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. 2018 Mar 16;20(6):1604-1607.
doi: 10.1021/acs.orglett.8b00344. Epub 2018 Mar 2.

Regiocontrolled Wacker Oxidation of Cinnamyl Azides

Angela S Carlson  1 , Cristian Calcanas  1 , Ryan M Brunner  1 , Joseph J Topczewski  1
Affiliations

Regiocontrolled Wacker Oxidation of Cinnamyl Azides

Angela S Carlson et al. Org Lett. .

Abstract

A highly regioselective Wacker oxidation has been developed for the oxidation of cinnamyl azides. The catalytic oxidation tolerates the azide functionality, and more than 15 β-azido ketones were isolated (25-92% yield). High regioselectivity for the aryl ketone is observed in all cases. A robustness screen was conducted to determine functional group tolerance. The products of the oxidaiton can be readily diversified.

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Conflict of interest statement

Notes

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1
β-Azido-Ketone Syntheses and Applications
Scheme 2
Scheme 2
Wacker Oxidation of Internal Alkenes
Scheme 3
Scheme 3
Robustness Screena aA = additive % remaining; S = starting material % remaining; P = product % formed. Reported values determined by GC−FID analysis. A and S were determined based on a single point calibration. P was calibrated by linear regression. Values reported are the average of duplicate trials. bBenzaldehyde was observed as the major product. c4-Phenyl-2-butanone was observed as the major product.
Scheme 4
Scheme 4
Substrate Scope of Azide-Directed Wacker Oxidationa aYields are of isolated and purified material. Values reported are the average of duplicate trials.
Scheme 5
Scheme 5
Wacker Oxidation on Equilibrating Azide
Scheme 6
Scheme 6
Gram-Scale Reaction and Diversification of Products
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References

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