Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Department of Chemical Science and Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8550, Japan.
J Am Chem Soc. 2021 Apr 21;143(15):5629-5635. doi: 10.1021/jacs.1c00887. Epub 2021 Mar 26.
We have developed photoboosted stannylation reactions of terminal alkynes (linear-selective hydrostannylation) and fluoroarenes (defluorostannylation), in which the stannyl anion is photoexcited to an excited triplet (T) stannyl diradical species. This unprecedented T-stannyl diradical species shows completely different reactivity and selectivity from those of stannyl anions and stannyl radicals. This methodology is operationally simple, has broad functional group tolerance, and proceeds in high yield without the need for any catalyst.
我们开发了末端炔烃的光增感锡化反应(线性选择性氢锡化)和氟代芳烃的光增感脱氟锡化反应,其中锡负离子被光激发到激发三重态(T)锡自由基双自由基物种。这种前所未有的 T-锡自由基双自由基物种表现出与锡负离子和锡自由基完全不同的反应性和选择性。该方法操作简单,具有广泛的官能团耐受性,并且在无需任何催化剂的情况下以高产率进行。