Department of Chemistry , Columbia University , New York , New York 10027 , United States.
J Am Chem Soc. 2019 May 1;141(17):6807-6811. doi: 10.1021/jacs.9b02156. Epub 2019 Apr 18.
We have developed a Rh(III)-catalyzed diastereoselective [2+1] annulation onto allylic alcohols initiated by alkenyl C-H activation of N-enoxyphthalimides to furnish substituted cyclopropyl-ketones. Notably, the traceless oxyphthalimide handle serves three functions: directing C-H activation, oxidation of Rh(III), and, collectively with the allylic alcohol, in directing cyclopropanation to control diastereoselectivity. Allylic alcohols are shown to be highly reactive olefin coupling partners leading to a directed diastereoselective cyclopropanation reaction, providing products not accessible by other routes.
我们开发了一种 Rh(III)催化的非对映选择性[2+1]环加成反应，通过烯基 C-H 活化 N-氧代邻苯二甲酰亚胺引发，用于合成取代的环丙基酮。值得注意的是，无痕迹的邻苯二甲酰亚胺基作为三种功能的试剂：导向 C-H 活化、Rh(III)的氧化，以及与烯丙醇一起，共同导向环丙烷化以控制非对映选择性。烯丙醇被证明是高度反应性的烯烃偶联试剂，导致定向非对映选择性环丙烷化反应，提供了其他途径无法获得的产物。
