An organocatalytic enantio- and diastereoselective synthesis
of
hexahydropyrrolo[2,3-b]indole-containing tetrasubstituted
α-amino allenoates, exhibiting both axial and central chirality,
has been accomplished via cascade dearomatization–cyclization
reaction. The γ-addition to β,γ-alkynyl-α-imino
esters provides a library of densely substituted highly enantioenriched
allenes in high yields and excellent stereoselectivities. In addition,
the scope of this methodology has been extended to tryptophol as well.
A scale-up reaction and synthetic transformations of the products
were performed to demonstrate the practical usefulness of this approach.