The cinnamates having an ortho-formyl group can potentially form vinylogous iminium ion species under the catalysis of chiral amines, which facilitates the Diels–Alder cycloaddition reaction with the concurrently generated trienamines between dienals and amine catalysts in a regioselectivity umpolung manner. A cascade intramolecular aldol reaction was followed, finally furnishing polyhydrophenanthrene frameworks with excellent diastereo- and enantioselectivity.

A relay catalytic protocol using pyrrolidine and palladium catalysis has been developed for asymmetric synthesis of 1,3-diamine derivatives from 3-substituted 1,3-dienes, sulfuric diamide, and aldehydes. This one-pot, three-component reaction features the advantages of a high atom step economy and operational simplicity, providing an efficient and straightforward access to valuable 1,3-diamines incorporating quaternary and tertiary stereogenic centers with moderate to good enantioselectivity.

We uncovered an asymmetric higher-order [10+2] cycloaddition reaction between diverse activated alkenes and a new type of π-allylpalladium complex-containing dipole-type 10π-cycloaddends, which were generated in situ from 2-methylene-1-indanols via a...