Regio- and Enantioselective Rhodium-Catalyzed Allylic Alkylation of Racemic Allylic Alcohols with 1,3-Diketones

• DOI: 10.1021/jacs.8b05126
• Publication Date: 2018-05-25T14:30:52Z
• Authors: Sheng-Biao Tang; Xiao Zhang; Hang-Fei Tu; Shu-Li You
• Keywords: 4. Education; 01 natural sciences; 0104 chemical sciences; 3. Good health

Highly regio- and enantioselective rhodium-catalyzed allylic alkylation of 1,3-diketones with racemic secondary allylic alcohols is reported. In the presence of a Rh-catalyst derived from the Carreira (P, olefin)-ligand and TFA as an additive, chiral branched α-allylated 1,3-diketones could be obtained in good to excellent yields, with excellent regio- and enantioselectivity ( b/ l > 19/1, 86-98% ee). The direct utilization of allyl alcohols as electrophiles represents an improvement from the viewpoint of an atom economy. Both aryl- and aliphatic-substituted allyl alcohols are suitable substrates with excellent reaction outcomes. This reaction features mild conditions, broad substrate scope, and readily available substrates.