Ledwith Peter R, Cooney Madelene L, Bahou Karim A, García-Cárceles Javier, Thomson Joshua, Bower John F
Department of Chemistry, University of Liverpool, Crown Street, Liverpool, United Kingdom, L69 7ZD.
School of Chemistry, University of Bristol, Cantock's Close, Bristol, United Kingdom, BS8 1TS.
Angew Chem Int Ed Engl. 2024 Dec 9;63(50):e202411555. doi: 10.1002/anie.202411555. Epub 2024 Oct 22.
We report a strategy for the formal C-N cross-coupling of tertiary amines via the in situ generation and displacement of N-acyl ammonium species. Specifically, treatment of diverse tertiary amines with TFAA or chloroformates in the presence of NaI leads to the efficient generation of alkyl iodides, which can be engaged directly in Ni-catalyzed cross-couplings. The protocol is applicable to acyclic and cyclic systems, including highly hindered variants. Applications to the late-stage modification of complex heterocycles are presented.
我们报道了一种通过原位生成和取代N-酰基铵物种实现叔胺正式C-N交叉偶联的策略。具体而言，在碘化钠存在下，用三氟乙酸酐（TFAA）或氯甲酸酯处理各种叔胺可有效生成烷基碘化物，这些烷基碘化物可直接参与镍催化的交叉偶联反应。该方案适用于无环和环状体系，包括高度受阻的变体。还展示了其在复杂杂环后期修饰中的应用。
