Interlayer expansion of layered zeolite precursors is achieved via the insertion of an additional T-atom in between the layers, typically by means of a silylating agent as source of the T-atom. (3-Mercaptopropyl)methyldimethoxysilane was used as Si-source in the interlayer expansion of the layered zeolite precursors RUB-36 and RUB-39. The structure expansion was confirmed with PXRD. The incorporation of the silylating agent was followed with Si-29 MAS NMR, C-13 CP MAS NMR and thermogravimetric analysis. The incorporated thiol groups were oxidized with H2O2 to obtain sulfonic acid groups in between the layers. C-13 CP MAS NMR was used to characterize the organic species and monitor the conversion of thiol to propylsulfonic groups. The shape-selective properties of the obtained materials were investigated in acid-catalyzed tetrahydropyranylation reactions. (C) 2014 Elsevier B.V. All rights reserved.