generate 2-thiophenyl benzothiazole 9a (Scheme 5). Notably, arylbenzothiazoles (including thio- ChemCatChem derivatives) [42][43][44][45][46] have emerged in recent years as important pharmacophores and building blocks. [47][48][49] In addition, we also synthesized 1,1,1,3,3-pentamethyl-3-(ptolylthio)disiloxane (3 f), and after evaporation of all volatiles, it was transferred to other tubes with 2-chlorobenzothiazole.…”

Transition metal catalysed direct sulfanylation of unreactive C–H bonds: an overview of the last two decades

“…In 2015, Alves and co-workers described a one-pot, two-step reaction sequence comprised of cyclocondensation and Cu (I)-catalysed direct sulfanylation for the synthesis of 4-(arylsulfanyl)-1H-pyrazoles (61) (Scheme 48). 42 In this study, the authors also developed the multicomponent version of this method; however, they observed higher yields for the onepot approach in which the arylhydrazines (58) and 1,3-diketones (59) were mixed in the first step for the in situ preparation of 1H-pyrazole derivatives (60). The second step Scheme 44 Cu(II)-catalysed direct sulfanylation of 8-amidoquinolines using thiols.…”

“…In 2021, Zhao and co-workers disclosed the Ag(I)-mediated direct sulfanylation of azoles (34) with Bunte salts (115) and Cu(II) as the additive (Scheme 86). 60 The authors noticed that the combination of Ag(I) and Cu(II) was required to afford moderate to good yields of the sulfenylated products (35). They recognized that coordination of the Nsp 2 lone pair of electrons from the azole (34) to Ag(I) could increase the activity of the Csp 2 -H bond at the C2 position towards transition metal activation.…”

DBU-Promoted Deaminative Thiolation of 1H-Benzo[d]imidazol-2-amines and Benzo[d]oxazol-2-amines

“…In previous reports, numerous synthetic strategies have been developed to access these two classes of N-heterocycles . The traditional approach for the construction of 2-thio-1 H -benzo­[ d ]­imidazoles and 2-thiobenzo­[ d ]­oxazoles relies on the reaction of 1 H -benzo­[ d ]­imidazole-2-thiols/benzo­[ d ]­oxazole-2-thiols with (bromomethyl)­benzenes through a nucleophilic substitution reaction process in the presence of bases at 60 °C (Scheme a) .…”