Isolable and Well-Defined Butadienyl Organocopper(I) Aggregates: Facile Synthesis, Structural Characterization, and Reaction Chemistry

Four types of alkenyl organocopper­(I) aggregates linked by 1,3-butadienyl and/or 1,3,5,7-octatetraenyl moieties were selectively realized in good isolated yields. All these organocopper­(I) aggregates were structurally characterized by single-crystal X-ray structural analysis. These unprecedented aggregates, stabilized by multiple Cu–Cu interactions and the conjugated 1,3-butadienyl or 1,3,5,7-octatetraenyl bridges, could undergo controlled structural transformations. The 1,4-dicopper 1,3-butadienyl aggregate <b>3</b> could be efficiently transformed to aggregate <b>2</b>, while LiI could disaggregate the 1,3-butadienyl-1,3,5,7-octatetraenyl aggregate <b>4</b> to 1,3,5,7-octatetraenyl aggregate <b>5</b> and 1,3-butadienyl aggregate <b>2</b>. Preliminary reaction chemistry and synthetic applications of these organocopper­(I) aggregates were also investigated

Cyclopentadiene–Phosphine/Palladium-Catalyzed Cleavage of C–N Bonds in Secondary Amines: Synthesis of Pyrrole and Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides

An efficient Pd-catalyzed cleavage of C­(sp³)–N bonds in secondary amines and a consequent C­(sp²)–N and C­(sp³)–N coupling process was developed. Various secondary amines could be used to react with alkenyl or aryl dibromides, affording pyrroles and indoles in high yields. Cyclopentadiene–phosphine ligands, a new type of P–olefin ligand, were found to be able to promote the efficiency of this Pd-catalyzed process remarkably. A reactive Pd complex coordinated with a cyclopentadiene–phosphine ligand was successfully isolated and structurally characterized

Isolable and Well-Defined Butadienyl Organocopper(I) Aggregates: Facile Synthesis, Structural Characterization, and Reaction Chemistry

Four types of alkenyl organocopper­(I) aggregates linked by 1,3-butadienyl and/or 1,3,5,7-octatetraenyl moieties were selectively realized in good isolated yields. All these organocopper­(I) aggregates were structurally characterized by single-crystal X-ray structural analysis. These unprecedented aggregates, stabilized by multiple Cu–Cu interactions and the conjugated 1,3-butadienyl or 1,3,5,7-octatetraenyl bridges, could undergo controlled structural transformations. The 1,4-dicopper 1,3-butadienyl aggregate <b>3</b> could be efficiently transformed to aggregate <b>2</b>, while LiI could disaggregate the 1,3-butadienyl-1,3,5,7-octatetraenyl aggregate <b>4</b> to 1,3,5,7-octatetraenyl aggregate <b>5</b> and 1,3-butadienyl aggregate <b>2</b>. Preliminary reaction chemistry and synthetic applications of these organocopper­(I) aggregates were also investigated

Cyclopentadiene–Phosphine/Palladium-Catalyzed Cleavage of C–N Bonds in Secondary Amines: Synthesis of Pyrrole and Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides

An efficient Pd-catalyzed cleavage of C­(sp³)–N bonds in secondary amines and a consequent C­(sp²)–N and C­(sp³)–N coupling process was developed. Various secondary amines could be used to react with alkenyl or aryl dibromides, affording pyrroles and indoles in high yields. Cyclopentadiene–phosphine ligands, a new type of P–olefin ligand, were found to be able to promote the efficiency of this Pd-catalyzed process remarkably. A reactive Pd complex coordinated with a cyclopentadiene–phosphine ligand was successfully isolated and structurally characterized

Cyclopentadiene–Phosphine/Palladium-Catalyzed Cleavage of C–N Bonds in Secondary Amines: Synthesis of Pyrrole and Indole Derivatives from Secondary Amines and Alkenyl or Aryl Dibromides

An efficient Pd-catalyzed cleavage of C­(sp³)–N bonds in secondary amines and a consequent C­(sp²)–N and C­(sp³)–N coupling process was developed. Various secondary amines could be used to react with alkenyl or aryl dibromides, affording pyrroles and indoles in high yields. Cyclopentadiene–phosphine ligands, a new type of P–olefin ligand, were found to be able to promote the efficiency of this Pd-catalyzed process remarkably. A reactive Pd complex coordinated with a cyclopentadiene–phosphine ligand was successfully isolated and structurally characterized

Well-Defined Butadienyl Organocopper(I) Aggregates from Zirconacyclopentadienes and CuCl: Synthesis and Structural Characterization

Two examples of mixed alkenyl/aryl organocopper­(I) aggregates possessing conjugated alkenyl/aryl C–Cu bonds were synthesized by transmetalation of zirconaindenes with CuCl. Single-crystal X-ray structural analysis revealed tetrameric and hexameric structures. Butadienyl copper­(I) aggregates were also synthesized and structurally characterized for further comparison. The preliminary reaction chemistry of the copper­(I) aggregates was studied