α,β‐Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5‐Alkoxy Migration of 1,6‐Enynes: Mechanisms and Applications

Gold-Catalyzed Rearrangements and Beyond

Cycloisomerizations of enynes are probably the most representative carbon-carbon bond forming reactions catalyzed by electrophilic metal complexes. These transformations are synthetically useful because chemists can use them to build complex architectures under mild conditions from readily assembled starting materials. However, these transformations can have complex mechanisms. In general, gold...

Gold(I)-catalyzed cycloisomerization of 3-methoxy-1,6-enynes featuring tandem cyclization and [3,3]-sigmatropic rearrangement.

Gold(I)-catalyzed 6-endo hydroxycyclization of 7-substituted-1,6-enynes

The cyclization of o-(alkynyl)-3-(methylbut-2-enyl)benzenes, 1,6-enynes having a condensed aromatic ring at C3-C4 positions, has been studied under the catalysis of cationic gold(I) complexes. The selective 6-endo-dig mode of cyclization observed for the 7-substituted substrates in the presence of water or methanol giving rise to hydroxy(methoxy)-functionalized dihydronaphthalene derivatives is...

Gold(I)-catalysed cycloisomerisation of 1,6-enynes into functionalised allenes.

1,6-Enynes can be transformed into vinylidenecyclopentanes via gold-promoted 5-exo dig cyclisation followed by 1,5-hydride or -alkoxide shift.

Enantioselective cyclizations of silyloxyenynes catalyzed by cationic metal phosphine complexes.

The discovery of complementary methods for enantioselective transition metal-catalyzed cyclization with silyloxyenynes has been accomplished using chiral phosphine ligands. Under palladium catalysis, 1,6-silyloxyenynes bearing a terminal alkyne led to the desired five-membered ring with high enantioselectivities (up to 91% ee). As for reactions under cationic gold catalysis, 1,6- and 1,5-silylo...