Catalytic asymmetric hydroamination of alkenes with Lewis basic amines is of great interest but remains a challenge in synthetic chemistry. Here, we developed a Co-catalyzed asymmetric hydroamination of arylalkenes directly using commercially accessible secondary amines. This process enables the efficient access to valuable α-chiral tertiary amines in good to excellent yields and enantioselectivities. Mechanistic studies suggest that the reaction includes a CoHmediated hydrogen atom transfer (MHAT) with arylalkenes, followed by a pivotal catalyst controlled S N 2-like pathway between in situ generated electrophilic cationic alkylcobalt(IV) species and free amines. This radicalpolar crossover strategy not only provides a straightforward and alternative approach for the synthesis of enantioenriched α-tertiary amines, but also underpins the substantial opportunities in developing asymmetric radical functionalization of alkenes with various free nucleophiles in oxidative MHAT catalysis.

An efficient and general intermolecular Cobalt(II)-catalyzed asymmetric alkylation of styrenes with (hetero)arenes including indoles, thiophene and electron rich arenes has been developed, providing straightforward access to enantioenriched alkyl(hetero)arenes with high enantioselectivity. Mechanistic studies suggest that the reaction underwent a CoH-mediated hydrogen atom transfer (HAT) with alkenes, followed by a pivotal catalyst-controlled S N 2-like pathway between in situ generated organocobalt(IV) species and aromatic nucleophiles. This is the first CoH-catalyzed asymmetric hydrofunctionalization using carbon nucleophiles, providing a new strategy for asymmetric Friedel-Crafts type alkylation.

Metal-hydride hydrogen atom transfer (MHAT) catalysis has emerged as a useful reaction platform for alkene hydrofunctionalization with high chemoselectivity and predictable branched selectivity. However, MHAT-mediated hydrofunctionalization involves carbon−carbon bond formation...

The catalytic synthesis of cyclic nitrones, an important type of functional molecules for both synthetic chemistry and related fields, remains underdeveloped. Herein we report the copper‐catalyzed Cope‐type hydroamination of oximes with pendant nonactivated olefins, which enables facile access to a series of five‐ and six‐membered cyclic nitrones under mild conditions. In this study, heterocycle‐tethered oximes were employed in the Cope‐type hydroamination reaction for the first time. High enantioselectivity was achieved for carbon‐tethered γ,δ‐vinyl oximes to afford enantioenriched five‐membered cyclic nitrones. The results of preliminary mechanistic studies indicate a mononuclear catalytic species and a unified catalytic pathway over a large temperature range.

A series of heteroleptic phthalocyaninato rare earth doubledecker complexes owning large two-photon absorption cross-sections were reported. The third-order nonlinear optical properties of these heteroleptic phthalocyaninato complexes were experimentally investigated by the Z-scan technique with application of femtosecond (800 nm) pulse lasers. Due to the highly delocalized π-electron system and intense π-π interactions between the phthalocyaninato macrocycles, all complexes were revealed to exhibit large two-photon absorption cross-sections with the value up to 1.83×10 5 GM, which are comparable to those efficient two-photon absorbing materials. The optical limiting behavior of these complexes in chloroform was also investigated by using femtosecond laser pulses. The excellent two-photon absorption properties and optical limiting performance indicate their good application potential in optoelectronic devices.