LAUSR

Copper-mediated carbon–heteroatom bond-forming reactions involving a wide range of substrates have been in the spotlight for many organic chemists. This review highlights developments between 2010 and 2019 in both stoichiometric and catalytic copper-mediated reactions, and also examples of nickel-mediated reactions, under modified Chan–Lam cross-coupling conditions using various nucleophiles; examples include chemo- and regioselective N-arylations or O-arylations. The utilization of various nucleophiles as coupling partners together with reaction optimization (including the choice of copper source, ligands, base, and other additives), limitations, scope, and mechanisms are examined; these have benefitted the development of efficient and milder methods. The synthesis of medicinally valuable or pharmaceutically important nitrogen heterocycles, including isotope-labeled compounds, is also included. Chan–Lam coupling reaction can now form twelve different C–element bonds, making it one of the most diverse and mild reactions known in organic chemistry. 1 Introduction 2 Construction of C–N and C–O Bonds 2.1 C–N Bond Formation 2.1.1 Original Discovery via Stoichiometric Copper-Mediated C–N Bond Formation 2.1.2 Copper-Catalyzed C–N Bond Formation 2.1.3 Coupling with Azides, Sulfoximines, and Sulfonediimines as Nitrogen­ Nucleophiles 2.1.4 Coupling with N,N-Dialkylhydroxylamines 2.1.5 Enolate Coupling with sp3-Carbon Nucleophiles 2.1.6 Nickel-Catalyzed Chan–Lam Coupling 2.1.7 Coupling with Amino Acids 2.1.8 Coupling with Alkylboron Reagents 2.1.9 Coupling with Electron-Deficient Heteroarylamines 2.1.10 Selective C–N Bond Formation for the Synthesis of Heterocycle-Containing Compounds 2.1.11 Using Sulfonato-imino Copper(II) Complexes 2.2 C–O Bond Formation 2.2.1 Coupling with (Hetero)arylboron Reagents 2.2.2 Coupling with Alkyl- and Alkenylboron Reagents 3 C–Element (Element = S, P, C, F, Cl, Br, I, Se, Te, At) Bond Forma tion under Modified Chan–Lam Conditions 4 Conclusions