Elfert Jonas, Frye Nils Lennart, Rempel Isabel, Daniliuc Constantin Gabriel, Studer Armido
Organisch-Chemisches Institut, Universität Münster, Münster, Germany.
Nat Commun. 2024 Aug 22;15(1):7230. doi: 10.1038/s41467-024-51706-x.
We herein report radical hydroazidation and hydrohalogenation of mono-, di- and trisubstituted alkenes through iron catalysis. The alkene moiety that often occurs as a functionality in natural products is readily transformed into useful building blocks through this approach. Commercially available tosylates and α-halogenated esters are used as radical trapping reagents in combination with silanes as reductants. The reported radical Markovnikov hydroazidation, hydrobromination, hydrochlorination, and hydroiodination occur under mild conditions. These hydrofunctionalizations are valuable and practical alternatives to ionic hydrohalogenations with the corresponding mineral acids that have to be run under harsher acidic conditions, which diminishes the functional group tolerance. Good to excellent diastereoselectivities can be obtained for the hydrofunctionalization of cyclic alkenes.
我们在此报告通过铁催化实现单取代、二取代和三取代烯烃的自由基氢叠氮化和氢卤化反应。天然产物中经常作为官能团出现的烯烃部分，通过这种方法很容易转化为有用的结构单元。市售的甲苯磺酸盐和α-卤代酯与硅烷作为还原剂结合用作自由基捕获试剂。所报道的自由基马氏氢叠氮化、氢溴化、氢氯化和氢碘化反应在温和条件下进行。这些氢官能团化反应是使用相应无机酸进行离子氢卤化反应的有价值且实用的替代方法，后者必须在更苛刻的酸性条件下进行，这会降低官能团耐受性。对于环状烯烃的氢官能团化反应，可以获得良好至优异的非对映选择性。
