Selective Radical-Radical Cross-Couplings: Design of a Formal β-Mannich Reaction.
Selective Radical-Radical Cross-Couplings: Design of a Formal β-Mannich Reaction.
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DOI：
10.1021/jacs.5b05376
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发表时间：
2015-07-08
影响因子：
15
通讯作者：
MacMillan DW
中科院分区：
文献类型：
--
作者：
Jeffrey JL;Petronijević FR;MacMillan DW
通过光氧化还原催化和有机催化的协同作用，实现了环酮与亚胺的直接β-偶联。通过烯胺和氧化性光氧化还原催化作用从酮衍生的瞬时β-烯胺基自由基很容易与持久的α-氨基自由基在高度选择性的杂原子自由基-自由基偶联中联合收割机结合。这种生成γ-氨基酮的新途径是基于使用DABCO作为碱和电子转移剂。该方案还正式允许通过芳基醛、胺和酮的化学选择性三组分偶联直接合成β-曼尼希产物。
A direct β-coupling of cyclic ketones with imines has been accomplished via the synergistic combination of photoredox catalysis and organocatalysis. Transient β-enaminyl radicals derived from ketones via enamine and oxidative photoredox catalysis readily combine with persistent α-amino radicals in a highly selective hetero radical–radical coupling. This novel pathway to γ-aminoketones is predicated upon the use of DABCO as both a base and an electron transfer agent. This protocol also formally allows for the direct synthesis of β-Mannich products via a chemoselective three-component coupling of aryl aldehydes, amines, and ketones.