Transition Metal-Catalyzed and-Promoted Reactions via Carbene and Vinylidene Complexes Generated from Alkynes

摘要

The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated.These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in pi-alkyne complexes,and have been found to serve as versatile intermediates in catalytic carbene transfer reactions.Highlighted and reviewed in this account are the generation and preparation of pyranylidene,furylcarbene,pyrrolylcarbene,and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes,catalytic cyclopropanation reactions,[2,3]sigmatropic rearrangement or condensation reactions via ylides,ring-opening and substitution reactions with heteroaromatic compounds,and catalytic isomerization of oligoynes.