Kuznetsova Elizaveta A, Rysaeva Regina R, Smolobochkin Andrey V, Gazizov Almir S, Gerasimova Tatyana P, Gerasimova Daria P, Lodochnikova Olga A, Morozov Vladimir I, Vatsadze Sergey Z, Burilov Alexander R, Pudovik Michail A
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, Arbuzova Street 8, Kazan 420088, Russian Federation.
Kazan National Research Technological University, Karla Marksa Street 68, Kazan 420015, Russian Federation.
Org Lett. 2024 May 24;26(20):4323-4328. doi: 10.1021/acs.orglett.4c01305. Epub 2024 May 9.
In contrast to hypervalent iodine compounds, the chemistry of their sulfur analogues has been considerably less explored. Herein, we report the direct C-H bond thiolation of electron-rich heterocycles, arenes, and 1,3-dicarbonyls by dichlorosulfuranes under mild conditions. Mechanistic studies and density functional theory calculations suggest the radical chain mechanism of the disclosed transformation. The key to success is attributed to a strikingly low S-Cl bond dissociation energy, which enables the generation of radical species upon exposure to daylight.
与高价碘化合物相比，其硫类似物的化学研究要少得多。在此，我们报道了在温和条件下，二氯硫烷对富电子杂环、芳烃和1,3 - 二羰基化合物进行直接的C - H键硫醇化反应。机理研究和密度泛函理论计算表明，所公开的转化反应遵循自由基链机制。成功的关键在于S - Cl键离解能极低，这使得在光照下能够产生自由基物种。
