Gold‐Catalyzed Reactions of Propargyl Esters, Propargyl Alcohols, and Related Compounds

Platinum-Catalyzed Tandem Cycloisomerization Reaction of Benzoendiynyl Esters: Regioselective Long-Range 1,5-Acyl Migration

“…During the past few decades, transition-metal-catalyzed electrophilic cycloisomerization reactions involving chain rearrangement of unsaturated π-conjugated propargylic esters have aroused considerable attention , because these types of rearrangements have proved to be highly efficient strategies for the cascade synthesis of complex aromatic molecules. For instances, in 2006, Toste and Oh reported the Au-catalyzed [3,3] sigmatropic rearrangement/6- endo - dig cyclization reaction of 1,6-diynyl esters to give naphthyl ketones.…”

Two-fold tandem acyl-group shift/cyclization via gold catalysis

“…21 This sequence involves an initial 1,3-acyloxy shift to provide the corresponding allenyl ester 7 (Cycle I in Scheme 4). [29][30][31] The cationic gold catalyst then coordinates to the least hindered unsaturation, namely the terminal alkyne fragment, triggering the cyclization of the most electron-rich allene in 7-Au. The favored 5-exo-dig process delivers vinylgold intermediate 8 that can subsequently evolve to 9 via a 1,5-acyl transfer (Cycle II in Scheme 4).…”

Gold-Catalyzed Synthesis of Small Rings

“…Propargylic carboxylates are prone to metal-catalyzed rearrangements. − Seminal works by Ohloff and Rautenstrauch showed that propargyl acetates underwent 1,2-acyloxy migration using ZnCl 2 or [PdCl 2 (CH 3 CN) 2 ], respectively. Later studies focused on the use of Ru, − Cu, , Ag, , Pt, Au, − , and Rh .…”