Several novel reactions are developed utilizing the electron-deficient nature of terminal alkyne-W (CO)
5 π-complexes and/or their isomerized vinylidene complexes. Terminal alkynes having a silyl enol ether moiety in the molecule undergo
endo-selective cyclization using a catalytic amount of W (CO)
5 (thf). In some cases, both
exo-and
endo-selective cyclizations are achieved depending on the reaction conditions. Iodinated vinylidene intermediates are generated from the corresponding iodoalkynes and W (CO)
5 (thf), and are employed for the related cyclizations. Electrocyclization of
o-ethynylphenyl ketones gives novel benzopyranylidene complexes, which undergo Diels-Alder reaction with electron-rich alkenes to give substituted naphthalenes. Furthermore, the reaction of
o-ethynylphenyl ketones and electron-rich alkenes in the presence of a catalytic amount of W (CO)
5 (thf) proceeds through the novel tungsten-containing carbonyl ylides, which react with the electron-rich alkenes in a [3+2] -cycloaddition manner to give polycyclic compounds.
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