iADOR yields diverse shape-selective solid Lewis acid catalysts

•New Sn-zeolite catalysts by iADOR method with either parallel or intersecting 12- and 8-ring pores.•Engineered Lewis acid centers with hydrolyzed Sn-O-Si bonds.•Switchable selectivity in citronellal transformation into citronellol or isopulegols. Lewis acid catalysts convert biomass compounds to green chemicals and fuels. Among these catalysts, stannosilicate zeolites display high thermal stability and reusability. However, only a few Sn-zeolites can be prepared using conventional synthesis methods, preventing us from developing shape-selective stannosilicate catalysts. Here, we propose a synthetic approach toward shape-selective Sn-zeolite catalysts, leveraging the Assembly, Disassembly, Organization, Reassembly (ADOR) strategy. By combining isomorphous Sn incorporation (i) into germanosilicate zeolites UOV, IWW, and IWR in the A step with structural modification in the DOR steps, we targeted new Sn-zeolite structures with either parallel or intersecting 12- and 8-ring pores predominantly containing Lewis acid centers with hydrolyzed Sn-O-Si bonds. The shape-selective performance of the designed Sn-zeolite catalysts was experimentally assessed and theoretically rationalized in transformations of citronellal into citronellol by Meerwein-Ponndorf-Verley reduction and into isopulegol isomers via intramolecular cyclization. Therefore, iADOR paves the way toward new zeolite catalysts with engineered Sn active sites for green chemistry. [Display omitted]