Iridium-Catalyzed Asymmetric Hydroarylation of Unactivated Alkenes with Heterobiaryls: Simultaneous Construction of Axial and Central Chirality.

There are only a few examples being reported for the simultaneous control of central chirality and axial chirality because it is more challenging. Herein, we report an iridium-catalyzed asymmetric hydroarylation of unactivated alkenes with heterobiaryls to simultaneously construct axial and central chirality. The reaction showed a broad substrate scope and delivered the products with satisfactory results. The results of the control experiments demonstrated that the FerroLANE ligand promotes the reaction to proceed along a specific modified Chalk-Harrod mechanism.

Iridium-Catalyzed 1,3-Rearrangement of Allylic Ethers.

The 1,3-rearrangement of allylic derivatives has rarely been reported, except for allylic alcohols. Herein, we describe an iridium-catalyzed 1,3-rearrangement of readily available allylic ethers to access the difficultly prepared allylic ethers with a large steric hindrance. The developed method shows a broad substrate scope and could be used in the late-stage modification of several natural products. In addition, a possible reaction pathway is also provided on the basis of the control experiments.

Iridium-Catalyzed Remote Site-Switchable Hydroarylation of Alkenes Controlled by Ligands.

An iridium-catalyzed remote site-switchable hydroarylation of alkenes was reported, delivering the products functionalized at the subterminal methylene and terminal methyl positions on an alkyl chain controlled by two different ligands, respectively, in good yields and with good to excellent site-selectivities. The catalytic system showed good functional group tolerance and a broad substrate scope, including unactivated and activated alkenes. More importantly, the regioconvergent transformations of mixtures of isomeric alkenes were also successfully realized. The results of the mechanistic studies demonstrate that the reaction undergoes a chain-walking process to give an [Ar-Ir-H] complex of terminal alkene. The subsequent processes proceed through the modified Chalk-Harrod-type mechanism via the migratory insertion of terminal alkene into the Ir-C bond followed by C-H reductive elimination to afford the hydrofunctionalization products site-selectively.