Reaction of enol ethers with alkynes catalyzed by transition metals: 5-exo-dig versus 6-endo-dig cyclizations via cyclopropyl platinum or gold carbene complexes

The intramolecular reaction of enol ethers with alkynes in methanol is catalyzed by electrophilic Pt(II), Pd(II), and Au(III) chlorides and by a Cu(I) complex to give five- or six-membered rings bearing dimethyl acetals. The reaction takes place by an anti addition of the enol ether and the metal to the alkyne. The possible involvement of vinylidene complexes in this reaction is excluded. In addition to the usual 5-exo-dig (or 6-exo-dig) pathways, a 6-endo-dig pathway has also been found to take place with certain enynes. One case of 5-endo-dig cyclization has also been found. A general scheme for the alkoxycyclization of enynes catalyzed by transition metals based on DFT calculation of PtCl(2) and AuCl(3) complexes that includes exo and endo cyclizations is presented.