Construction of Indium(III)-Organic Framework Based on a Flexible Cyclotriphosphazene-Derived Hexacarboxylate as a Reusable Green Catalyst for the Synthesis of Bioactive Aza-Heterocycles.

The constant demand for eco-friendly methods of synthesizing complex organic compounds inspired researchers to design and develop modern, highly efficient heterogeneous catalytic systems. Herein, In-HCPCP metal-organic framework (SRMIST-1), a heterogeneous Lewis acid catalyst containing less toxic indium and eco-friendly robust cyclotriphosphazene and exhibiting notable chemical and thermal stability, durable catalytic activity, and exceptional reusability was produced through the reaction between indium(III) nitrate hydrate and hexakis(4-carboxylatophenoxy)-cyclotriphosphazene. In the SRMIST-1 structure, secondary building units {InO 7 } are assembled by a connection of η 2 - and η 1 -carboxylic oxo atoms from different HCPCP ligands, forming a three-dimensional network. The occurrence of regularly distributed In(III) sites in SRMIST-1 confers superior reactivity on the catalyst toward the synthesis of 2,3-dihydroquinazolin-4(1 H )-ones and 3,4-dihydro-2 H -1,2,4-benzothiadiazine-1,1-dioxides by the cyclization reaction of 2-aminobenzamides and 2-aminobenzenesulphonamides with aldehydes under optimized reaction conditions, respectively. The notable features of this method include broad functional group compatibility, low catalyst loading (1-5 mol %), mild reaction conditions, easy workup procedures, good to excellent reaction yields, ethanol as a green solvent, reusability of the catalyst (five cycles), and economic attractiveness, which is mainly due to sustainability of SRMIST-1 as a reusable green catalyst. Our findings demonstrate that the highly reactive and reusable green catalyst finds widespread applications in medicinal chemistry.