School of Chemistry, University of Bristol, Bristol, BS8 1TS, United Kingdom.
Physical and Theoretical Laboratory, University of Oxford, Oxford, OX1 3QZ, United Kingdom.
J Am Chem Soc. 2020 Nov 11;142(45):19006-19011. doi: 10.1021/jacs.0c08973. Epub 2020 Oct 30.
Temporary directing groups (TDGs) underpin a range of C-C bond activation methodologies; however, the use of TDGs for the regiocontrolled activation of cyclopropane C-C bonds is underdeveloped. In this report, we show how an unusual ring contraction process can be harnessed for TDG-based carbonylative C-C bond activations of cyclopropanes. The method involves the transient installation of an isocyanate-derived TDG, rather than relying on carbonyl condensation events as used in previous TDG-enabled C-C bond activations.
临时导向基团（TDGs）是一系列 C-C 键活化方法的基础；然而，TDG 用于环丙烷 C-C 键的区域控制活化的应用还不够成熟。在本报告中，我们展示了如何利用不寻常的环收缩过程，基于 TDG 实现对环丙烷的羰基化 C-C 键的区域控制活化。该方法涉及到异氰酸酯衍生的 TDG 的瞬时安装，而不是像以前的 TDG 激活 C-C 键所依赖的羰基缩合反应。
