title: Au(I)-Catalyzed cycloisomerizations terminated by sp(3) C-H bond insertion.
abstract: The gold(I)-catalyzed cycloisomerization of 1,5-enynes and 1,4-allylallenes to tetracyclododecane and tetracyclotridecane derivatives, respectively, is reported. Complexation of the cationic gold(I) complex to either the alkyne or allene moiety induces an intramolecular addition of the alkene, leading to a gold(I)-stabilized carbenoid intermediate. This intermediate undergoes a formal sp(3) C-H insertion to generate the tetracyclic adduct. A series of deuterium labeling experiments showed that the C-H functionalization step proceeds with an inverse kinetic isotope effect.
authors.affiliation: Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan. horino@eng.u-toyama.ac.jp
authors.forename: Yoshikazu
authors.initials: Y
authors.lastname: Horino
authors.forename: Takuya
authors.initials: T
authors.lastname: Yamamoto
authors.forename: Kohki
authors.initials: K
authors.lastname: Ueda
authors.forename: Shigeyasu
authors.initials: S
authors.lastname: Kuroda
authors.forename: F Dean
authors.initials: FD
authors.lastname: Toste
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D001952:Bridged-Ring Compounds / Q000138:chemical synthesis*; D002384:Catalysis; D002414:Cations, Monovalent / Q000737:chemistry; D003500:Cyclization; D006046:Gold / Q000737:chemistry*; D007536:Isomerism
chemical_list: D000480:Alkynes; D000498:Allyl Compounds; D001952:Bridged-Ring Compounds; D002414:Cations, Monovalent; D006046:Gold