Facile synthesis of a new covalent organic nanosheet (CON-KEY1) based on polyamide links as an effective heterogeneous catalyst in C-C cross coupling reactions

Hassan Keypour; Jamal Kouhdareh; Rahman Karimi-Nami; Idris Karakaya; Molood Abdollahi-Moghadam; Khadijeh Rabiei; Sedigheh Alavinia

doi:10.1039/d3ra05664c

Facile synthesis of a new covalent organic nanosheet (CON-KEY1) based on polyamide links as an effective heterogeneous catalyst in C-C cross coupling reactions

RSC Adv. 2023 Oct 2;13(41):28686-28702. doi: 10.1039/d3ra05664c. eCollection 2023 Sep 26.

Authors

Hassan Keypour¹, Jamal Kouhdareh¹, Rahman Karimi-Nami², Idris Karakaya³, Molood Abdollahi-Moghadam¹, Khadijeh Rabiei⁴, Sedigheh Alavinia¹

Affiliations

¹ Faculty of Chemistry, Bu-Ali Sina University Hamedan 65174 Iran haskey1@yahoo.com.
² Department of Chemistry, Faculty of Science, University of Maragheh Maragheh Iran.
³ Department of Chemistry, College of Basic Sciences, Gebze Technical University 41400 Gebze Turkey.
⁴ Department of Chemistry, Faculty of Science, Qom University of Technology Qom Iran.

Abstract

C-C coupling reactions represent a fundamental synthetic methodology widely employed in academic and industrial settings. Herein, we present a report on developing and synthesizing a heterogeneous catalyst that is environmentally compatible and has recycling capabilities. Furthermore, the utilization of this catalyst for C-C coupling reactions was explored. A novel amide-based CON was prepared via the reaction of a novel [2,2'-bipyridine]-5,5'-diamine (BDA) and 1,3,5-tris(4-carboxyphenyl) (TCB). TCB was activated with carbonyl diimidazole (CDI) and then reacted with BDA to synthesize favorable CON (i.e., CON-KEY1). Finally, the CON synthesized was reacted with palladium chloride ions, and the palladium-containing organocatalytic complex was decorated with the abbreviated Pd/CON-KEY1. This new heterogeneous complex was fully characterized through the required techniques, including FT-IR, EDX, XRD, TEM, SEM, ICP, TGA-DTA, N₂ isotherms, and elemental mapping analysis. Computer simulation results include a multi-sheet 2D framework proposed by CON-KEY1. As a result, palladium ions were found to be arranged between the layers and on the CON surface. This heterogeneous complex functioned as a catalyst precursor in both the Suzuki-Miyaura coupling reaction of aryl boronic acids with aryl halides and the Heck reaction of aryl halides with acrylate derivatives or styrene. The desired coupling products with various functional groups were successfully attained with excellent yields of up to 98%. Simple set-up, improved yields, short reaction times, non-toxic solvents, catalyst durability, and high turnover frequency are among the distinct advantages of this synthetic method. Some other outstanding features of this catalytic system include convenient separation of catalysts and products, high yields, almost complete conversion, high selectivity, and good turnover frequency (TOF). The results show that the highest product efficiency in the reaction was achieved in the shortest possible time using Pd/CON-KEY1. Theoretical studies demonstrated the precedence of the palladium complexation with nitrogen atoms of CON-KEY1 rather than oxygen ones. Natural Bond Orbital (NBO) analysis affirmed that the system with Pd-N bonds (E_g = 0.089 eV) is more reactive with high electron conductivity compared to the Pd-O system (E_g = 0.120 eV).