Dey Jayanta, Banerjee Nayan, Daw Swikriti, Guin Joyram
School of Chemical Sciences, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Jadavpur, Kolkata, 700032, India.
Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202312384. doi: 10.1002/anie.202312384. Epub 2023 Sep 18.
Utilization of oxime ethers as bifunctional reagents remains unknown. Herein, we present a mechanistically distinct strategy that enables oximesulfonylation of olefins using sulfonyl-oxime-ethers as bifunctional reagents under metal-free photochemical conditions. Via concomitant C-S and C-C bond formation, the process permits incorporation of oxime and sulfonyl groups into olefins in a complete atom-economic fashion, providing rapid access to multi-functionalized β-sulfonyl oxime ethers with good yields and stereoselectivity. The method is amenable to functionalization of complex bioactive molecules and is shown to be scalable. A radical chain mechanism initiated via photochemical Hydrogen Atom Transfer (HAT) mediated N-O bond cleavage is suggested for the process, based on our results on mechanistic investigations.
肟醚作为双功能试剂的应用尚不清楚。在此，我们提出了一种机制独特的策略，该策略能够在无金属光化学条件下使用磺酰基肟醚作为双功能试剂实现烯烃的肟磺酰化反应。通过同时形成C-S键和C-C键，该过程能够以完全原子经济的方式将肟基和磺酰基引入烯烃中，从而以良好的产率和立体选择性快速获得多官能化的β-磺酰基肟醚。该方法适用于复杂生物活性分子的官能化，并且具有可扩展性。基于我们的机理研究结果，我们认为该过程是通过光化学氢原子转移（HAT）介导的N-O键断裂引发的自由基链机制。
