Palladium-Catalyzed C–H Activation/Cross-Coupling of Pyridine <i>N</i>‑Oxides with Nonactivated Secondary Alkyl Bromides

An unexpected C–H activation/C–C cross-coupling reaction has been found to occur between pyridine <i>N</i>-oxides and general nonactivated secondary and even tertiary alkyl bromides. It provides a practically useful approach for the synthesis of alkylated pyridine derivatives. Experimental observations indicated that the C–Br cleavage step involves a radical-type process. Thus, the title reaction provides a rather extraordinary example of Pd-catalyzed cross-coupling of secondary and tertiary aliphatic electrophiles

Palladium-Catalyzed C–H Activation/Cross-Coupling of Pyridine <i>N</i>‑Oxides with Nonactivated Secondary Alkyl Bromides

An unexpected C–H activation/C–C cross-coupling reaction has been found to occur between pyridine <i>N</i>-oxides and general nonactivated secondary and even tertiary alkyl bromides. It provides a practically useful approach for the synthesis of alkylated pyridine derivatives. Experimental observations indicated that the C–Br cleavage step involves a radical-type process. Thus, the title reaction provides a rather extraordinary example of Pd-catalyzed cross-coupling of secondary and tertiary aliphatic electrophiles

Portlandia indet.

An unexpected C–H activation/C–C cross-coupling reaction has been found to occur between pyridine <i>N</i>-oxides and general nonactivated secondary and even tertiary alkyl bromides. It provides a practically useful approach for the synthesis of alkylated pyridine derivatives. Experimental observations indicated that the C–Br cleavage step involves a radical-type process. Thus, the title reaction provides a rather extraordinary example of Pd-catalyzed cross-coupling of secondary and tertiary aliphatic electrophiles

Rh(III)-Catalyzed C–H Activation with Allenes To Synthesize Conjugated Olefins

Rh^III-catalyzed C–H activation with allenes produces highly unsaturated conjugated olefins. The reaction is applicable to both olefin and arene C­(sp²)–H and is compatible with a variety of functional groups. The products can be further transformed into other important skeletons through Diels–Alder reaction and intramolecular transesterification

Rhodium-Catalyzed Directed C–H Cyanation of Arenes with <i>N-</i>Cyano‑<i>N</i>‑phenyl‑<i>p</i>‑toluenesulfonamide

A Rh-catalyzed directed C–H cyanation reaction was developed for the first time as a practical method for the synthesis of aromatic nitriles. <i>N</i>-Cyano-<i>N</i>-phenyl-<i>p</i>-toluenesulfonamide, a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this C–H cyanation process, and the reaction tolerates a variety of synthetically important functional groups

Copper-Promoted Sandmeyer Trifluoromethylation Reaction

A copper-promoted trifluoromethylation reaction of aromatic amines is described. This transformation proceeds smoothly under mild conditions and exhibits good tolerance of many synthetically relevant functional groups. It provides an alternative approach for the synthesis of trifluoromethylated arenes and heteroarenes. It also constitutes a new example of the Sandmeyer reaction

Rhodium-Catalyzed Directed C–H Cyanation of Arenes with <i>N-</i>Cyano‑<i>N</i>‑phenyl‑<i>p</i>‑toluenesulfonamide

A Rh-catalyzed directed C–H cyanation reaction was developed for the first time as a practical method for the synthesis of aromatic nitriles. <i>N</i>-Cyano-<i>N</i>-phenyl-<i>p</i>-toluenesulfonamide, a user-friendly cyanation reagent, was used in the transformation. Many different directing groups can be used in this C–H cyanation process, and the reaction tolerates a variety of synthetically important functional groups

Copper-Promoted Sandmeyer Trifluoromethylation Reaction

A copper-promoted trifluoromethylation reaction of aromatic amines is described. This transformation proceeds smoothly under mild conditions and exhibits good tolerance of many synthetically relevant functional groups. It provides an alternative approach for the synthesis of trifluoromethylated arenes and heteroarenes. It also constitutes a new example of the Sandmeyer reaction

Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C–N Bond Formation from Nonactivated Aliphatic Carboxylic Acids

Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C–N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C–N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon–heteroatom cross-coupling