Fei YE

New Schiff bases derived from chiral d-camphor were determined to be effective phosphine ligands for the asymmetric palladium-catalyzed allylic alkylation of activated methylene compounds, the allylic etherification of alcohols, and the allylic amination of primary amines or secondary amines, in which the corresponding products with various functional groups were achieved in good yields with excellent enantioselectivities (up to >99 % ee). Remarkably, the palladium catalyst derived from Schiff base L2 afforded the highest level of enantioselectivity reported to date for allylic substitution reactions, including allylic etherification and allylic amination, which revealed the privileged role of d-camphor-derived Schiff bases in palladium-catalyzed allylic substitution reactions.

d-Camphor as a springboard: The palladium-catalyzed asymmetric allylic alkylation of structurally diverse nucleophiles provides products in excellent yields with high enantioselectivities (up to >99 % ee) in the presence of a rigid d-camphor-derived Schiff base with nitrogen and phosphorus atoms.

Reported herein is the first enantioselective β-elimination reaction catalyzed by a chiral cation-binding polyether. By using this catalytic protocol, a wide range of β-sulfonyl ketones could be effectively resolved with high stereoselectivity (S up to >300). Key to the success of this process is the favorable secondary interactions of the catalyst with the Lewis basic groups on the sulfone substrate. The enone product of this process can be easily converted into the racemic starting material, and allows an effective recycling and overall synthesis of chiral β-sulfonyl ketones in high yield and excellent enantioselectivity.

Paired off: The title reaction leads to effective resolution of a wide range of β-sulfonyl ketones (1) with high stereoselectivity. Key to the success of this process is the favorable secondary interactions of the catalyst with the Lewis basic groups on the substrate. The enone product can be easily converted into the racemic starting material and allows effective recycling, and thus isolation of β-sulfonyl ketones in high yield and excellent enantioselectivity.

The asymmetric transfer hydrogenation (ATH) of racemic 1,2-(α-ketotetramethylene)ferrocene using the [N-(tosyl)-1,2-diphenylethylendiamine]ruthenium(II) complex [TsDPEN-Ru(II)] as catalyst takes place with a high level of kinetic resolution to deliver the ketone in up to 99% ee. The X-ray crystallographic structure of a derivative of the alcohol co-product serves to confirm conclusively both the absolute configuration of 1,2-(α-ketotetramethylene)ferrocene and the endo-reduction selectivity.