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.

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.

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.