Sustainable Sulfonic Acid Functionalized Tubular Shape Mesoporous Silica as a Heterogeneous Catalyst for Selective Unsymmetrical Friedel–Crafts Alkylation in One Pot

Abstract

The development of general and more sustainable heterogeneous catalytic processes for Friedel–Crafts (FC) alkylation reactions is a key objective of interest for the synthesis of pharmaceuticals and commodity chemicals. Sustainable heterogeneous catalysis for the typical FC alkylation of an easily accessible carbonyl electrophile and arenes or with two different arene nucleophiles in one-pot is a prime challenge. Herein, we present a resolution to these issues through the design and utilization of a mesoporous silica catalyst that has been functionalized with sulfonic acid. For the synthesis of sulfonic acid-functionalized mesoporous silica (MSN-SO 3 H), thiol-functionalized mesoporous silica was first synthesized by the co-condensation method, followed by oxidation of the thiol functionality to the sulfonic acid group. Sulfonation of mesoporous silica was confirmed by 13 C CP MAS NMR spectroscopy. Further, the devised heterogeneous catalysis using MSN-SO 3 H has been successfully employed in the construction of diverse polyalkanes including various bioactive molecules, viz arundine, tatarinoid-C, and late-stage functionalization of natural products like menthol and Eugenol. Further, we have utilized this sustainable technique to facilitate the formation of unsymmetrical C–S bonds in a one-pot fashion. In addition, the catalyst was successfully recovered and recycled for eight cycles, demonstrating the high sustainability and cost-effectiveness of this protocol for both academic and industrial applications.

Functionalized graphene oxide by 4-amino-3-hydroxy-1-naphthalenesulfonic acid as a heterogeneous nanocatalyst for the one-pot synthesis of tetraketone and tetrahydrobenzo[b]pyran derivatives under green conditions

“…In this context, performing the reactions for the synthesis of pharmaceutical intermediates or final active pharmaceutical ingredients (APIs) in EtOH, as a green solvent, is one of the best strategies. 9,41,52,53…”

An organocatalytic domino annulation approach via C(sp2)–OMe cleavage to unlock the synthesis of pyranochromenones enabled by HFIP

“…Previously, our laboratory and other research groups 13 have begun to exploit the catalytically active aggregates formed between Brønsted acids and solvents such as hexafluoroisopropanol (HFIP) to enable challenging transformations. As part of our ongoing interest in C–C bond formation, 14–16 we recently reported HFIP/ p TSA-catalyzed FC alkylation to afford symmetrical and unsymmetrical products via cooperative catalysis. 13 Inspired by this discovery, we conceived the possible construction of fused pyranochromenones from feedstock precursors via one-pot, domino annulation.…”