A research team reports they have created an organic reaction called α -allylation with simple ketones and allyl alcohols. This work holds the potential for use in the development of next-generation catalysts.
The research is published in the journal ACS Catalys is on March 2, 2026.
Allylation is the organic chemistry reaction process that introduces an allyl group into a molecule. The resulting product’s molecular structure and properties are altered. Allylation reactions are useful in the synthesis of pharmaceuticals and agrochemicals. “This study aimed to enable the allylation of simple ketones using allyl alcohols as the allylating agent. Simple ketones and allyl alcohols represent the least reactive nucleophiles and allylating agents, respectively, and their direct coupling has long been considered challenging,” said Professor Ken Motokura, with the Faculty of Engineering at YOKOHAMA National University.
Researchers have conducted extensive studies on the allylation of active methylene compounds using allylating agents with reactive leaving groups, such as allyl halides, acetates, and carbonates. However, studies on allylation reactions using allylic alcohols and less reactive nucleophiles, are limited.
In earlier studies the team had demonstrated that introducing multiple catalytically active species with well-defined structures onto solid surfaces can accelerate organic reactions through cooperative effects. With this recent study, the team found that a multifunctional catalyst incorporating both palladium and copper complexes on mesoporous silica enabled the simultaneous activation of ketones and allyl alcohols. This process efficiently promoted the allylation reaction. Before this, only a few examples of this reaction have been reported because the low reactivity of allyl alcohols compared with other allylating agents. The team noted that the coexistence of organic functional groups, such as phenyl groups, on the mesoporous silica surface further amplified the catalytic activity.
Compared with a catalyst that had only immobilized palladium complexes, the team discovered that the overall catalytic activity of the proposed catalyst improved. “We found that co-immobilizing palladium and copper complexes together with organic functional groups within mesoporous silica markedly accelerated the reaction between simple ketones and allyl alcohols. Compared with a catalyst bearing only the palladium complex, the activity increased by up to a factor of 15.5,” said Motokura.
The team also discovered that this catalytic system could be applied to the allylation of various carbonyl compounds, and the catalyst is easily separated and reused. They conducted three recycling tests using indanone as the substrate. These recycling tests yielded a total palladium-based turnover number of 600.
The team used various spectroscopic analyses, isotope-labeling experiments, and density
functional theory calculations in their study. These indicated that the copper complex activates the ketone to facilitate the reaction. Their results also suggested that organic functional groups coexisting on the solid surface promote the reaction by optimizing the spatial arrangement of the palladium and copper complexes.
The team’s strategy of introducing multiple structurally well-defined catalytic species onto a solid surface represents a novel approach to enhance catalytic activity that is distinct
from earlier conventional methods such as active-site control and ligand design. “To the best of our knowledge, this study is the first to develop a heterogeneous catalyst for the allylation of simple ketones with allyl alcohols,” said Motokura. Looking ahead, the team suggests that combining palladium and/or copper complexes with a chiral ligand could enable highly efficient enantioselective allylation in the future.
This work demonstrates that assembling multiple active sites, such as metal complexes, on solid surfaces or within mesoporous channels can significantly promote difficult catalytic transformations. “Rather than relying on conventional catalyst development strategies such as metal selection or ligand design, we propose that accelerating reactions through the spatial accumulation of active sites can serve as a generalized design principle for next-generation catalysts,” says Motokura.
The research team includes Shunichi Sakai, Shingo Hasegawa, and Ken Motokura from the Department of Chemistry and Life Science, YOKOHAMA National University, Japan.
The research is funded by a Grant-in-Aid for Scientific Research and a Grant-in-Aid for Early-Career Scientists from the Japan Society for the Promotion of Science.
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ACS Catalysis
Experimental study
Not applicable
Heterogeneous Synergistic Acceleration of Ketone α-Allylation with Allyl Alcohol by Pd/Cu Complexes on Organomodified Mesoporous Silica
2-Mar-2026