Platinum and ruthenium chloride-catalyzed cycloisomerization of 1-alkyl-2-ethynylbenzenes: interception of pi-activated alkynes with a benzylic C-H bond.
Air-stable and commercially available alkynophilic metal salts, such as PtCl2, PtCl4, and [RuCl2(CO)3]2, catalyze the cycloisomerization of 1-alkyl-2-ethynylbenzenes to produce substituted indenes even at an ambient temperature. Electrophilically activated alkynes can be intercepted by simple benzylic C-H bonds at primary, secondary, and tertiary carbon centers. Mechanistic studies, such as labeling studies and kinetic isotope and substituent effects, indicate that the cycloisomerization proceeds through the formation of a vinylidene intermediate and turnover-limiting 1,5-shift of benzylic hydrogen.
Tobisu
Mamoru
M
Frontier Research Base for Global Young Researchers, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan.
Nakai
Hiromi
H
Chatani
Naoto
N