What question did this study set out to answer?

To enhance the regioselectivity and substrate scope of Markovnikov selective hydroamination using novel catalytic conditions.

February 5, 2026

Markovnikov Selective Hydroamination of Aliphatic Alkenes with Anilines and Azoles through a Light-Driven Multiple Catalysis

Key Points

To enhance the regioselectivity and substrate scope of Markovnikov selective hydroamination using novel catalytic conditions.
Utilized blue LED irradiation to drive a triple catalysis system.
Employed cobalt, photoredox, and weak Brønsted acid catalysts.
Investigated the reaction mechanism involving alkyl cobalt(IV) species.
Developed a quadruple catalytic system with Lewis pair catalysts for azoles.
Achieved high regioselectivity in hydroamination of aliphatic alkenes.
Effectively suppressed Friedel-Crafts alkylation through SN2 reactivity of cobalt(IV) species.
Expanded the formation of N-alkylanilines and N,N-dialkylanilines significantly.
Facilitated N-alkylation of azoles using an optimized catalytic system.

Abstract

Abstract Conventional acid catalysis for Markovnikov selective hydroamination of alkenes using anilines suffered from limitations on substrate scope and low regioselectivity attributed to buffering effect of anilines and competing Friedel-Crafts alkylation, respectively. Herein we demonstrate Markovnikov hydroamination of aliphatic alkenes using anilines through light-driven triple catalysis consisting of cobalt, photoredox, and weak Brønsted acid catalysts under blue LED irradiation. Our protocol enables to generate an alkyl cobalt(IV) species from aliphatic alkenes under weak acidic conditions, expanding the accessible N-alkylanilines and N,N-dialkylanilines. Since the alkyl cobalt(IV) species reacts with anilines through SN2 manner unlike a free carbocation, Friedel-Crafts alkylation is completely suppressed. When Brønsted acid catalyst is replaced with Lewis base/acid pair catalysts, the quadruple catalytic system is amenable to N-alkylation of azoles.

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