Mechanistic investigation into the C(sp3)-H acetoxylation of morpholinones.
Royal Society of Chemistry (RSC)
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Buettner, C., Willcox, D., Chappell, B. G., & Gaunt, M. (2019). Mechanistic investigation into the C(sp3)-H acetoxylation of morpholinones.. Chem Sci, 10 (1), 83-89. https://doi.org/10.1039/c8sc03434f
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.
Engineering and Physical Sciences Research Council (EP/N031792/1)
External DOI: https://doi.org/10.1039/c8sc03434f
This record's URL: https://www.repository.cam.ac.uk/handle/1810/285609
Attribution 4.0 International
Licence URL: https://creativecommons.org/licenses/by/4.0/