Gold(I)-Catalyzed Intermolecular Addition of Carbon Nucleophiles to 1,5- and 1,6-Enynes

• Published in: Journal of organic chemistry Vol. 73; no. 19; pp. 7721 - 7730
• Main Authors: Amijs, Catelijne H. M, López-Carrillo, Verónica, Raducan, Mihai, Pérez-Galán, Patricia, Ferrer, Catalina, Echavarren, Antonio M
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 03.10.2008; Amer Chemical Soc
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Catalysis; Catalysts: preparations and properties; Chemistry; Chemistry, Organic; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with only one n hetero atom and condensed derivatives; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; SKELETAL REORGANIZATION; ENYNE METATHESIS; GOLD CATALYSIS; PLATINUM; STEREOSELECTIVE-SYNTHESIS; ALKYNES; CYCLIZATION; HIGHLY SUBSTITUTED FURANS; CATALYZED CYCLOISOMERIZATION REACTIONS; PROPARGYLIC CARBOXYLATES; Catalytic reaction; Cyclopropane derivatives; Gold I Complexes; Acetylenic compound; Nitrogen heterocycle; Ligand; Selectivity; Diketone; Enynic compound; Pyrrole derivatives; Carbene; Alkene; Cyclization; Aromatic compound; Catalyst; Ethylenic compound; Heterocyclic compound; Alkyne; Nucleophile; Gold I
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo8014769

Gold(I)-catalyzed addition of carbon nucleophiles to 1,6-enynes gives two different type of products by reaction at the cyclopropane or at the carbene carbons of the intermediate cyclopropyl gold carbenes. The 5-exo-dig cyclization is followed by most 1,6-enynes, although those bearing internal alkynes and alkenes react by the 6-endo-dig pathway. The cyclopropane versus carbene site-selectivity can be controlled in some cases by the ligand on the gold catalyst. In addition to electron-rich arenes and heteroarenes, allylsilanes and 1,3-dicarbonyl compounds can be used as the nucleophiles. In the reaction of 1,5-enynes with carbon nucleophiles, the 5-endo-dig pathway is preferred.