Enantioselective Alkoxycyclization of 1,6‐Enynes with Gold(I)‐Cavitands: Total Synthesis of Mafaicheenamine C
Inmaculada Martín‐Torres, Gala Ogalla, Jin‐Ming Yang, Antonia Rinaldi, Antonio M. Echavarren
Abstract
Chiral gold(I)-cavitand complexes have been developed for the enantioselective alkoxycyclization of 1,6-enynes. This enantioselective cyclization has been applied for the first total synthesis of carbazole alkaloid (+)-mafaicheenamine C and its enantiomer, establishing its configuration as R. The cavity effect was also evaluated in the cycloisomerization of dienynes. A combination of experiments and theoretical studies demonstrates that the cavity of the gold(I) complexes forces the enynes to adopt constrained conformations, which results in the high observed regio- and stereoselectivities.
Topics & Concepts
CycloisomerizationEnantioselective synthesisCavitandChemistryEnantiomerCarbazoleStereochemistryCombinatorial chemistryCinchonaOrganic chemistryMoleculeCatalysisSupramolecular chemistryCatalytic Alkyne ReactionsTraditional and Medicinal Uses of AnnonaceaeCatalytic C–H Functionalization Methods