A convenient and versatile oxidative intra/intermolecular oxyamination and diamination of unactivated alkenes has been developed through copper-catalyzed radical reactions of β,γ- and γ,δ-unsaturated ketoximes with electron-rich aryl and aliphatic amines. These reactions were carried out by employing di-tert-butyl peroxide (DTBP) or air as the terminal oxidant, and a series of useful nitrogen-containing 4,5-dihydroisoxazoles and cyclic nitrones were formed.

A 4-HO-TEMPO-catalyzed redox strategy for the synthesis of pyridines through the annulation of cyclopropanols and oxime acetates has been developed. This protocol features good functional group tolerance and high chemoselectivity and also promises to be efficient for the late-stage functionalization of skeletons of drugs and natural products. Mechanism studies indicate that the reaction involves the in situ generated α,β-unsaturated ketones and imines as the key intermediates, which are derived from cyclopropanols and oxime acetates via a TEMPO/TEMPOH redox cycle, respectively. The pyridine products are formed as a result of annulation of enones with imines followed by TEMPO-catalyzed oxidative aromatization by excess oxime acetates. This method not only realizes the TEMPO-catalyzed redox reaction but also broadens the frontiers for TEMPO in catalysis.

A facile, mild, and efficient dioxygen activation for the synthesis of isoxazoline/cyclic nitrone-featured α-ketols has been achieved by Cu-catalyzed trifunctionalization of internal unactivated alkynes of unsaturated ketoximes at room temperature. 18O isotope tracing and DFT calculation reveal that a cascade iminoxyl radical dichotomous 5-exo-dig cyclization/oxygen activation/peroxy radical 4-endo-trig cyclization process was involved in the reaction.

A decarboxylative borylation of aliphatic acids for the synthesis of a variety of alkylboronates has been developed by mixing m-chloroperoxybenzoic acid (mCPBA)activated fatty acids with bis(catecholato)diboron in N,Ndimethylformamide (DMF) at room temperature. A radical chain process is involved in the reaction which initiates from the B−B bond homolysis followed by the radical transfer from the boron atom to the carbon atom with subsequent decarboxylation and borylation.

An ovel radical 1,4/5-amino shift from the oxygen center of alkene-tethered diphenyl ketoxime ethers to the carbon center to achieve high value-added fluoroalkyl-containing primary b(g)-amino-ketones is reported. Mechanism studies reveal that the migration is triggered by the alkene addition of fluoroalkyl radical derived from the electron donor-acceptor (EDA) complex of Tognisr eagent II or fluoroalkyl iodides and quinuclidine,a nd involves au nique 5(6)-exo-trig cyclization of the carbon-centered radical onto the N-atom of ketoxime ethers followed by acascade sequence of NÀObond cleavage and dehydrogenation. Notably,besides Tognisreagent II and fluoroalkyl iodides,this protocol is also compatible with other radical precursors to provide various functionalizedprimary aminoketones.

This work represents the first [4+2] annulation of hydroxamic acids with olefins for the synthesis of benzo[c][1,2]oxazines scaffold via anode‐selective electrochemical oxidation. This protocol features mild conditions, is oxidant free, shows high regioselectivity and stereoselectivity, broad substrate scope of both alkenes and hydroxamic acids, and is compatible with terpenes, peptides, and steroids. Significantly, the dioxygenation of olefins employing hydroxamic acid is also successfully achieved by switching the anode material under the same reaction conditions. The study not only reveals a new reactivity of hydroxamic acids and its first application in electrosynthesis but also provides a successful example of anode material‐tuned product selectivity.

A novel distal radical rearrangement of alkoxyphosphine is developed for the first time and applied to the regioselective radical fluoroalkylphosphorylation of unactivated olefins. By employing a one‐pot two‐step reaction of (bis)homoallylic alcohols, organophosphine chlorides, and fluoroalkyl iodides under CFL (compact fluorescence light) irradiation, a series of fluoroalkylphosphorylated alkyl iodides and alcohols are easily synthesized by regiospecific installing a phosphonyl onto the inner carbon of terminal olefins and further iodination/hydroxylation. Mechanism studies reveal that the migration undergoes a distinctive radical cyclization/β‐scission on the lone electron pair of phosphorus, resulting in C−P bond formation and C−O bond cleavage.

A novel iminoxyl radical-promoted dichotomous regioselective 5-exo-trig cyclization onto vinylic halogen/1,2-halogen radical shift sequence is developed for the synthesis of halomethyl isoxazoles/cyclic nitrones using β-halo-β,γ- and γ-halo-γ,δ-unsaturated ketoximes as the substrates and PhI(OAc)/TEMPO as the oxidation system. DFT calculations reveal that a halogen-bridged three-membered ring transition state is involved in the 1,2-Cl-/Br-atom shift, while the 1,2-I atom migration can be taken into account with an elimination/readdition mechanism. The migration ability was indicated to be ranked in the following order: I > Br > Cl.