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Enantioselective Alkoxycyclization of 1,6‐Enynes with Gold(I)‐Cavitands: Total Synthesis of Mafaicheenamine C
Author(s) -
MartínTorres Inmaculada,
Ogalla Gala,
Yang JinMing,
Rinaldi Antonia,
Echavarren Antonio M.
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202017035
Subject(s) - cycloisomerization , enantioselective synthesis , chemistry , cavitand , carbazole , enantiomer , stereochemistry , total synthesis , combinatorial chemistry , organic chemistry , molecule , catalysis , supramolecular chemistry
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.