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 October 6, 2017 | public
Journal Article Open

Enantioselective Pd-Catalyzed Decarboxylative Allylic Alkylation of Thiopyranones. Access to Acyclic, Stereogenic α-Quaternary Ketones


A catalytic, enantioselective decarboxylative allylic alkylation of 4-thiopyranones is reported. The α-quaternary 4-thiopyranones produced are challenging to access by standard enolate alkylation owing to facile ring-opening β-sulfur elimination. In addition, reduction of the carbon–sulfur bonds provides access to elusive acyclic α-quaternary ketones. The alkylated products are obtained in up to 92% yield and 94% enantiomeric excess.

Additional Information

© 2017 American Chemical Society. Received: July 30, 2017; Published: September 13, 2017. We thank NIH-NIGMS (R01GM080269), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support. E.J.A. is grateful to the National Science Foundation for a predoctoral fellowship. We thank Dr. David VanderVelde (Caltech) for NMR expertise, and Dr. Mona Shahgholi (Caltech) and Naseem Torian (Caltech) for mass spectrometry assistance. The authors declare no competing financial interest.

Attached Files

Accepted Version - nihms906117.pdf

Supplemental Material - ol7b02354_si_001.pdf

Supplemental Material - ol7b02354_si_002.pdf


Files (7.2 MB)
Name Size Download all
6.0 MB Preview Download
529.3 kB Preview Download
672.5 kB Preview Download

Additional details

August 19, 2023
August 19, 2023