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Tandem Cyclization of Alkynes via Rhodium Alkynyl and Alkenylidene Catalysis

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journal contribution
posted on 22.11.2006, 00:00 by Jung Min Joo, Yu Yuan, Chulbom Lee
A rhodium(I)-catalyzed tandem cyclization of alkynes has been developed. The reaction allows for multiple bond formations to occur at both the α- and β-positions of alkynes under mild conditions to yield a variety of fused ring systems as the products. In the presence of triethylamine and the complex derived from [Rh(COD)Cl]2 and P(4-F-C6H4)3, a terminal alkyne is converted to a rhodium alkynyl species which reacts with a tethered alkyl halide at the β-position to provide a β,β-disubstituted alkenylidene complex. The rhodium alkenylidene species then undergoes additional ring closures with a range of pendent functional groups such as alkene, hydroxyl, and phenyl groups through [2 + 2] cycloaddition, nucleophilic addition, and 6π-electrocyclization processes, respectively.