Selvakumar Sermadurai, Sakamoto Ryu, Maruoka Keiji
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto, 606-8502, Japan), Fax: (+81)75-753-4041.
Chemistry. 2016 May 4;22(19):6552-5. doi: 10.1002/chem.201600425. Epub 2016 Mar 24.
Diastereoselective radical hydroacylation of chiral alkylidenemalonates with aliphatic aldehydes is realized by the combination of a hypervalent iodine(III) reagent and UV-light irradiation. The reaction is initiated by the photolysis of hypervalent iodine(III) reagents under mild, metal-free conditions, and is the first example of diastereoselective addition of acyl radicals to olefins to afford chiral ketones in a highly stereoselective fashion. The obtained optically active ketones are useful chiral synthons, as exemplified by the short formal synthesis of (-)-methyleneolactocin.
通过高价碘（III）试剂与紫外光照射相结合，实现了手性亚烷基丙二酸酯与脂肪醛的非对映选择性自由基氢酰化反应。该反应在温和、无金属的条件下由高价碘（III）试剂的光解引发，是酰基自由基以高度立体选择性方式对烯烃进行非对映选择性加成以得到手性酮的首个实例。所得到的光学活性酮是有用的手性合成子，（-）-亚甲基乳杆菌素的简短形式合成即为例证。
