Development of Facile Heterogeneous Copper Catalytic Systems and Applications in Organic Reactions

다국어 초록 (Multilingual Abstract)

The development of efficient, sustainable, and broadly applicable catalytic platforms remains a central pursuit in contemporary synthetic organic chemistry. Among the available transition metals, copper offers a compelling balance of redox versatility, tunable coordination environments, and economic viability. In particular, copper catalysts modified with biocompatible ligands have attracted attention for improving activity, selectivity, and environmental sustainability. Nicotinamide (vitamin B3), a readily accessible and biologically relevant ligand, provides structural adaptability through its ability to coordinate via either the pyridine nitrogen or the amide oxygen. This dual-site coordination can modulate the electronic environment of copper (II), potentially enhancing catalytic performance. Despite these advantages, copper (II)–nicotinamide complexes have been far more extensively explored in medicinal and materials chemistry than in synthetic methodology. Only limited studies have demonstrated their utility in C–S and C–N bond formation or in cycloaddition reactions. To expand their synthetic relevance, a family of crystalline copper (II)–nicotinamide complexes (CuX@ViB3) was investigated as catalysts for C–C, C–N, and C–O bond-forming reactions, with particular emphasis on substrate scope, operational simplicity, and sustainability. The second research direction focuses on polydopamine (PDA), an adhesive, catechol- and amine-rich polymer formed through the self-polymerization of dopamine under alkaline conditions. PDA readily forms uniform, tunable coatings on a broad range of substrates, including metals and polymers. PDA-coated iron oxide nanoparticles (Fe₃O₄@PDA) have been widely studied for their magnetic responsiveness, biocompatibility, and chemical stability; however, their potential as catalytic materials in organic synthesis remains comparatively underexplored. Leveraging the metal-binding capabilities of PDA, a hybrid system composed of Fe₃O₄@PDA and copper salts was developed to catalyze the ipso-hydroxylation of arylboronic acids to phenols in aqueous media. Phenols serve as indispensable intermediates in pharmaceuticals, polymers, and natural products, yet conventional synthetic routes often rely on harsh conditions or stoichiometric oxidants. The Fe₃O₄@PDA–Cu system provides a recyclable, reusable, and efficient platform for the aerobic hydroxylation of arylboronic acids, offering a greener alternative to traditional methodologies. Collectively, these studies demonstrate the potential of copper–nicotinamide complexes, and PDA-coated Fe₃O₄ nanoparticles incorporating copper as promising, sustainable platforms for diverse carbon-carbon bond-forming reactions.

목차 (Table of Contents)

• Chapter 1. Versatility of Copper–Nicotinamide Complexes (CuX@ViB3): Scope and Limitations across Several Organic Transformations
• Ⅰ. Introduction 2
• Ⅱ. Experimental 4
• 1.2.1 Preparation of Copper (II)-nicotinamide complex (Cu@ViB3) 4
• 1.2.2 Typical synthetic route for coupling Grignard reagents with acid
• chlorides in the presence of CuX@ViB3 4
• 1.2.3 Typical Procedure for the aza-Michael addition 5
• 1.2.4 Typical Procedure for the Ipso-Hydroxylation 5
• Ⅲ. Results and Discussions 6
• 1.3.1 Characterization of CuX@ViB3 complexes 6
• 1.3.2 Applications in organic reactions 10
• 1.3.3 1H and 13C NMR data 26
• Ⅳ. Conclusions 33
• V. References 34
• Chapter 2. Polydopamine-modified magnetic nanoparticles (Fe3O4@PDA) for the copper catalyzed ipso-hydroxylation of arylboronic acids and subsequent O-benzylation in aqueous media
• Ⅰ. Introduction 42
• Ⅱ. Experimental 45
• 2.2.1 Preparation of PDA coated magnetite (Fe3O4@PDA) 45
• Ⅲ. Results and Discussions 46
• 2.3.1 Characterization of Fe3O4@PDA platform 46
• 2.3.2 ipso-hydroxylation of arylboronic acids using Fe3O4@PDA platform 50
• 2.3.3 1H and 13C NMR data 61
• Ⅳ. Conclusions 68
• V. References 69
• List of Figure 73
• List of Table 74
• 국문 초록 75