A highly enantioselective rhodium-catalyzed [4+2+2] cycloaddition of terminal alkynes and dienyl isocyanates has been developed. The cycloaddition provides a rapid entry to highly functionalized and enantioenriched bicyclic azocines. This reaction represents the first [4+2+2] cycloaddition strategy to construct nitrogen-containing eight-membered rings.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2774260PMC
http://dx.doi.org/10.1021/ja906641dDOI Listing

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