Meher Prahallad, Parida Sushanta Kumar, Mahapatra Sanat Kumar, Roy Lisa, Murarka Sandip
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Rajasthan, 342037, India.
IOC Odisha Campus Bhubaneswar, Institute of Chemical Technology Mumbai, Bhubaneswar, 751013, India.
Chemistry. 2024 Nov 4;30(61):e202402969. doi: 10.1002/chem.202402969. Epub 2024 Oct 16.
In recent times, diaryliodonium reagents (DAIRs) have witnessed a resurgence as arylating reagents, especially under photoinduced conditions. However, reactions proceeding through electron donor-acceptor (EDA) complex formation with DAIRs are restricted to electron-rich reacting partners serving as donors due to the well-known cage effect. We discovered a practical and high-yielding visible-light-induced EDA platform to generate aryl radicals from the corresponding DAIRs and use them to synthesize key chalcogenides. In this process, an array of DAIRs and dichalcogenides react in the presence of 1,4 diazabicyclo[2.2.2]octane (DABCO) as a cheap and readily available donor, furnishing a variety of di(hetero)aryl and aryl/alkyl chalcogenides in good yields. The method is scalable, features a broad scope with good yields, and operates under open-to-air conditions. The photoinduced chalcogenation technology is suitable for late-stage functionalizations and disulfide bioconjugations and facilitates access to biologically relevant thioesters, dithiocarbamates, sulfoximines, and sulfones. Moreover, the method applies to synthesizing diverse pharmaceuticals, such as vortioxetine, promazine, mequitazine, and dapsone, under amenable conditions.
近年来，二芳基碘鎓试剂（DAIRs）作为芳基化试剂再度兴起，尤其是在光诱导条件下。然而，由于众所周知的笼效应，通过与DAIRs形成电子供体-受体（EDA）络合物进行的反应仅限于作为供体的富电子反应伙伴。我们发现了一个实用且高产的可见光诱导EDA平台，可从相应的DAIRs生成芳基自由基，并利用它们合成关键的硫族化物。在此过程中，一系列DAIRs和二硫族化物在1,4-二氮杂双环[2.2.2]辛烷（DABCO）作为廉价且易于获得的供体存在下反应，以良好的产率提供各种二（杂）芳基和芳基/烷基硫族化物。该方法具有可扩展性，适用范围广且产率良好，并在露天条件下操作。光诱导硫族化技术适用于后期官能团化和二硫键生物共轭，并有助于获得与生物相关的硫酯、二硫代氨基甲酸盐、磺胺肟和砜。此外，该方法适用于在合适的条件下合成多种药物，如伏硫西汀、丙嗪、美喹他嗪和氨苯砜。
