Yamane Mina, Kanzaki Yamato, Mitsunuma Harunobu, Kanai Motomu
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Org Lett. 2022 Feb 25;24(7):1486-1490. doi: 10.1021/acs.orglett.2c00138. Epub 2022 Feb 15.
Despite the sophistication of C-H functionalization as one of the most powerful tools in organic synthesis, methodology for performing hydrogen-atom transfer of unactivated alkanes remains rather scarce. Herein, we describe chlorine radical-catalyzed C(sp)-H photoalkylation using titanium(IV) chloride via a ligand-to-metal charge transfer process. Enabled by the unique properties of this abundant metal salt, the reaction not only effected the coupling of various alkanes with radical acceptors but also was shown to be applicable to direct photoalkylation of aromatic ketones.
尽管碳氢官能团化作为有机合成中最强大的工具之一已经非常成熟，但用于未活化烷烃氢原子转移的方法仍然相当稀少。在此，我们描述了通过配体到金属的电荷转移过程，使用四氯化钛进行氯自由基催化的C(sp)-H光烷基化反应。受这种丰富金属盐独特性质的影响，该反应不仅实现了各种烷烃与自由基受体的偶联，而且还被证明适用于芳香酮的直接光烷基化反应。
