Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published July 24, 2013 | Accepted Version + Supplemental Material
Journal Article Open

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.

Attached Files

Accepted Version - nihms504692.pdf

Supplemental Material - ja4052075_si_001.pdf

Supplemental Material - ja4052075_si_002.cif


Files (5.9 MB)
Name Size Download all
4.2 MB Preview Download
1.0 MB Download
626.7 kB Preview Download

Additional details

August 19, 2023
October 24, 2023