Issue 1, 2019

Mechanistic investigation into the C(sp3)–H acetoxylation of morpholinones

Abstract

The study of a selective palladium(II)-catalyzed C(sp3)–H acetoxylation reaction on a class of cyclic alkyl amines is reported. Computational modelling and kinetic studies were used to provide support for a mechanism involving selective C–O bond formation from a γ-aminoalkyl-Pd(IV) intermediate. The C–O bond forming step was computed to occur by a dissociative ionization mechanism followed by an SN2 process involving external acetate attack at the C–Pd(IV) bond. This pathway was computed to be of lowest energy with no competing C–N products observed. Additionally, with a few modifications to reaction conditions, preliminary studies showed that this process could be rendered enantioselective in the presence of a non-racemic BINOL-phosphoric acid.

Graphical abstract: Mechanistic investigation into the C(sp3)–H acetoxylation of morpholinones

Supplementary files

Article information

Article type
Edge Article
Submitted
02 aug 2018
Accepted
28 sep 2018
First published
01 okt 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 83-89

Mechanistic investigation into the C(sp3)–H acetoxylation of morpholinones

C. S. Buettner, D. Willcox, Ben. G. N. Chappell and M. J. Gaunt, Chem. Sci., 2019, 10, 83 DOI: 10.1039/C8SC03434F

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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