A novel copper-catalyzed intermolecular trifluoromethylazidation of alkenes has been developed under mild reaction conditions. A variety of CF3 -containing organoazides were directly synthesized from a wide range of olefins, including activated and unactivated alkenes, and the resulting products can be easily transformed into the corresponding CF3 -containing amine derivatives.

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available alkenes with electrophiles and/or nucleophiles. Nickel complexes serve as effective catalysts owing to their tendency to undergo facile oxidative addition and slow β-hydride elimination, and their capability to access both two-electron and radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, and stereoselectivities by tethering one of the coupling partners to the alkene substrate. Three-component reactions, however, often incorporate directing groups to control the selectivity. Only a few examples of directing-group-free difunctionalizations of unactivated alkenes have been reported. Therefore, great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities.

A novel asymmetric 6-endo aminoacetoxylation of unactivated alkenes by palladium catalysis, which yields chiral β-acetoxylated piperidines with excellent chemo-, regio- and enantioselectivities under very mild reaction conditions, has been established herein by employing a new designed pyridine-oxazoline (Pyox) ligand. Importantly, introducing a sterically bulky group into the C-6 position of Pyox is crucial to enhance the reactivity of the aminoacetoxylation of alkenes.

A novel palladium-catalyzed intermolecular aminocarbonylation of alkenes has been developed in which the employment of hypervalent iodine reagent can accelerate the intermolecular aminopalladation, which thus provides the successful catalytic transformation. The current transformation presents one of the most convenient methods to generate β-amino acid derivatives from simple alkenes.

The first Pd‐catalyzed enantioselective azidation of unactivated alkenes has been established by using readily accessible 1‐azido‐1,2‐benziodoxol‐3(1H)‐one (ABX) as an azidating reagent, which affords a wide variety of structurally diverse 3‐N3‐substituted piperidines in good yields with excellent enantioselectivity. The reaction features good functional‐group compatibility and mild reaction conditions. Notably, both an electrophilic azidating reagent and the sterically bulky chiral pyridinyl‐oxazoline (Pyox) ligand are crucial to the successful reaction.

A catalytic intermolecular allylic C-H trifluoromethoxylation reaction of alkenes has been developed based on the use of a palladium catalyst, CsOCF as the trifluoromethoxide source, and benzoquinone as the oxidant. This reaction provides an efficient route for directly accessing allylic trifluoromethoxy derivatives with excellent regioselectivities from terminal alkenes via an allylic C-H bond activation process.

A novel palladium-catalyzed intermolecular oxidative fluorocarbonylation of alkenes has been developed, in which employment of a cooperative process with electrophilic ArIF -meidated alkenes activation and palladium-catalyzed carbonylation is crucial for the successful catalytic transformation. The current transformation presents the first convenient method to generate β-fluorinated carboxylic acid derivatives under mild reaction conditions from simple alkenes with excellent regioselectivity.

A novel method for intermolecular functionalization of terminal and internal alkenes has been designed. The electrophilic reagent, hypervalent iodine, plays a key role in this process by activating the alkene C=C bond for nucleophilic addition of the palladium catalyst. This process generates an iodonium-containing palladium species which undergoes CO insertion. The new approach, intermolecular oxycarbonylaton reactions of alkenes, has been achieved and carried out under mild reaction conditions to produce the corresponding β-oxycarbonylic acids with excellent efficiencies and levels of regio- and diastereoselectivity.