We have shown that Me-DuPHOS monoxide (BozPHOS) is a very effective ligand in the copper-catalyzed addition of dialkylzinc to N-phosphinoylimines providing access to alpha-chiral amines. The new ligand is particularly effective for the addition of the lesser reactive dimethylzinc. The major advantages of this process are high yields, broad substrate scope, and high enantioselectivities with low catalyst loading (3 mol %).

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Chiral N‐heterocyclic carbenes are good ligands for the copper‐catalyzed conjugate addition of dialkylzinc reagents to various Michael acceptors. With as little as 4% of chiral ligand, the enantioselectivity may reach 93% on cycloheptenone.

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The alpha-alkylation of amide enolates by using a pseudo-C(2) symmetry trans 4-phenyl-2-trifluoromethyloxazolidine (trans-Fox) as a chiral auxiliary occurs with an extremely high diastereoselectivity (>99 % de). The origin of this excellent stereocontrol was investigated by an experimental and theoretical (DFT) study. With this trans chiral auxiliary, both F...metal and pi...metal interactions compete to give the same diastereomer through Re face alkylation of the enolate. A 5.5 kcal mol(-1) energy difference found between the Re face and the Si face attack transition states is consistent with the complete diastereoselectivity that has been experimentally achieved. On the other hand, in the case of the cis chiral auxiliary (cis-Fox) the competition between the F...metal and pi...metal interactions is unfavourable to the diastereoselectivity. In this case, the Re face and the Si face attack transition states were found to be nearly isoenergetic (0.3 kcal mol(-1) difference), which is in good agreement with the very low diastereoselectivity observed.

Using a trifluoromethylated oxazolidine (Fox) chiral auxiliary, the hydroxylation reaction of enolates was very efficiently performed under smooth and friendly conditions with molecular oxygen as oxidizer. This reaction occurred with an extremely high diastereoselectivity. After cleavage, the chiral auxiliary is efficiently recovered and highly valuable enantiopure oxygenated carboxylic acids and alcohols are released.