The chiral oxamide–phosphine (COAP) ligands were developed for the palladium-catalyzed asymmetric allylic amination of vinyl benzoxazinones with alkylamines, affording a series of optically active diamines in good yields with high enantioselectivity.

An asymmetric linear selective allylic alkylation of vinylaziridines with 3-aryl oxindoles has been developed by using a chiral oxamide-phosphine (COAP-Bn-OMe-p)/palladium complex in methanol, which furnished a wide variety of 3,3-disubstituted oxindole derivatives in good yields with excellent regio- and enantioselectivities.

A chiral oxalamide phosphine (COAP)-Pd-catalyzed asymmetric cascade formal [4+1] annulation was developed between racemic vinyl benzoxazinones and N-tosylhydrazone sodium salts. The corresponding trans-2,3-disubstituted indoline products with contiguous stereogenic centers was...

Chiral bis-oxalamide (CBOA)/rare-earth metal complexes-catalyzed asymmetric inverse-electrondemand oxa-hetero-Diels-Alder (HDA) reactions were investigated under mild reaction conditions, which was performed between β,γ-unsaturated α-ketoesters and various electron-riched dienophiles, such as cyclopentadiene, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, tetrahydropyridine as well as phenyl(vinyl)sulfane. Several series of optically active functionalized 3,4-dihydro-2H-pyran or ring fused dihydropyran derivatives were obtained in high yields with high diastereo-and enantioselectivity. The procedure was able to tolerate a relatively wide range of substrates. The coordination mode of chiral bis-oxalamide with Sc(III) was demonstrated by the X-ray crystallographic structure, and DFT calculations were carried out to uncover the regio-and stereocontrol.

A Pd‐catalyzed enantioselective linear‐allylic alkylation of vinyl benzoxazinanones with a series of 3‐substituted oxindoles was reported in the presence of a chiral oxamide‐phosphine ligand (COAP−Bn) under mild reaction conditions. A series of optically active multifunctional 3,3′‐disubstituted oxindole derivatives bearing a quaternary stereogenic center and a linear aryl amino side chain were respectively obtained in 55–98% yields with 96–99% ee for 3‐(hetero)aryl substituted oxindoles. The developed protocol demonstrates that the COAP ligands could serve as a privileged chiral ligand to construct diverse chiral 3,3‐disubstituted oxindole compounds with various quaternary stereogenic centers, such as aza‐, thio‐ or all‐carbon quaternary stereogenic centers. The salient features of the method include broad substrate scope, N‐protecting group free, base‐free, and high regio‐ and enantioselectivity.