Copper-Catalyzed Oxidative Carbon–Carbon and/or Carbon–Heteroatom Bond Formation with O2 or Internal Oxidants

• DOI: 10.1021/acs.accounts.7b00611
• Publication Date: 2018-04-12T18:57:40Z
• Authors: Xiaodong Tang; Wanqing Wu; Wei Zeng; Huanfeng Jiang
• Keywords: Heteroatom; Hypervalent molecule; Carbon fibers; Organic Synthesis

ConspectusSelective oxidation, a fundamental organic transformation of critical importance, produces value-added products from simple molecules. This process is extensively used to incorporate heteroatoms into carbon-based molecules, where high-valent metal salts, hypervalent halogen reagents, and peroxides are widely as oxidants. Oxidation reactions extremely challenging because their selectivity hard control and/or they form significant quantities unwanted waste derived the stoichiometric Undoubtedly, utilization green oxidants such molecular oxygen (O2) or internal provides tunable oxidation abilities no environmentally hazardous byproducts. Thus, synthetic chemists have devoted increasing attention obtain valuable products.Since first industrial application noble metal-catalyzed i.e., Pd/Cu/O2-mediated Wacker precious undergone development in both laboratory industry. However, high cost considerable toxicity metals compel explore catalytic activities earth-abundant, first-row transition metals. Copper abundant, easy utilize, relatively insensitive water air. Controllable access Cu(0), Cu(I), Cu(II), Cu(III) states ensures that copper can be applied multifunctional catalyst. Copper-catalyzed transformations involve single-electron transfer (SET), two-electron processes (TEPs) even cooperation SET TEPs. More importantly, Cu/O2 systems, ligands, additives, solvents tune state Cu(I) Cu(III). As result, copper-catalyzed aerobic oxidative possible desirable.Progress these methods will enable breakthroughs natural product synthesis, materials science, bioorganic chemistry. Account describes our efforts over last several years develop C–C C-heteroatom bond formation with oxidant. We primarily focused on reaction substrates, including cross-couplings, cycloadditions, cyclizations, condensations. These provide convenient efficient strategies for constructing multiple bonds, C–C/C–O C–C/C–N C–N/C–S one pot. Various alkynes, furans, benzofurans, lactones, sulfones, thioethers, nitrogen-containing heterocyclic compounds were synthesized atom economy commercially available inexpensive starting materials. successfully construction drug molecules skeletons products. Additionally, designed experiments serendipitous observations given us mechanistic insights oxidation. Uncovering activity involving oxime esters has allowed extend scope those reactions. believe made more eco-friendly economical synthesis compounds.