One-Pot Cross-Coupling/C–H Functionalization Reactions: Quinoline as a Substrate and Ligand through N–Pd Interaction

Abstract

Herein, we report a one-pot process that marries mechanistically distinct, traditional cross-coupling reactions with C–H functionalization using the same precatalyst. The reactions proceed in yields of up to 95%, in air, and require no extraneous ligand. The reactions are thought to be facilitated by harnessing the substrate quinoline as an N-ligand, and evidence of the palladium–quinoline interaction is provided by 1H-15N HMBC NMR spectroscopy and X-ray crystallographic structures. Application of the methodology is demonstrated by the quick formation of fluorescent, π-extended frameworks.

Спектрально-люминесцентные свойства циклометаллированных комплексов Pd(II) на основе метилового эфира цинхофена

“…В ЯМР 1 Н спектре соединения 1 наблюдаются группы сигналов фенильных протонов (Н 2 ′ -H 6 ′ ) в области 7.45−8.24 ppm, протонов хинолинового кольца (Н 1 -Н 8 ) в области 7.64-8.51 ppm, а также протонов метильной группы (СН 3 ) при 3.97 ppm, что согласуется с литературными данными [19][20][21][22][23][24][25]. Маркерным принят сигнал протона Н 3 хинолинового цикла в орто-положении к метилкарбоксилатной группе, проявляющийся в виде синглета при 8.39 ppm.…”

Insights into the κ-P,N Coordination of 1,3,5-Triaza-7-phosphaadamantane and Derivatives: κ-P,N-Heterometallic Complexes and a 15N Nuclear Magnetic Resonance Survey

“…Nevertheless, this issue can be bypassed by the detection of 1 N via 1 H through long-range correlation experiments, today run by using routine and robust pulse sequences as heteronuclear multiple-bond correlation (HMBC) or heteronuclear multiple quantum correlation. It is well established that 1 H– 15 N HMBC is a very useful tool for the structural assignments in protein sequences and was also used for the characterization of natural products − and the structural resolution of isomers . Also, various studies were published, including 15 N-enriched coordination compounds such as bimetallic clusters, and in recent years, organometallic complexes were also characterized by this technique. − In this work, we used the 1 H– 15 N HMBC pulse sequence to investigate in solution some noncoordinated PTA derivatives (Figure ) as well as some previously published representative Ru half-sandwich complexes displaying κ P- and κ P,N coordination (Figure ). Additionally, the new monometallic ( 20–22 ) and polymetallic ( 13 and 14 ) complexes containing dmoPTA and/or PTA were synthesized and characterized by single-crystal X-ray diffraction, expanding the family of PTA-κ P,N -complexes, illuminating new aspects of the coordination behavior of the PTA and dmoPTA ligand in the solid state and solution.…”

Switchable, Reagent-Controlled C(sp3)-H Selective Iodination and Acetoxylation of 8-Methylquinolines

“…It is well known that quinoline is a versatile N-based heterocyclic system found in many natural products, agrochemicals, pharmaceuticals, functional materials, and ligands in transition-metal catalysis . Thus, the development of efficient synthetic methods for substituted quinolines is of significance.…”