CaltechAUTHORS
Published November 6, 2015 | Version Published + Supplemental Material
Journal Article Open

Palladium-Catalyzed Enantioselective Decarboxylative Allylic Alkylation of Cyclopentanones

Creators

Abstract

The first general method for the enantioselective construction of all-carbon quaternary centers on cyclopentanones by enantioselective palladium-catalyzed decarboxylative allylic alkylation is described. Employing the electronically modified (S)-(p-CF_3)_3-t-BuPHOX ligand, α-quaternary cyclopentanones were isolated in yields up to >99% with ee's up to 94%. Additionally, in order to facilitate large-scale application of this method, a low catalyst loading protocol was employed, using as little as 0.15 mol % Pd, furnishing the product without any loss in ee.

Additional Information

© 2015 American Chemical Society. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: August 17, 2015; Publication Date (Web): October 26, 2015. We thank the NIH-NIGMS (R01GM080269 and postdoctoral fellowship F32GM073332 to A.M.H.), Amgen, the Gordon and Betty Moore Foundation, and Caltech for financial support. R.A.C. gratefully acknowledges the support of this work provided by a predoctoral fellowship from the National Cancer Institute of the National Institutes of Health under Award No. F31A17435. Additionally, we thank Eli Lilly (predoctoral fellowship to J.T.M.) and the Fannie and John Hertz Foundation (predoctoral fellowship to D.C.B.). R.A.C. and S.A.L. contributed equally. The authors declare no competing financial interest.

Attached Files

Published - ol5b02376.pdf

Supplemental Material - ol5b02376_si_001.pdf

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Additional details

Identifiers

PMCID
PMC4640231
Eprint ID
61763
DOI
10.1021/acs.orglett.5b02376
Resolver ID
CaltechAUTHORS:20151102-100307186

Funding

NIH
R01GM080269
NIH Postdoctoral Fellowship
F32GM073332
Amgen
Gordon and Betty Moore Foundation
Caltech
NIH Predoctoral Fellowship
F31A174359
Fannie and John Hertz Foundation

Dates

Created
2015-11-02
Created from EPrint's datestamp field
Updated
2022-05-17
Created from EPrint's last_modified field