Zhu Shaoqun, Pathigoolla Atchutarao, Lowe Grace, Walsh Darren A, Cooper Mick, Lewis William, Lam Hon Wai
The GSK Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU, UK.
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.
Chemistry. 2017 Dec 11;23(69):17598-17604. doi: 10.1002/chem.201704380. Epub 2017 Nov 16.
The generation of sulfonyl radicals from sulfonyl azides using visible light and a photoactive iridium complex in THF is described. This process was used to promote sulfonylative and azidosulfonylative cyclizations of enynes to give several classes of highly functionalized heterocycles. The use of THF as the solvent is critical for successful reactions. The proposed mechanism of radical initiation involves the photosensitized formation of a triplet sulfonyl nitrene, which abstracts a hydrogen atom from THF to give a tetrahydrofuran-2-yl radical, which then reacts with the sulfonyl azide to generate the sulfonyl radical.
描述了在四氢呋喃（THF）中使用可见光和光活性铱配合物从磺酰叠氮化物生成磺酰基自由基的过程。该过程用于促进烯炔的磺酰化和叠氮磺酰化环化反应，以得到几类高度官能化的杂环化合物。使用THF作为溶剂对于反应的成功至关重要。提出的自由基引发机制涉及三重态磺酰基氮烯的光敏形成，其从THF中提取一个氢原子生成四氢呋喃-2-基自由基，然后该自由基与磺酰叠氮化物反应生成磺酰基自由基。
