摘要/Abstract
报道了一种可见光驱动的双功能中心手性金属铑配合物催化的不对称自由基加成反应,由对胺基苯乙酸生成的对胺基苄基自由基对α,β-不饱和酰基咪唑进行立体选择性的1,4-加成,以中高收率和高对映选择性合成了一系列加成产物.该反应具有对映选择性高、反应条件温和、操作简单等特点.根据对双功能中心手性金属配合物催化的研究和文献报道,提出了一个合理的反应机理.
关键词: 可见光催化, 双功能手性铑配合物, Giese自由基加成反应, 对胺基苄基自由基
A visible-light driven asymmetric Giese radical addition catalyzed by a bifunctional chiral-at-metal rhodium complex has been developed. para-Aminobenzyl radicals generated from para-aminophenylacetic acids could undergo a 1,4-addition in a highly enantioselective approach to α,β-unsaturated 2-acyl imidazoles, and a variety of corresponding adducts were obtained in moderate to high yields with excellent enantioselectivities. This reaction features high enantioselectivity, mild reaction conditions and an operationally simple procedure. A plausible reaction mechanism is proposed based on our research and literature precedents on dual functional chiral-at-metal catalysis.
Key words: visible-light photoredox catalysis, bifunctional chiral-at-metal rhodium complex, Giese radical addition, para-aminobenzyl radical
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