Ruthenium-catalyzed C-H functionalization was successfully combined with palladium-catalyzed asymmetric allylic alkylation in one pot. The novel dual-metal-catalyzed reaction provides a variety of 3-allyl-3-aryl oxindoles from the corresponding α-diazoamides in up to 99% yield with up to 85% ee. The appropriate ligand choice is important to promote the sequential reaction, avoiding undesired metal interaction or ligand exchange.

Cyclic hypervalent iodine reagents are now frequently used in synthetic organic chemistry, either as oxidants or group-transfer reagents. Vinylbenziodoxol(on)es (VBXs) bearing alkene substituents have been less investigated than the corresponding trifluoromethyl or alkynyl reagents. Nevertheless, since 2016 the development of new synthetic methods to access VBXs has awakened the interest of the synthetic community, leading to new transformations highlighting their unique reactivity as electrophilic alkene synthons. In this review, an overview of the synthesis and applications of VBX reagents will be presented. The review is organized according to the two main classes of VBX reagents reported so far-simple alkyl/aryl-substituted VBXs and heteroatom (S, O, N, X)-substituted VBXs-as they differ significantly from the point of view of synthetic access.

We report the oxyalkynylation of thiiranes and thietanes using ethynylbenziodoxolone reagents (EBXs) to readily access functionalized building blocks bearing an alkynyl, a benzoate, and an iodide group. The reaction proceeds with high atom efficiency most likely through an alkynyl−episulfonium intermediate. The transformation is copper-catalyzed and compatible with a large array of thiiranes and thietanes.

The intramolecular [4+ +2] cycloaddition between arenes and allenes first reported by Himbert gives rapid access to rigid polycyclic scaffolds.H erein, we report ao ne-pot oxyalkynylation/cycloaddition reaction proceeding under mild conditions (23-90 8 8C) and providing complex polycyclic architectures with high efficiency,and atom and step economy. The bicyclo[2.2.2]octadiene products were obtained with aw ide variety of useful functional groups and were successfully applied as chiral ligands for metal catalysis.C omputational studies gave af irst rationalization of the low activation energy for the cycloaddition based on counter-intuitive favorable dispersive interactions in the transition state.

A copper­(I)-catalyzed vinylation of diazo compounds with vinylbenziodoxolone reagents (VBX) as partners is reported. The transformation tolerates diverse functionalities on both reagents delivering polyfunctionalized vinylated products. The strategy was successfully extended to a three-component/intermolecular version with alcohols. The obtained products contain synthetically versatile functional groups, such as an aryl iodide, an ester, and an allylic leaving group, enabling further modification.