Gold(I) Carbenes by Retro-Buchner Reaction: Generation and Fate

Abstract

The fate of the aryl gold(I) carbenes generated by retro-Buchner reaction of ortho-substituted 7-aryl-1,3,5-cycloheptatrienes is dependent on the constitution of the ortho substituent. Indenes and fluorenes are obtained by intramolecular reaction of highly electrophilic gold(I) carbenes with alkenes and arenes. According to density functional theory calculations, the gold-catalyzed retro-Buchner process occurs stepwise, although the two carbon–carbon cleavages occur on a rather flat potential energy surface.

Gold(I)‐Catalyzed Cycloisomerizations and Alkoxycyclizations of ortho‐(Alkynyl)styrenes

“…[20] The previous study allowed us to identify the structural requirements of the initial o-(alkynyl)styrenes to get 1H-indene derivatives. [21] At this point, the importance of developing new methods to synthesize this skeleton should be remarked. Thus, 1H-indenes are found in pharmaceuticals, [22] functional materials [23] or as ligands in metal catalysis.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…Gold carbene complexes (e.g.1419, Scheme 116) were generated through retro-Buchner reactions of arylcycloheptatrienes (e.g. 1417) [1264]. Several processes were demonstrated for the carbene complexes alkylidenecyclopropanes (e.g.…”

Synthesis of α,α,α′,α′-Tetrachloro-Δ1-bipyrrolines and 4,8-Dichloro-2,6-diazasemibuvallenes

“…1c−e The ring-closure intermediate 8 would be formed from the carbene intermediate 7. 12 Subsequent 1,2-chloro shift in 8 gave the product 4.…”