A general and practical strategy for remote site-selective functionalization of unactivated aliphatic C-H bonds in various amides by radical chemistry is introduced. C-H bond functionalization is achieved by using the readily installed N-allylsulfonyl moiety as an N-radical precursor. The in situ generated N-radical engages in intramolecular 1,5-hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C-H functionalized amides. The generality of the approach is documented by the successful remote C-N , C-Cl, C-Br, C-SCF , C-SPh, and C-C bond formation. Unactivated tertiary and secondary C-H bonds, as well as activated primary C-H bonds, can be readily functionalized by this method.

Four new hybrid architectures containing a [CoMoHO] polyoxoanion, (en)[Cu(ptz)(HO)][CoMoHO]·24HO (1), (Hbim)[{Cu(bim)(HO)}{CoMoHO}]·5HO (2), H[Cu(dpdo)(HO)][{Cu(dpdo)(HO)(CHCN)}{CoMoHO}]·9HO (3), and (Hbpp)[{Cu(HO)}{NaCoMoHO}]·10HO (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [CoMoHO] as the guest. Compound 2 is constructed from [CoMoHO] polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [CoMoHO] polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [CoMoHO] polyoxoanions joined together by Na and Cu cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

Direct γ-lactone formation via visible-light photoredox catalysis has been achieved efficiently including hydroxylalkylation of aromatic alkenes and transesterification. The present photocatalytic protocol has good regioselectivity and substrate compatibility, affording a novel way to intermolecular γ-lactone synthesis by the reaction of styrenes with α-bromo esters in the absence of any external oxidants.