Construction of Vicinal Tertiary and All-Carbon Quaternary Stereocenters via Ir-Catalyzed Regio-, Diastereo-, and Enantioselective Allylic Alkylation and Applications in Sequential Pd Catalysis
Highly congested vicinal stereocenters comprised of tertiary and all-carbon quaternary centers were generated via Ir-catalyzed asymmetric allylic alkylation of β-ketoesters. These catalytic reactions proceed in excellent yields with a broad scope on either reaction partner and with outstanding regio-, diastereo-, and enantiocontrol. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers.
Additional Information© 2013 American Chemical Society. Received: May 23, 2013; Published: July 7, 2013. The authors wish to thank NIH-NIGMS (R01GM080269), Amgen, 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. Dr. Mona Shahgholi and Naseem Torian are acknowledged for mass spectrometry assistance. Lawrence Henling is acknowledged for X-ray crystallographic structural determination. The authors thank Mr. Jeff Holder for the preparation of [Ir(cod)Cl]2. The authors are thankful to Professor Shu-Li You and Mr. Robert Craig for L3 and (R)-L8, respectively, and for helpful discussions.
Accepted Version - nihms504692.pdf
Supplemental Material - ja4052075_si_001.pdf
Supplemental Material - ja4052075_si_002.cif