Krivovicheva Vasilisa, Gangireddy Madhu Sudhana Reddy, Liu Anqi, Maya Leonardo B, Mebel Alexander M, Bukhryakov Konstantin V
Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States.
J Am Chem Soc. 2025 Jun 18;147(24):20212-20217. doi: 10.1021/jacs.5c05880. Epub 2025 Jun 6.
The incorporation of carbon isotopes into bioactive compounds is of great importance in chemistry, biology, and medicine. Especially valuable are catalytic procedures that rely on a limited collection of available labeled materials. Recently we introduced a conceptually novel solution to carbon isotope exchange (CIE) for terminal olefins based on the preference of V alkylidenes for degenerate metathesis. However, the previous report utilized a V catalyst that suffered from functional group tolerance due to the high electrophilicity of the V center, making it impractical for biological compounds. Herein, we utilized V catalysts containing electron-donating groups to overcome those challenges. We utilize isotopically labeled substituted styrene as a labeled ═CH moiety source, prepared from C-labeled iodomethane. The isotope source can be easily removed from the reaction mixture, recovered, and reused. A diverse range of terminal alkenes, including bioactive molecules, were tested to showcase the capabilities and limitations of the developed method.
碳同位素掺入生物活性化合物在化学、生物学和医学中具有重要意义。特别有价值的是那些依赖于有限种类可用标记材料的催化过程。最近，我们基于V亚烷基对简并复分解的偏好，为末端烯烃引入了一种概念上新颖的碳同位素交换（CIE）解决方案。然而，先前的报告使用的V催化剂由于V中心的高亲电性而存在官能团耐受性问题，这使得它对于生物化合物不实用。在此，我们利用含有供电子基团的V催化剂来克服这些挑战。我们使用由C标记的碘甲烷制备的同位素标记的取代苯乙烯作为标记的═CH部分来源。同位素源可以很容易地从反应混合物中除去、回收并重复使用。测试了包括生物活性分子在内的多种末端烯烃，以展示所开发方法的能力和局限性。
