Zhiping Li

Vicinal oxygenated scaffolds are prevalent in natural products and pharmaceuticals, yet a general method for divergent access to vicinal oxygenated motifs is still a synthetic challenge. We report a visible-light photoredox esterification−peroxidation of alkenes with carboxylic acids and tert-butyl hydroperoxide. Independent conversion of the peroxy and ester groups gives diverse vicinal oxygenated skeletons. This protocol establishes a unified platform for the divergent construction of vicinal oxygenated scaffolds and concise synthesis of phenylpropanoid natural products.

Substitution dominates benzene chemistry because σ-adducts formed during bond construction usually rearomatize. We report a photocatalytic three-component reaction that retains the σ-adduct as a 1,4-dioxygenated cyclohexadiene. A highly reactive carbonyloxy radical adds to the arene, whereas a longer lived peroxyl radical intercepts the resulting cyclohexadienyl radical before rearomatization. A reactivity–polarity analysis rationalizes the distinct requirements for entry and capture, and time-resolved electron paramagnetic resonance detects cyclohexadienyl and tert-butylperoxyl radicals under related conditions. The reaction extends to substituted, fused, and electron-rich heteroarenes and provides benzene-derived intermediates that can be converted to hydroquinone, conduritols, and inositol isomers. These results establish kinetic differentiation of radical partners as a strategy for controlling the fate of arene σ-adducts.

We report a visible‐light‐induced three‐component peroxidation of alkenes with ethers and tert ‐butyl hydroperoxide (TBHP) using Rhodamine B as an organophotoredox catalyst. This environmentally friendly protocol provides efficient access to a variety of multisubstituted tert ‐butyl peroxides. The resulting tert ‐butylperoxy group can be selectively converted into carbonyl or hydroxyl groups under mild conditions, highlighting the synthetic utility of this peroxidation strategy.

A concise one-pot three-component protocol for the assembly of 1,3,4-oxadiazole-tethered 1,2,3-triazoles from readily available starting materials has been disclosed.

Organic peroxides constitute a privileged family of O-O-containing compounds that serve as indispensable reagents or synthetic intermediates in industrial processes, pharmaceutical manufacturing, and polymer sciences. Herein, we disclose a photocatalytic ring-opening transformation of arylcyclopropanes with carboxylic acids and tert-butyl hydroperoxide, which enables the facile construction of structurally diverse 1,3-peroxyesterification products. This protocol proceeds under exceptionally mild, metal-free conditions with exquisite site-selectivity and broad functional-group tolerance. Besides, late-stage functionalization of bioactive molecules and downstream transformations are also performed.

A palladium-catalyzed cascade coupling/retro-Claisen reaction of CF₃-substituted β-diketones with readily available gem-difluorocyclopropanes has been developed. This methodology allows for the expedient synthesis of γ-fluorinated γ,δ-unsaturated ketones in a one-pot procedure with a broad scope and good to excellent yields.

Oxygen-centered radicals are highly reactive intermediates that serve key roles in radical-mediated organic transformations.

We present a Pd-IPent-catalyzed ring-opening defluorinative annulation reaction of gem-difluorocyclopropanes with enamides, which provides a convenient and efficient strategy for the synthesis of multisubstituted N-H pyrrole derivatives. This transformation selectively cleaves the C₁-C₃ bond, two C-F bonds, and the C-N bond in a one-pot procedure. Additionally, this protocol allows for the modification of several bioactive molecules.

The palladium-catalyzed cross-coupling of (E)-2-fluoroallyl carbonates and allylboronates is reported.

A regioselective cascade C−C/C−F cleavage/annulation of gem‐F₂CPs with enaminones catalyzed by Pd/IPr^BIDEA is reported. The NHC ligand IPr^BIDEA plays a pivotal role in enhancing the reaction efficiency. With this protocol, a variety of fully substituted pyrroles were obtained in good to excellent yields. Furthermore, this approach facilitates the modification of some bioactive scaffolds.