Photo-induced radical-ionic bis-functional-group transfer reactions from single, readily available oxime-based surrogates containing a sulfinyl tether

该项目旨在开发一种新的试剂家族，在光化学照射下，能够将两个分子片段从一个替代物转移到C-C多重键上。试剂设计由可访问性（简单的合成操作，然后是直接的纯化程序）和可扩展性（多克规模）以及可编程模块化指导。这些边界条件是满足一种新的肟基平台含有亚磺酰基基团作为系链。与其他肟衍生系统的光化学能量转移催化不同，目标试剂的光氧化还原催化活化涉及单电子转移，从而导致其断裂成自由基和阴离子沿着二氧化硫。自由基将添加到不饱和C-C键，然后通过光催化剂的氧化淬灭进行自由基-极性交叉。然后，所得的阳离子中间体被先前释放的阴离子捕获。这种策略的可行性已经被我们用于烯烃、联烯和炔的二卤代反应，使用易于制备的二卤代物。通过采用更精细的亚磺酰基束缚的肟基试剂，我们计划完成卤化氰和氯硅烷的转移，以及C-C键的形成，氯氟烃和酰氯到烯烃和其他多重键。

This project aims at the development of a new family of reagents that, under photochemical irradiation, enables the transfer of two molecular fragments from one surrogate onto C–C multiple bonds. The reagent design is guided by accessibility (simple synthetic operations followed by straightforward purification procedures) and scalability (multigram scale) as well as programmable modularity. These boundary conditions are met by a novel oxime-based platform containing a sulfinyl group as a tether. Unlike photochemical energy-transfer catalysis with other oxime-derived systems, the photoredox-catalyzed activation of the targeted reagents involves single-electron transfer, thereby leading to their fragmentation into a radical and an anion along with sulfur dioxide. The radical would add to the unsaturated C–C bond followed by radical–polar crossover through oxidative quenching by the photocatalyst. The resulting cationic intermediate is then captured by the previously released anion. The viability of this strategy has already been shown by us for a dihalogenation of alkenes, allenes, and alkynes using an easy-to-make dihalogen surrogate. By employing more elaborate sulfinyl-tethered, oxime-based reagents, we plan to accomplish the transfer of cyanogen halides and silyl chlorides as well as, with C–C bond formation, chlorofluorocarbons and acyl chloride to alkenes and other multiple bonds.