Copper(I) complexes bearing pyrrole-bridged S,N and N-donor ligands as catalysts for tandem hydroamination-alkynylation: effect of anions on product formation

• Published in: Dalton transactions : an international journal of inorganic chemistry 2024-08, Vol.53 (33), p.13996-14010
• Main Authors: Mondal, Munmun, Mani, Ganesan
• Format: Article
• Language: English
• Subjects: Alkynes; Amines; Anions; Catalysts; Chemical synthesis; Copper; Copper compounds; Copper converters; Crystallography; Halides; Ligands; Single crystals
• ISSN: 1477-9226; 1477-9234; 1477-9234
• DOI: 10.1039/d4dt01937g

In this study, the reaction between 2-(3,5-dimethylpyrazolylmethyl)-5-(dimethylaminomethyl)pyrrole and thiophenol under heating conditions afforded the new ligand 2-(3,5-dimethylpyrazolylmethyl)-5-(phenylthiomethyl)pyrrole 2. The reaction of 2 with -chloroperbenzoic acid provided sulfoxide 3 and sulfone 4 group-containing ligands. The reaction of 2 with copper(I) halides provided the binuclear complexes [Cu(μ-X){μ-C H N-2-(CH Me pz)-5-(CH SPh)-κ -S,N}] (X = Cl, Br and I, 5-7) in high yields. Conversely, the analogous reaction of 4 with copper(I) halides yielded two types of complexes, three coordinate bi- and mononuclear of the type [Cu(μ-Cl){C H N-2-(CH Me pz)-5-(CH SO Ph)-κ - }] 8 and [CuX{C H N-2-(CH Me pz)-5-(CH SO Ph)-κ - } ], X = Br, 9 and I, 10. When the reaction was carried out in the presence of KPF , the two-coordinate complex [Cu{C H N-2-(CH Me pz)-5-(CH SO Ph)-κ - } ]PF 11a was isolated, whereas its BF analogue 11b was synthesized by the reaction of 8 with AgBF . The structures of these complexes were determined using single-crystal X-ray crystallography. These copper complexes catalyzed the hydroamination-alkynylation reaction between several secondary amines and alkyl and aryl terminal alkynes. Using 1 mol% of complexes 5-10 as catalysts, both tri- and tetra-substituted propargylamines were isolated. Alternatively, phenylacetylene and different secondary amines afforded the corresponding trisubstituted propargylamines as the major products and alkyl terminal alkynes gave the tetrasubstituted products in excellent yields. In addition, the role of counter anions such as TfO , PF , BF , PO and Ph B on the product selectivity was studied. When fluorinated anions such as TfO , PF , and BF were present with the copper complexes, the hydroamination-hydrovinylation product 1-aminodiene 23 was observed, which was not formed with PO , Ph B or halide ions. Specifically, TfO and PF favored the formation of 23, while BF favored the tetrasubstituted product as the major product. This was further supported by the isolated copper(I) complexes containing PF and BF and by other specific reactions. The peaks for enamines and [LCu] species in the HRMS spectra of the reaction mixtures and the isolation of the morpholinium copper(I) salt support the proposed mechanism.