Selective introduction of fluorine into molecules by the cleavage of inert C-H bonds is of central academic and synthetic interest, yet remains challenging. Given the central role of alcohols in organic chemistry as the most ubiquitous building blocks, a versatile and selective C(sp )-H and C(sp )-H fluorination of simple alcohols, enabled by novel designed exo-directing groups, is described. C(sp )-H bond fluorination was achieved by using a simple acetone oxime as auxiliary, whereas a new, modular and easily accessible bidentate auxiliary was developed for the efficient and site-selective fluorination of various primary methyl, methylene, and benzylic C(sp )-H bonds. Fluorinated alcohols can readily be accessed by the removal of auxiliaries, and significantly expands the synthetic prospect of the present procedure.

A palladium catalyzed selective C(sp3)–H arylation and acetoxylation of alcohols using a practical bidentate auxiliary were developed.

Selective C­(sp3)–C­(sp2) bond construction is of central interest in chemical synthesis. Despite the success of classic cross-coupling reactions, the cross-dehydrogenative coupling between inert C­(sp3)–H and C­(sp2)–H bonds represents an attractive alternative toward new C­(sp3)–C­(sp2) bonds. Herein, we establish a selective inter- and intramolecular C­(sp3)–H arylation of alcohols with nondirected arenes that thereby provides a general pathway to access a wide range of β-arylated alcohols, including tetrahydronaphthalen-2-ols and benzopyran-3-ols, with high to excellent chemo- and regioselectivity.

Herein we report a novel Cu-catalyzed regioselective C2−H alkylation of benzimidazoles with aromatic alkenes. The reaction features exclusive regioselectivity and broad substrate scope in the intermolecular alkylation of benzimidazoles with terminal and internal aromatic alkenes, constituting a modular access toward benzimidazole-containing 1,1-di(hetero)aryl alkanes. The intramolecular C2−H alkylation of benzimidazoles with aromatic alkenes has been achieved in an endo-selective manner. The enantioselective C2 alkylation of benzimidazoles has also been realized with moderate to good stereocontrol.

A detailed mechanism study on the anion ligand promoted selective C–H bond fluorination is reported.

An efficient Pd-catalysed β-C(sp3)–H arylation of diverse native amides with aryl iodides was developed. This protocol overcomes the necessity of Thorpe−Ingold effect and features broad substrate scope and good functional...

A nitrate-promoted Pd-catalysed mild cross-dehydrogenative C(sp2)-H bond oxidation of oximes or azobenzenes with diverse carboxylic acids has been developed. In contrast to the previous catalytic systems, this protocol features mild...

The aromatic C–H bond etherification with alcohols is one of the most atom-efficient ways to construct aryl ethers. However, it often requires a large excess of alcohols as etherification reagents, which limits the substrate scope (especially for the valuable alcohols). Herein, an alternative mechanochemical C–H bond etherification of oximes with diverse primary and secondary alcohols was developed for the first time. Given the solvent-less condition of ball milling technique, the amount of alcohols used in this chemistry has been significantly reduced (1.5–3.0 equiv to the substrates), thus enabling the incorporation of a wide range of alcohols in the C–H bond etherification for the first time. The present mechanochemical protocol enhances the application prospect of the cross dehydrogenative C–H etherification strategy in the late-stage synthesis of complex aromatic ethers.