Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.
J Org Chem. 2013 Jun 21;78(12):6309-15. doi: 10.1021/jo400671q. Epub 2013 Jun 4.
A modified protocol has been identified for Pd-catalyzed intermolecular aminoacetoxylation of terminal and internal alkenes that enables the alkene to be used as the limiting reagent. The results prompt a reassessment of the stereochemical course of these reactions. X-ray crystallographic characterization of two of the products, together with isotopic labeling studies, show that the amidopalladation step switches from a cis-selective process under aerobic conditions to a trans-selective process in the presence of diacetoxyiodobenzene.
已确定一种用于 Pd 催化的末端和内部烯烃的氨基乙氧羰基化的改进方案，该方案可以使烯烃成为限制试剂。结果促使对这些反应的立体化学过程进行重新评估。通过对两个产物的 X 射线晶体学表征以及同位素标记研究，表明在有氧条件下，酰胺钯化步骤由顺式选择性过程转变为在二醋酸碘苯存在下的反式选择性过程。
