Porous Metal–Organic Framework Catalyzing the Three-Component Coupling of Sulfonyl Azide, Alkyne, and Amine

Abstract

The robustly porous metal-organic framework MOF-Cu2I2(BTTP4) (BTTP4 = benzene-1,3,5-triyl triisonicotinate) was shown to work as an efficiently heterogeneous catalyst for the three-component coupling of sulfonyl azides, alkynes, and amines, leading to the formation of N-sulfonyl amidines in good yields. MOF-Cu2I2(BTTP4) can be recycled by simple filtration and reused at least four times without any loss in yield. Studies of the ligand effects on the three-component coupling reactions showed that BTTP4 could enhance the rate, as well as the chemoselectivity, when aromatic alkynes were employed. The catalytic process has been thoroughly studied by means of single-crystal and powder X-ray diffraction, gas and solvent adsorption, in situ (1)H NMR and FT-IR spectroscopy, X-ray photoelectron spectra (XPS), and ICP analysis of Cu leaching.

Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts

“…One initial methodology developed for the formation of sulfonylamidines was based on the cleavage of the bond between the N-4 and C-benzene in thiadiazine ring-type molecules [9]. To date, only few examples of copper-based catalysts have been reported to enable access to such compounds [10][11][12][13]. Chang and co-workers were pioneers in this area [10][11][12].…”

Air‐Induced One‐Pot Synthesis of N‐Sulfonylformamidines from Sulfonyl Chlorides, NaN3, and Tertiary/Secondary Amines

“…However, Hinsberg reaction generally suffers from several drawbacks, such as narrow reaction scopes, unsatisfactory yields and unavailable starting materials (Scheme a). In recent years, Cu‐catalyzed three‐component coupling reactions of sulfonyl azides, alkynes, and secondary amines have been well explored and applied for the synthesis of N ‐sulfonylamidines . In this kind of reactions, some by‐products are easily formed, such as alkyne–alkyne coupling products and triazole, which significantly decrease the yield of N ‐sulfonylamidines.…”

Temperature-Controlled Assembly/Reassembly of Two Dicarboxylate-Based Three-Dimensional Co(II) Coordination Polymers with an Antiferromagnetic Metallic Layer and a Ferromagnetic Metallic Chain

“…Magnetically coupled interactions, ferromagnetic (FO), or antiferromagnetic (AF), depend on the types of spin carriers and a detailed understanding of the coupling pathway between them. The system and topology of magnetic interactions through space can be further adjusted if the starting metal centers, short bridging ligands, building blocks, co-ligands, templates, and related structures are carefully selected and accurately assembled into CPs [37,38,39].…”