Enable biomass-derived alcohols mediated alkylation and transfer hydrogenation

• Published in: Nature communications Vol. 15; no. 1; pp. 7012 - 15
• Main Authors: Liu, Xixi, Huang, Liang, Ma, Yuandie, She, Guoqiang, Zhou, Peng, Zhu, Liangfang, Zhang, Zehui
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 15.08.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 140/133; 140/146; 140/58; 147/143; 639/638/224/685; 639/638/77/884; 639/638/77/887; Alcohol; Alcohols; Aldehydes; Alkylation; Amides; Amines; Biomass; Carbonyl compounds; Carbonyls; Catalysts; Chemical bonds; Chemical synthesis; Dehydrogenation; Esters; Humanities and Social Sciences; Hydrogenation; Ketones; Lewis acid; multidisciplinary; Nitriles; Nitrogen; Reagents; Science; Science (multidisciplinary); Single atom catalysts; Zinc
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-51307-8

A single-atom catalyst with generally regarded inert Zn–N 4 motifs derived from ZIF-8 is unexpectedly efficient for the activation of alcohols, enabling alcohol-mediated alkylation and transfer hydrogenation. C-alkylation of nitriles, ketones, alcohols, N -heterocycles, amides, keto acids, and esters, and N -alkylation of amines and amides all go smoothly with the developed method. Taking the α-alkylation of nitriles with alcohols as an example, the α-alkylation starts from the (1) nitrogen-doped carbon support catalyzed dehydrogenation of alcohols into aldehydes, which further condensed with nitriles to give vinyl nitriles, followed by (2) transfer hydrogenation of C=C bonds in vinyl nitriles on Zn–N 4 sites. The experimental results and DFT calculations reveal that the Lewis acidic Zn-N 4 sites promote step (2) by activating the alcohols. This is the first example of highly efficient single-atom catalysts for various organic transformations with biomass-derived alcohols as the alkylating reagents and hydrogen donors. Using carbonyl compounds or alcohols as alkylating reagents for the synthesis of α-alkylated nitriles is appealing from a sustainability perspective. Here, a single-atom catalyst with Zn–N 4 motifs acting as Lewis acid sites effectively activates alcohols, thus promoting various alkylation and transfer hydrogenation reactions using biomass-derived alcohols as both the alkylating reagents and hydrogen donors.