Yu Fuchao, Valles Daniel A, Chen Weijie, Daniel Scott D, Ghiviriga Ion, Seidel Daniel
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
Faculty of Life Science and Technology, Kunming University of Science and Technology, Kunming 650500, P. R. China.
Org Lett. 2022 Sep 9;24(35):6364-6368. doi: 10.1021/acs.orglett.2c02148. Epub 2022 Aug 29.
Secondary alicyclic amines are converted to α-aminonitriles via addition of TMSCN to their corresponding imines, intermediates that are produced in situ via the oxidation of amine-derived lithium amides with simple ketone oxidants. Amines with an existing α-substituent undergo regioselective α'-cyanation even if the C-H bonds at that site are less activated. Amine α-arylation can be combined with α'-cyanation to generate difunctionalized products in a single operation.
仲脂环胺通过将三甲基氰硅烷(TMSCN)加成到其相应的亚胺上转化为α-氨基腈,这些亚胺中间体是通过胺衍生的锂酰胺与简单的酮氧化剂原位氧化产生的。即使α位的碳氢键活性较低,具有现有α-取代基的胺也会发生区域选择性α'-氰化反应。胺α-芳基化可与α'-氰化反应相结合,在一次操作中生成双官能化产物。