Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, Shanghai 200062, China.
Chem Commun (Camb). 2020 Nov 18;56(89):13852-13855. doi: 10.1039/d0cc06465c. Epub 2020 Oct 21.
The importance of γ-keto sulfones in medicinal chemistry and organic synthesis is known. An efficient route to γ-keto sulfones via a metal-free reaction of cyclopropanols, sulfur dioxide and electron-deficient olefins is achieved. This reaction proceeds smoothly under mild conditions without the need of catalyst, oxidant or additive. A plausible mechanism is proposed, which occurs through a γ-keto sulfinate intermediate generated in situ from the reaction of cyclopropanol with sulfur dioxide. The γ-keto sulfinate intermediate would be trapped by the electron-deficient olefin, resulting in the formation of γ-keto sulfones. Various functional groups in the cyclopropanols and electron-deficient olefins are compatible in this transformation.
γ-酮砜在药物化学和有机合成中的重要性是众所周知的。本文实现了一种通过无金属反应，由环丙醇、二氧化硫和缺电子烯烃来合成γ-酮砜的有效方法。该反应在温和的条件下顺利进行，无需催化剂、氧化剂或添加剂。提出了一种合理的反应机理，该机理是通过环丙醇与二氧化硫反应原位生成γ-酮亚磺酸盐中间体来实现的。γ-酮亚磺酸盐中间体被缺电子烯烃捕获，生成γ-酮砜。在这个转化过程中，环丙醇和缺电子烯烃中的各种官能团都具有兼容性。
