General Synthesis of γ-Arylamino Alcohols via Difunctionalization of Terminal Alkenes Using a Supported Cobalt Single-Atom Catalyst.

Abstract

Despite the broad utility of γ-amino alcohols, their direct and diverse synthesis from cheap, abundant feedstocks remains challenging. Here, by developing a bifunctional single-atom cobalt catalyst supported on hierarchical ordered porous carbon matrix (Co-N4/HPC), it enables hydroxyaminomethylation of nonactivated terminal alkenes with nitroarenes and formaldehyde using HCOOH reductant. This difunctionalization reaction features operational simplicity, high atom/step economy, broad substrate scope, excellent functionality tolerance, high selectivity, and catalyst reusability, offering a practical platform for the general synthesis of γ-arylamino alcohols from bulk chemicals. Notably, the Co-N4 sites mediate mild reduction, while the mesoporous N-doped carbon support enriches formaldehyde via physical adsorption, facilitating the capture of hydroxylamines formed in situ from nitroarene reduction. Subsequent 1,3-dipolar cycloaddition of the resulting nitrones with alkenes, followed by reduction of the cycloadducts, delivers the desired products. The concept of exploiting metal-support synergy for mild reduction and efficient intermediate conversion will open a door to the further development of useful tandem reactions through rational catalyst design.