Non-Directed C-H Arylation of Anisole Derivatives via Pd/S,O-Ligand Catalysis.

Non-directed C-H arylation is one of the most efficient methods to synthesize biaryl compounds without the need of the prefuctionalization of starting materials, or the installment and removal of directing groups on the substrate. A direct C-H arylation of simple arenes as limiting reactants remains a challenge. Here we disclose a non-directed C-H arylation of anisole derivatives as limiting reagents with aryl iodides under mild reaction conditions. The arylated products are obtained in synthetically useful yields and the arylation of bioactive molecules is also demonstrated. Key to the success of this methodology is the use of a one-step synthesized S,O-ligand.

Selective Para-C-H Alkynylation of Aniline Derivatives by Pd/S,O-Ligand Catalysis.

Herein, we report a nondirected para-selective C-H alkynylation of aniline derivatives by a Pd/S,O-ligand-based catalyst. The reaction proceeds under mild conditions and is compatible with a variety of substituted anilines. The scalability and further derivatizations of the alkynylated products have been also demonstrated.

Ruthenium(II)-Catalyzed α-Fluoroalkenylation of Oxime Ethers with gem-Difluorostyrenes via C-H Activation and C-F Cleavage.

A novel route for ruthenium(II)-catalyzed α-fluoroalkenylation of oxime ethers with gem-difluorostyrenes via C-H activation and C-F cleavage has been developed for the first time. Notably, the alkenyl units of products exhibit exclusive Z-configuration. This reaction features a broad substrate scope and good functional group tolerance. A plausible reaction mechanism is confirmed by an available cycloruthenated intermediate. Besides, the O-methyl oximyl-directing group can be readily removed to access the α-fluoroalkenylated acetophenones.

Rhodium(III)-catalyzed C4-amidation of indole-oximes with dioxazolones via C-H activation.

A novel method for the Rh(iii)-catalyzed oxime-directed C-H amidation of indoles with dioxazolones has been developed. This strategy provides an exclusive site selectivity and the directing group can be easily removed. This transformation features a wide substrate scope, good functional group tolerance and excellent yields, and may serve as a significant tool to construct structurally diverse indole derivatives for the screening of potential pharmaceuticals in the future.

2-Amino-5,6-difluorophenyl-1H-pyrazole-Directed PdII Catalysis: Arylation of Unactivated ß-C(sp3)-H Bonds.

Palladium-catalyzed arylation of unactivated ß-C(sp3)-H bonds in carboxylic acid derivatives with aryl iodides is described for the first time using 2-amino-5,6-difluorophenyl-1H-pyrazole as an efficient and readily removable directing group. Two fluoro groups are installed at the 5- and 6-position of the anilino moiety in 2-aminophenyl-1H-pyrazole, clearly enhancing the directing ability of the auxiliary. In addition, the protocol employs Cu(OAc)2/Ag3PO4 (1.2/0.3) as additives, evidently reducing the stoichiometric amount of expensive silver salts. Furthermore, this process exhibits high ß-site selectivity, compatibility with diverse substrates containing α-hydrogen atoms, and excellent functional group tolerance.

Copper-mediated direct thiolation of aryl C-H bonds with disulfides.

An efficient copper-mediated ortho-C(sp2)-H thiolation of aromatic amides directed by a novel directing group [4-chloro-2-(1H-pyrazol-1-yl)phenyl]amine has been developed without the need of other additives or oxidants, allowing for an increased usefulness. With the high compatibility of sterically demanding substrates, this reaction is scalable and can tolerate a wide scope of functional groups to provide alkyl and aryl thioethers in good to excellent yields (up to 93%). Furthermore, the protocol has been successfully implemented for the selenylation as well.

C-H Borylation of Diphenylamines through Adamantane-1-carbonyl Auxiliary by BBr3.

A method for ortho-C-H borylation of diphenylamines using BBr3 as the boron source has been reported. The noncatalytic adamantane-1-carbonyl directed reaction exhibited site exclusivity and good functional group tolerance. Generally, the borylation occurred at the more electron-rich aromatic ring and the borylated products could be converted to various useful intermediates. Besides, the derived arylation and removal of auxiliary of the product could be achieved in a one-pot fashion.

Tandem C-C/C-N Formation via Palladium-Catalyzed C-H Activation/Styrenation and Sequential Annulation of O-Methylketoxime with Styrenes.

A novel route for tandem C-C/C-N formation via palladium-catalyzed C-H activation/styrenation and annulation of O-methylketoxime with styrenes to synthesize benzothienopyridines and benzofuropyridines has been developed. Furthermore, the intermolecular alkenylation of the ketoxime with acrylates produces 3-alkenyl O-methylketoximes in good to excellent yields. The method features mild reaction conditions and good functional group tolerance, providing a direct approach for the preparation of fused heterocycles.