Biosourced Polymetallic Catalysts: An Efficient Means To Synthesize Underexploited Platform Molecules from Carbohydrates

Polymetallic hyperaccumulating plants growing on wastes from former mining activity were used as the starting material in the preparation of novel plant‐based Lewis acid catalysts. The preparation of biosourced Lewis acid catalysts is a new way to make use of mining wastes. These catalysts were characterized by X‐ray fluorescence, X‐ray diffraction, inductively coupled plasma mass spectrometry, and direct infusion electrospray ionization mass spectrometry. These analyses revealed a complex composition of metal species, present mainly as polymetallic chlorides. The catalysts proved to be efficient and recyclable in a solid‐state version of the Garcia Gonzalez reaction, which has been underexploited until now in efforts to use carbohydrates from biomass. This methodology was extended to various carbohydrates to obtain the corresponding polyhydroxyalkyl furans in 38–98 % yield. These plant‐based catalysts may be a better alternative to classical Lewis acid catalysts that were previously used for the Garcia Gonzalez reaction, such as ZnCl2, FeCl3, and CeCl3, which are often unrecyclable, require aqueous treatments, or rely on metals, the current known reserves of which will be consumed in the coming decades. Moreover, the plant‐based catalysts allowed novel control of the Garcia Gonzalez reaction, as two different products were obtained depending on the reaction conditions. Common‐or‐garden variety catalyst: Polymetallic hyperaccumulating plants are used in the preparation of Lewis acid plant‐based catalysts. The catalysts efficiently mediate the Garcia Gonzalez reaction to furnish platform molecules from carbohydrates. Efficiency, generality of application, ease of control of the reaction selectivity, use of solid‐state reactions, and the capacity to recover and reuse polymetallic catalysts are the key advantages of the presented approach.