A highly efficient
enantioselective synthesis of multisubstituted
tetrahydrobenzofuran derivatives with four contiguous stereocenters
was established by the dual catalysis of a gold(I)/chiral N,N′-dioxide-cobalt(II) complex
via a tandem cycloisomerization/Diels–Alder reaction of 2-alkynyl-2-alkenones
and electron-deficient olefins. This strategy was not only featured
with atom economy, remarkable efficiency and stereoselectivity but
also was highlighted by further transformations of the furan-based
products into polycyclic molecules. Moreover, a possible transition-state
model was proposed to elucidate the origin of stereoselectivity.