Anti-Markovnikov primary alcohols via terminal epoxide hydrogenation by Y-doped Al2O3-supported CoNi nanoparticles

Abstract

The anti-Markovnikov hydrogenation of terminal epoxides represents a straightforward strategy for the synthesis of primary alcohols. However, the reductive ring-opening of epoxides typically follows Markovnikov's rule, with secondary alcohols as the major products; thus, the development of catalytic processes that favor primary alcohols as the main products remains a significant challenge. Herein, we report the design and fabrication of a heterogeneous catalyst consisting of yttrium (Y)-doped cobalt (Co) and nickel (Ni) bimetallic species supported on alumina (Al₂O₃), which enables the selective reductive opening of epoxides using molecular hydrogen (H₂) to generate primary alcohols. Benefiting from the tailored electronic properties and acid–base characteristics of the NiCo/Al₂O₃ catalyst induced by Y doping, as well as the synergistic effect of Ni–Co bimetallic species in facilitating the heterolytic cleavage of H₂, the resulting NiCo/Y-Al₂O₃ catalyst achieves a conversion of up to 99% and a primary alcohol selectivity of 96% under mild reaction conditions. Importantly, this catalyst maintains a conversion of 82% and a selectivity of 88% even at a substrate concentration of 40 wt%. Furthermore, it also exhibits excellent stability over five consecutive catalytic cycles without significant degradation in performance.