Enantioselective γ-Alkylation of α,β-Unsaturated Malonates and Ketoesters by a Sequential Ir-Catalyzed Asymmetric Allylic Alkylation/Cope Rearrangement
A catalytic, enantioselective γ-alkylation of α,β-unsaturated malonates and ketoesters is reported. This strategy entails a highly regio- and enantioselective iridium-catalyzed α-alkylation of an extended enolate, and a subsequent translocation of chirality to the γ-position via a Cope rearrangement.
Additional Information© 2016 American Chemical Society. Received: February 26, 2016. Published: April 7, 2016. We thank NIH-NIGMS (R01GM080269), the Gordon and Betty Moore Foundation, and Caltech for financial support. Shanghai Institute of Organic Chemistry (SIOC) is thanked for a postdoctoral fellowship to W.-B.L. Hiroshima International University is thanked for a postdoctoral fellowship to N.O. E.J.A. is grateful to the National Science Foundation for a predoctoral fellowship. K.T. acknowledges support from California HIV/AIDS Research Program (F08-CT-201). Mr. Lawrence Henlingand Dr. Michael Takase are acknowledged for X-ray analyses. We thank Dr. David VanderVelde for NMR expertise, and Dr. Mona Shahgholi and Naseem Torian for mass spectrometry assistance. The authors are also thankful to Professor Shu-Li You for the generous donation of N-aryl ligands and for helpful discussions.
Accepted Version - nihms867687.pdf
Supplemental Material - ja6b02153_si_001.pdf
Supplemental Material - ja6b02153_si_002.pdf
Supplemental Material - ja6b02153_si_003.cif
Supplemental Material - ja6b02153_si_004.cif