Copper(II)-Catalyzed Amidations of Alkynyl Bromides as a General Synthesis of Ynamides and Z-Enamides. An Intramolecular Amidation for the Synthesis of Macrocyclic Ynamides

• Published in: Journal of organic chemistry Vol. 71; no. 11; pp. 4170 - 4177
• Main Authors: Zhang, Xuejun, Zhang, Yanshi, Huang, Jian, Hsung, Richard P, Kurtz, Kimberly C. M, Oppenheimer, Jossian, Petersen, Matthew E, Sagamanova, Irina K, Shen, Lichun, Tracey, Michael R
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 26.05.2006; Amer Chemical Soc
• Subjects: Amides - chemical synthesis; Bromides - chemistry; Catalysis; Chemistry; Chemistry, Organic; Copper - chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Macrocyclic Compounds - chemical synthesis; Molecular Conformation; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; N-ALKYNYLATION; CYCLOADDITION REACTIONS; RING-CLOSING METATHESIS; CHIRAL YNAMIDES; CATALYZED SYNTHESIS; DIELS-ALDER REACTION; BOND FORMATION; SAUCY-MARBET REARRANGEMENT; TRANSITION-METALS; MARINE ALKALOIDS; Copper II; Intramolecular reaction; Catalytic reaction; Acetylenic compound; Nitrogen heterocycle; Enamine; Carboxamide; Organic bromine compounds; Chemical synthesis; Amidation; Macrocycle; Phenanthroline-ortho
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo060230h

A general and efficient method for the coupling of a wide range of amides with alkynyl bromides is described here. This novel amidation reaction involves a catalytic protocol using copper(II) sulfate-pentahydrate and 1,10-phenanthroline to direct the sp-C−N bond formation, leading to a structurally diverse array of ynamides including macrocyclic ynamides via an intramolecular amidation. Given the surging interest in ynamide chemistry, this atom economical synthesis of ynamides should invoke further attention from the synthetic organic community.