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 S_N2 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.

中文翻译：

---

吗啉酮 C（sp ³）-H乙酰氧基化的机理研究†

报道了对一类环状烷基胺的选择性钯（II）催化的C（sp ³）-H乙酰氧基化反应的研究。计算模型和动力学研究被用来为涉及由γ-氨基烷基-Pd（IV）中间体选择性形成C-O键的机理提供支持。C–O键形成步骤的计算是通过离解电离机理，随后是S _N 2过程，涉及C–Pd的外部乙酸盐侵蚀（IV）债券。计算得出该途径的能量最低，没有观察到竞争的C–N产物。另外，对反应条件进行了一些修改，初步研究表明，在非外消旋的BINOL-磷酸存在下，该过程可以使对映选择性。