You Lin, Chen Chuo
Department of Biochemistry, UT Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, TX 75390-9038, USA.
Tetrahedron. 2018 Feb 22;74(8):769-772. doi: 10.1016/j.tet.2017.12.027. Epub 2017 Dec 15.
The ability of triplet ketones to abstract a hydrogen atom from hydrocarbons is reminiscent of that of the high-spin metal-oxo complexes in C-H oxidation enzymes. In practice, the reactivity of triplet ketones is easier to control and applicable to promoting a wider range of reactions. We demonstrate herein the synthetic utility of triplet ketone-mediated -addition of methanol to cyclopentenone derivatives with an expedient synthesis of the core skeleton of the [3+2]-type dimeric pyrrole-imidazole alkaloids. Remarkably, this photochemical C-H functionalization reaction is highly regioselective and can tolerate a good range of functional groups.
三重态酮从碳氢化合物中提取氢原子的能力让人联想到C-H氧化酶中的高自旋金属氧配合物。实际上，三重态酮的反应性更易于控制，并且适用于促进更广泛的反应。我们在此展示了三重态酮介导的甲醇与环戊烯酮衍生物的 - 加成反应在合成[3+2]型二聚吡咯 - 咪唑生物碱核心骨架方面的实用性，该合成方法简便快捷。值得注意的是，这种光化学C-H官能团化反应具有高度的区域选择性，并且能够耐受多种官能团。
