With the aid of a novel S-methyl-S-2-pyridyl-sulfoximine (MPyS) directing group (DG), the unactivated primary β-C(sp(3))-H bond of MPyS-N-amides oxidizes at room temperature. The catalytic conditions are applicable to the diacetoxylation of primary β,β'-C(sp(3))-H bonds, and the carboxylic acid solvent is pivotal in the formation of the C-O bond. The MPyS-DG cleaves from the oxidation products and is recovered. This method provides convenient access to α,α'-disubstituted-β-hydroxycarboxylic acids.

Sulfoximines direct: a new protocol for the chemo- and regioselective ortho C-H acetoxylation of arenes in N-benzoylated sulfoximines is reported. The sulfoximine directing group is easily detached from the C-H oxidation product through acid-promoted hydrolysis, isolated, and reused. The meta-substituted phenols are synthesized following this strategy and the stereointegrity of the sulfoximine is preserved in this transformation. C(sp(3))-H acetoxylation of the methyl group is also demonstrated.

A methyl phenyl sulfoximine (MPS) is used as a directing group in the ruthenium-catalyzed intramolecular hydroarylation of alkene-tethered benzoic acid derivatives to afford dihydrobenzofurans and indolines in good to excellent yields. A one-pot, unsymmetrical, twofold C-H functionalization involving intramolecular C-C and intermolecular C-C/C-N bond formations is successfully demonstrated by using a single set of catalytic reaction conditions, which is unprecedented thus far. A novel isoquinolone-bearing dihydrobenzofuran is constructed through an unsymmetrical twofold C-H functionalization.

S-methyl-S-2-pyridyl-sulfoximine (MPyS) directed bromination and chlorination of the 1°-β-C(sp(3))-H bond of MPyS-N-amides is realized under the influence of N-Br/Cl-phthalimides and a Pd(II)-catalyst. The sequential halogenation and acetoxylation of α-dimethyl MPyS-N-amides constructs highly functionalized α-trisubstituted aliphatic acid derivatives. The MPyS directing group is cleaved from the halogenated products and recovered.

The Ru(II)-catalyzed intermolecular o-C-H amidation of arenes in N-benzoylated sulfoximine with sulfonyl azides is demonstrated. The reaction proceeds with broad substrate scope and tolerates various functional groups. Base hydrolysis of the amidation product provides the anthranilic acid derivatives and methylphenyl sulfoximine (MPS) directing group. This method is successfully employed for the synthesis of HMR 1766.

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An operationally simple electrochemical method for the transition-metal-free ipso-thiocyanation of arylboronic acids and aryl trifluoroborates has been developed. The SCN electrophile is generated in situ by anodic oxidation of thiocyanate anions, which avoids formation of salt waste and prevents unwanted side reactions arising from chemical oxidants. The reaction proceeds regiospecifically, and the scope extends to non-activated aromatic systems. Scheme 1. Aryl thiocyanates as key building blocks. Scheme 2. Overview on syntheses of aryl thiocyanates. Scheme 3. Proposed mechanism for the electrochemical thiocyanation. COMMUNICATIONS asc.wiley-vch.de Scheme 4. Transformations of thiocyanate 3 b. a) TMSCF

The direct imidation strategy proficiently constructs C-N bonds and creates the useful amine functional group in the molecular template. This review briefly discusses the synthetic methods developed for the direct imidation of unactivated C(sp/sp/sp)-H bonds. Transition-metal catalysts, metal-free processes, and/or photo-induced methods are invariably employed for accomplishing C-H imidation transformations. The contents summarized herein would benefit the research community to use the C-H imidation reactions for broad synthetic applications and to unravel novel C-N bond forming processes.