Modulation of ketyl radical reactivity to mediate the selective synthesis of coupling and carbonyl compounds
The importance of selective synthesis of high-value-added chemicals from renewable resources is paramount but remains a crucial challenge in organic synthesis and chemical reformation.Herein,we report the selective photosynthesis of C-C coupling products and carbonyl compounds from biomass-derived alcohols.The key to ensuring high end-to-end selectivity is the modulation of the reactivity of ketyl radical(*RCHOH)intermediates by employing different metal co-catalysts(Au,Pt,Pd,Ru)supported on Cd0.6Zn0.4S solid solution(CZS)photocatalysts.In particular,the C-C coupling product,hydrobenzion,and fully oxidized benzaldehyde were obtained from benzyl alcohol with high selectivity(＞98％)over Au-CZS and Ru-CZS,respectively.Combined experimental and theo-retical analyses demonstrated that the affinity of*RCHOH for the surface of metals governs their subsequent transformations,in which weak and strong radical adsorption on Au and Ru results in C-C coupling products and carbonyl compounds,respectively.
Biomass valorizationPhotocatalysisKetyl radical reactivitySelectivity controlAdsorption energy
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