The development of silica‐supported molecular catalysts for tandem reactions is an important research direction of heterogeneous catalysis. Besides their significant merits in sustainable catalytic processes, numerous strategies have been utilized to construct silica‐supported molecular catalysts. Here, we emphasize tandem reactions and summarize the recent advances in sequential organic transformations. This paper is composed of four parts. The beginning part introduces silica as supports. The second part provides a large number of examples for the construction of non‐chiral molecular catalysts used for tandem reactions. The third part offers an outline for the construction of chiral molecular catalysts used for enantioselective tandem reactions. Finally, the perspectives for the further development of silica‐supported molecular catalysts for tandem reactions are addressed.

A chiral (mesitylene)RuCl(monosulfonated diamine) catalysed dynamic kinetic resolution (DKR)-asymmetric transfer hydrogenation (ATH) process is developed for highly enantio- (up to 99% ee) and diastereo- (up to 98 : 2 dr) selective reduction of challenging racemic α-aryl-γ-keto malononitriles. A spontaneous cyclization reaction of the hydrogenation products delivers a cascade process for efficient synthesis of useful enantioenriched 3,4-dihydro-2H-pyran-carbonitriles.

The rhodium-catalyzed enantioselective C–H iodination of 1-aryl isoquinolines under mild conditions is disclosed. Direct C–H iodination of 1-aryl isoquinolines with N-iodosuccinimide (NIS) catalyzed by chiral CpRh(III) complexes afforded a series of axially chiral biaryl iodides in excellent yields and enantioselectivity (up to 99% yield and 97% ee). Furthermore, the atroposelective C–H bromination and chlorination reactions were also compatible. Notably, the axially chiral biaryl iodides could be easily transformed to QUINAP-type and N,N-type chiral ligands.