Cu In Oxides Research Articles

Direct synthesis of 3-arylquinolines by a nano Pd-catalyzed regioselective C3-H arylation of quinolines

3-Arylquinolines are biologically and medicinally very important compounds. Direct and regioselective C3-H arylation offers a straight forward methodology for their synthesis. In this work, we report their synthesis by a Pd nanoparticle catalyzed reaction with aryliodonium salts as the arylating agent in the presence of stoichiometric oxidant Cu(OAc)2. The reaction works with different quinolines and diaryliodonium salts with both electron donating and electron withdrawing groups. The advantage of the methodology is that it does not require any ligand and the catalyst also is recoverable and recyclable.

ChemInform Abstract: Ruthenium‐Catalyzed C—H Amidation and Alkenylation of Cyclic N‐Sulfonyl Ketimines.

A highly regioselective ruthenium-catalyzed C–H amidation of cyclic N-sulfonyl ketimines with organic sulfonyl azides is described. An alkenylation at the C–H bond of cyclic N-sulfonyl ketimines with various alkenes was also carried out. Only a catalytic amount of the oxidant Cu(OAc)2 was used in the reaction; the remainder of the required amount of oxidant was formed by regeneration of Cu(OAc)2 under an air atmosphere.

ChemInform Abstract: Peroxide‐Free Pd(II)‐Catalyzed ortho Aroylation and ortho Halogenation of Directing Arenes.

A Pd(II)-catalyzed peroxide-free ortho aroylation of directing arenes has been developed via cross dehydrogenative coupling (CDC) in the presence of the terminal oxidant Cu(OAc)2·H2O. Ortho aroylation of directing arenes proceeds via decarbonylation of the in situ generated phenyl glyoxal, which is obtained from 2-acetoxyacetophenone in the presence of the oxidant Cu(OAc)2·H2O. However, changing the oxidant to CuX2 (X = Cl, Br) provided exclusive di-ortho-halogenated 2-arylbenzothiazoles. During the halogenation, CuX2 served the dual role of a halogen source as well as a co-oxidant.

Ruthenium‐Catalyzed C–H Amidation and Alkenylation of Cyclic N‐Sulfonyl Ketimines

A highly regioselective ruthenium‐catalyzed C–H amidation of cyclic N‐sulfonyl ketimines with organic sulfonyl azides is described. An alkenylation at the C–H bond of cyclic N‐sulfonyl ketimines with various alkenes was also carried out. Only a catalytic amount of the oxidant Cu(OAc)2 was used in the reaction; the remainder of the required amount of oxidant was formed by regeneration of Cu(OAc)2 under an air atmosphere.

Peroxide-Free Pd(II)-Catalyzed Ortho Aroylation and Ortho Halogenation of Directing Arenes.

A Pd(II)-catalyzed peroxide-free ortho aroylation of directing arenes has been developed via cross dehydrogenative coupling (CDC) in the presence of the terminal oxidant Cu(OAc)2·H2O. Ortho aroylation of directing arenes proceeds via decarbonylation of the in situ generated phenyl glyoxal, which is obtained from 2-acetoxyacetophenone in the presence of the oxidant Cu(OAc)2·H2O. However, changing the oxidant to CuX2 (X = Cl, Br) provided exclusive di-ortho-halogenated 2-arylbenzothiazoles. During the halogenation, CuX2 served the dual role of a halogen source as well as a co-oxidant.

ChemInform Abstract: Direct Oxidative Coupling of Arenes with Olefins by Rh‐Catalyzed C—H Activation in Air: Observation of a Strong Cooperation of the Acid.

AbstractA series of monosubstituted or 1,2‐ or 1,3‐disubstituted arenes undergo the coupling with acrylates, styrene, allylbenzene or olefin (Xb) in the presence of air as terminal oxidant, Cu(OAc)2 as co‐oxidant, and CCl3COOH as highly efficient additive.

C—C Bond Formation via C—H Bond Activation: Catalytic Arylation and Alkenylation of Alkane Segments.

AbstractFor Abstract see ChemInform Abstract in Full Text.

C-C bond formation via C-H bond activation: catalytic arylation and alkenylation of alkane segments.

A new system for catalytic arylation and alkenylation of alkane segments has been developed. The ortho-tert-butylaniline substrates and 2-pivaloylpyridine may be arylated and alkenylated at the tert-butyl group, while no functionalization occurred at more reactive C-H and other bonds. Arylation and alkenylation of these substrates are achieved in the presence of Ph2Si(OH)Me and Ph-CH=CH-Si(OH)Me2, respectively, and the catalytic amount of Pd(OAc)2 and stoichiometric oxidant (Cu(OAc)2, 2 equiv) in DMF. In contrast, the ortho-i-propylaniline substrate underwent cyclopalladation, but no arylation product was obtained. Complex compound 14 was synthesized via tandem arylation-alkenylation of tert-butylaniline 11. We hypothesize that the high selectivity of this system stems from the confluence of directing effect of the Schiff base or pyridine moiety and unique reactivity properties of a phenyl-palladium acetate species (Ph-Pd-OAc.Ln).