A formal [5 + 3] cycloaddition of zwitterionic allylpalladium intermediates with 1,3-dipoles is developed, providing N,O-containing eight-membered heterocyclic compounds in high yields. Catalytically generated zwitterionic allylpalladium intermediates in situ from vinylethylene carbonates or vinyloxiranes acted as dipolarophile.
With the use of a commercially available chiral phosphine as the catalyst, the first catalytic enantioselective [4 + 3] annulation of allenoates with C,N-cyclic azomethine imines is developed. The reaction works efficiently under mild reaction conditions to afford seven-membered ring-fused quinazoline-based tricyclic heterocycles in high yields with good to excellent diastereo- and enantioselectivities.
The
nine-membered ring-bearing bicyclo[5.2.2]tetrahydrooxonines
frameworks have enantioselectively been constructed via a tandem [3
+ 2] cycloaddition/Cope rearrangement reaction of vinylethylene carbonates
(VECs) with coumalates or pyrones. Under mild conditions, palladium-catalyzed
asymmetric tandem reaction of various substituted VECs and coumalates
or pyrones proceeds smoothly to produce the corresponding medium-sized
heterocyclic compounds in high yields with very high enantioselectivities.
Moreover, the reaction on the gram scale and further diverse transformations
of the products were workable. The reaction mechanism was investigated
through control experiments and DFT calculations, which show the reaction
proceeds via a tandem [3 + 2] cycloaddition/Cope rearrangement pathway
rather than via a [5 + 4] cycloaddition pathway.
A palladium-catalyzed enantioselective [4 + 2] cycloaddition reaction of vinyl benzoxazinones with sulfamate-derived cyclic imines is described, affording the tetrahydroquinazolines bearing several functional rings in high yields (up to 99% yield) with good to excellent diastereoselectivities and excellent enantioselectivities (up to 96% ee). This reaction represents the first Pd-catalyzed asymmetric decarboxylative cycloaddition of vinyl benzoxazinones with imines.
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