Enantioselective Alkoxycyclization of 1

Identificador:  imarina:9172962

Handle: https://hdl.handle.net/20.500.11797/imarina9172962

Autors:  Martin-Torres, Inmaculada; Ogalla, Gala; Yang, Jin-Ming; Rinaldi, Antonia; Echavarren, Antonio M

Resum:
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.