Visible-Light-Mediated Alkenylation, Allylation, and Cyanation of Potassium Alkyltrifluoroborates with Organic Photoredox Catalysts.
Visible-Light-Mediated Alkenylation, Allylation, and Cyanation of Potassium Alkyltrifluoroborates with Organic Photoredox Catalysts.
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DOI：
10.1021/acs.joc.6b01207
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发表时间：
2016-08-19
期刊：
影响因子：
--
通讯作者：
Molander GA
中科院分区：
文献类型：
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作者：
Heitz DR;Rizwan K;Molander GA
报道了在光氧化还原条件下制备受保护的烯丙胺和烷基腈的不含铱和钌的方法。一种廉价的有机染料曙红 Y 通过 α-氨甲基自由基加成-消除途径催化 Boc 保护的 α-氨甲基三氟硼酸钾与各种取代的烯基砜的偶联。烯丙基胺和高烯丙基胺以中等产率形成，具有高 E/Z 选择性。使用甲苯磺酰氰作为自由基捕获剂扩展了机械方法，从而能够通过福住吖啶鎓催化过程将烷基三氟硼酸盐转化为腈。
Iridium- and ruthenium-free approaches to protected allylic amines and alkyl nitriles under photoredox conditions are reported. An inexpensive organic dye, eosin Y, catalyzes coupling of Boc-protected potassium α-aminomethyltrifluoroborates with a variety of substituted alkenyl sulfones through an α-aminomethyl radical addition–elimination pathway. Allylic and homoallylic amines were formed in moderate yields with high E/Z selectivity. The mechanistic approach was extended using tosyl cyanide as a radical trap, enabling the conversion of alkyltrifluoroborates to nitriles via a Fukuzumi acridinium-catalyzed process.