Shu Xiao-Rong, Li Mu-Han, Wu Cuiyan, Luo Xi-Ni, Yang Dong-Qing, Yang Ming-Qi, Lu Yue-Jiao, Ge Guo-Ping, Liu Jidan, Wei Wen-Ting
School of Materials Science and Chemical Engineering, Ningbo University, Zhejiang, 315211, China.
School of Chemistry and Chemical Engineering/Institute of Clean Energy and Materials/Guangzhou Key Laboratory for Clean Energy and Materials, Guangzhou University, Guangzhou, 510006, China.
Org Lett. 2024 Jul 12;26(27):5705-5712. doi: 10.1021/acs.orglett.4c01798. Epub 2024 Jun 27.
Selenosulfones, as pivotal pharmaceutical molecule frameworks, have become a research hotspot in modern organic synthesis due to their vital need for efficient preparation. Herein, we have developed an iron-catalyzed four-component controllable radical tandem reaction of allenes involving cycloketone oxime esters, 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct (DABSO), and diphenyl diselenides for the synthesis of complex selenosulfones. This is the first case of achieving the 1,2-selenosulfonylation of allenes via a radical process, wherein precise control of radical rates and polarity matching enhance high regioselective conversion. The reaction conditions are ecofriendly and mild with step-efficiency by forming two new C-S bonds and one C-Se bond in one pot. Moreover, the 1,2-selenosulfonylation of allenes can be achieved by replacing cycloketone oxime esters with aryldiazonium tetrafluoroborates in this system.
硒砜作为关键的药物分子骨架，因其高效制备的迫切需求，已成为现代有机合成中的一个研究热点。在此，我们开发了一种铁催化的、涉及环酮肟酯、1,4-二氮杂双环[2.2.2]辛烷双（二氧化硫）加合物（DABSO）和二苯基二硒醚的丙二烯四组分可控自由基串联反应，用于合成复杂的硒砜。这是首例通过自由基过程实现丙二烯的1,2-硒砜基化反应，其中对自由基速率的精确控制和极性匹配提高了区域选择性转化。该反应条件环保且温和，通过一锅法形成两个新的C-S键和一个C-Se键，具有步骤高效性。此外，在该体系中用四氟硼酸芳基重氮盐取代环酮肟酯，也可实现丙二烯的1,2-硒砜基化反应。
