Exploiting Imine Photochemistry for Masked N-Centered Radical Reactivity
Exploiting Imine Photochemistry for Masked N-Centered Radical Reactivity
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DOI：
10.1002/anie.201909492
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发表时间：
2019-11-08
影响因子：
16.6
通讯作者：
Stephenson, Corey R. J.
中科院分区：
文献类型：
--
作者：
Staveness, Daryl;Collins, James L., III;Stephenson, Corey R. J.
这份报告详细介绍了一种以N为中心的掩蔽自由基策略的发展，该策略利用光能驱动环丙亚胺转化为1-氨基冰片。这一过程利用了光激亚胺的N-中心自由基特性，促进了环丙烷环的均质裂解和随后的自由基环化序列，在通往降冰片核心的途中形成了两个新的C-C键。作为激发态Schiff碱的N中心自由基性质的函数来实现成键反应性是独特的，在这种情况下只需要紫光。这种方法源源不断地运行，增强了翻译超越学术部门的潜力。这种光化学过程的操作简单性和(杂化)芳基稠合1-氨基冰片产品的结构新颖性预计将为制药和农用化工行业的发现工作提供宝贵的补充。
This report details the development of a masked N-centered radical strategy that harvests the energy of light to drive the conversion of cyclopropylimines to 1-aminonorbornanes. This process employs the N-centered radical character of a photoexcited imine to facilitate the homolytic fragmentation of the cyclopropane ring and the subsequent radical cyclization sequence that forms two new C-C bonds en route to the norbornane core. Achieving bond-forming reactivity as a function of the N-centered radical character of an excited state Schiff base is unique, requiring only violet light in this instance. This methodology operates in continuous flow, enhancing the potential to translate beyond the academic sector. The operational simplicity of this photochemical process and the structural novelty of the (hetero)aryl-fused 1-aminonorbornane products are anticipated to provide a valuable addition to discovery efforts in pharmaceutical and agrochemical industries.