The role of cyclobutenes in gold(I)-catalysed skeletal rearrangement of 1,6-enynes.

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.

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

Ready Access to the Echinopines Skeleton via Gold(I)-Catalyzed Alkoxycyclizations of Enynes

The [3,5,5,7] tetracyclic skeleton of echinopines has been stereoselectively accessed through a gold(I)-catalyzed alkoxycyclization of cyclopropyl-tethered 1,6-enynes. The key bicyclo[4.2.1]nonane core of the enyne precursors was readily assembled by means of a Co-catalyzed [6 + 2] cycloaddition. Furthermore, the attempted alkoxycyclization of 1,5-enyne substrates revealed an uncovered cyclopro...

Gold and Platinum Catalysis of Enyne Cycloisomerization

This account provides a comprehensive overview of the development of gold and platinum catalysis of the enyne cycloisomerization. The use of these soft, alkynophilic metals enables mild, chemoselective and efficient transformations of a variety of readily available acyclic enynes to a wide range of synthetically useful carbocyclic and heterocyclic products. The review is organized according to ...

Synthesis of polyfluoroalkyl cyclobutenes from 3-aza-1,5-enynes via an aza-Claisen rearrangement/cyclization cascade.

A facile synthetic route to access polyfluoroalkyl functionalized cyclobutenes bearing an exo cyclic double bond from 3-aza-1,5-enynes is reported. The reaction proceeds via a thermal aza-Claisen rearrangement to give an allene-imine intermediate; subsequent cyclization affords the cyclobutene core. The kinetics of the transformation of starting material and the intermediate was studied by (1)H...