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

Authors
Buettner, Cornelia S 
Chappell, Ben GN 

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Article
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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.

Publication Date
2019-01-07
Online Publication Date
2018-10
Acceptance Date
2018-09-28
Keywords
3405 Organic Chemistry, 34 Chemical Sciences
Journal Title
Chem Sci
Journal ISSN
2041-6520
2041-6539
Volume Title
10
Publisher
Royal Society of Chemistry (RSC)
Sponsorship
Engineering and Physical Sciences Research Council (EP/N031792/1)