Nickel-Catalyzed Direct C (sp³)–H Arylation of Aliphatic Amides with Thiophenes

Nickel-catalyzed heteroarylation of the inactive methyl C­(sp³)–H bond of aliphatic amide with heteroarenes is described. The method takes advantage of chelation assistance by an 8-aminoquinolinyl moiety. The synthetic reaction has good tolerance toward functional groups, and it can be used in the construction of various kinds of alkyl-substituted heteroarenes

Direct Aerobic Oxidative Esterification and Arylation of P(O)–OH Compounds with Alcohols and Diaryliodonium Triflates

Copper-catalyzed aerobic oxidative esterification of P­(O)–OH compounds is achieved using alcohols as efficient esterification reagents, giving the expected products with good to moderate yields. Furthermore, it is shown that the arylation of P­(O)–OH compounds proceeds efficiently to produce the corresponding products via the treatment of diaryliodonium triflates under mild reaction conditions. It is a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. The protocol is convenient for practical application. A plausible mechanism has been proposed for the reaction

Copper-Mediated Remote C–H Bond Chalcogenation of Quinolines on the C5 Position

An efficient and convenient method is developed for the remote C–H bond chalcogenation of 8-aminoquinoline scaffolds on the C5 position that is geometrically inaccessible. The protocol makes use of inexpensive CuBr₂ as mediator and shows good tolerance toward numerous disulfides/diselenides and aliphatic amides, giving the corresponding products in good to excellent yield

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

Nickel-catalyzed thiolation of the inactivated methyl C­(sp³)–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

Intramolecular, Site-Selective, Iodine-Mediated, Amination of Unactivated (<i>sp</i>³)C–H Bonds for the Synthesis of Indoline Derivatives

The Iodine-mediated oxidative intramolecular amination of anilines via cleavage of unactivated (<i>sp</i>³)­C–H and N–H bonds for the production of indolines is described. This transition-metal-free approach provides a straightforward strategy for producing (<i>sp</i>³)­C–N bonds for use in the preferential functionalization of unactivated (<i>sp</i>³)­C–H bonds over (<i>sp</i>²)­C–H bonds. The reaction could be performed on a gram scale for the synthesis of functionalized indolines

Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis–Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and 31P NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation

Intramolecular, Site-Selective, Iodine-Mediated, Amination of Unactivated (<i>sp</i>³)C–H Bonds for the Synthesis of Indoline Derivatives

The Iodine-mediated oxidative intramolecular amination of anilines via cleavage of unactivated (<i>sp</i>³)­C–H and N–H bonds for the production of indolines is described. This transition-metal-free approach provides a straightforward strategy for producing (<i>sp</i>³)­C–N bonds for use in the preferential functionalization of unactivated (<i>sp</i>³)­C–H bonds over (<i>sp</i>²)­C–H bonds. The reaction could be performed on a gram scale for the synthesis of functionalized indolines

Zn-Catalyzed Dehydroxylative Phosphorylation of Allylic Alcohols with P(III)-Nucleophiles

A novel and efficient protocol for the synthesis of diarylallyl-functionalized phosphonates, phosphinates, and phosphine oxides through the zinc-catalyzed dehydroxylative phosphorylation of allylic alcohols with P(III)-nucleophiles via a Michaelis–Arbuzov-type rearrangement is reported. A broad range of allylic alcohols and P(III)-nucleophiles (P(OR)3, ArP(OR)2, and Ar2P(OR)) are well tolerated in this reaction, and the expected dehydroxylative phosphorylation products could be synthesized with good to excellent yields under the optimal reaction conditions. The reaction can be easily scaled up at a gram-synthesis level. Furthermore, through the step-by-step control experiments, kinetic study experiments, and 31P NMR tracking experiments, we acquired insights into the reaction and proposed the possible mechanism for this transformation

Ni-Catalyzed Dimerization and Hydroperfluoroarylation of 1,3‑Dienes

A nickel-catalyzed three-component coupling reaction between perfluoroarenes and two molecules of a 1,3-diene in the presence of an alkyl Grignard reagent, which acted as a hydride source, provided 3-perfluoroarylated-1,7-octadienes via 1,3-diene dimerization and subsequent perfluoroarylation upon C–F bond cleavage. The reaction proceeded smoothly in a regioselective manner by simply combining NiCl₂ and PPh₃ as a catalyst and tolerated various functional groups on the perfluoroarenes. When substituted perfluoroarenes were employed, the reaction selectively occurred at the <i>para</i>-position. Mechanistic studies revealed that an anionic Ni complex, generated upon the reaction of Ni(0) with two molecules of a 1,3-diene and an alkyl Grignard reagent, played an important role in the C–C bond forming step with perfluoroarenes. The C–F bond cleavage was found to be a relatively fast step in the catalytic cycle