Pure Appl. Chem., 2008, Vol. 80, No. 5, pp. 1055-1062
doi:10.1351/pac200880051055
Cu(I)-catalyzed asymmetric allylation of ketones and ketimines*
Motomu Kanai, Reiko Wada, Tomoyuki Shibuguchi, and Masakatsu Shibasaki
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
Abstract:
Chiral CuF-catalyzed asymmetric allylation of ketones and ketimines is described. Nucleophile activation via transmetallation (allylboronate to allylcopper), which is facilitated by a cocatalyst [La(OiPr)3 or LiOiPr], is key for these reactions. A CuOTf-3KOtBu-DUPHOS complex is a comparably effective catalyst that reduces the required amount of chiral phosphines.
Keywords: allylation; asymmetric catalysis; copper; ketimines; ketones; tetrasubstituted carbon.
*Paper based on a presentation at the 14th International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14), 2-6 August 2007, Nara, Japan. Other presentations are published in this issue, pp. 807-1194.