Diastereo-
and Enantioselective Iridium-Catalyzed
Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands
and Barium Enolates

Behenna D. C.; Braun M.; Braun M.; Braun M.; Chen J.-P.; Chen M.; Chen W.; Chen W.; Chen W.; Devine P. N.; Doyle A. G.; Evans D. A.; Graening T.; Hamilton J. Y.; Hartwig J. F.; Hashimoto T.; He H.; Imai M.; Job A.; John F. Hartwig; Kano T.; Kim D.; Kobayashi S.; Krautwald S.; Krautwald S.; Lei B.-L.; List B.; Liu W.-B.; Liu W.-B.; Liu W.-B.; Liu W.-B.; Liu W.-B.; Madrahimov S. T.; Madrahimov S. T.; Markovic D.; Mastracchio A.; Melchiorre P.; Meyers A. I.; Ming Chen; Murakata M.; Myers A. G.; Oppolzer W.; Raskatov J. A.; Roggen M.; Saito S.; Schmierer R.; Spiess S.; Stanley L. M.; Stivala C. E.; Teichert J. F.; Tosatti P.; Trost B. M.; Trost B. M.; Trost B. M.; Trost B. M.; Weix D. J.; Wenyong Chen; Xu Q.-L.; Yamada Y. M. A.; Yamamoto H.; Yanagisawa A.; Ye K.-Y.; Zhang X.; Zheng W.-H.; Zhuo C.-X.

Diastereo- and Enantioselective Iridium-Catalyzed Allylation of Cyclic Ketone Enolates: Synergetic Effect of Ligands and Barium Enolates

Abstract

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (<i>R</i>)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures