Gold-Catalyzed Cyclizations of cis-Enediynes: Insights into the Nature of Gold–Aryne Interactions


  • L.Z. thanks the NSF (CAREER CHE-0969157 and CHE-1301343) and NIGMS (R01 GM084254) for generous financial support. D.H.A. acknowledges support from the Center for Scientific Computing at the CNSI and MRL (NSF MRSEC DMR-1121053 and NSF CNS-0960316), as well as the National Center for Supercomputing Applications (NSF TG-CHE100123) utilizing the NCSA Gordon and Blacklight systems.


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Golden aryne? Gold aryne complexes are inferred as transition states in dual gold-catalyzed cyclizations of cis-enediynes (see scheme; DCE=1,2-dichloroethane). They are better described as ortho-aurophenyl cations, which react with weak nucleophiles and undergo facile intramolecular insertions into C(sp3)[BOND]H bonds. Indanes, fused heteroarenes, and phenol derivatives are readily prepared using this method.