Olefin Amine (OLA) Reagents for the Synthesis of Bridged Bicyclic and Spirocyclic Saturated N-Heterocycles by Catalytic HAT Reactions,Journal of the American Chemical Society

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Olefin Amine (OLA) Reagents for the Synthesis of Bridged Bicyclic and Spirocyclic Saturated N-Heterocycles by Catalytic HAT Reactions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-05-22 , DOI: 10.1021/jacs.9b05074
Ya-Yi Wang ₁ , Jeffrey W Bode ₁

Affiliation

Spiro- and bridged bicyclic structures are in demand for their sp3-rich frameworks that offer unique physiochemical properties and precisely positioned substituent groups. In order to rapidly access such molecules in a cross-coupling fashion we describe olefin amine (OLA) reagents for the transformation of aldehydes and ketones into all three topological types of bicyclic N-heterocycles: bridged, spiro-, and fused rings. The OLA reagents are easily prepared and allow the synthesis of complex molecular frameworks under operationally simple conditions that tolerate a wide array of functional groups. Investigations into the Mn or Fe promoted reaction pathway support a metal hydride hydrogen atom transfer (MH-HAT) to generate a C-centered radical that undergoes addition to an unactivated imine, leading to an N-centered radical. A catalytic cycle featuring regeneration of the metal catalyst by O2 and a second HAT to form the unprotected saturated N-heterocycle appears to be operative.

中文翻译：

用于通过催化 HAT 反应合成桥连双环和螺环饱和 N-杂环的烯烃胺 (OLA) 试剂

螺旋和桥连双环结构需要富含 sp3 的框架，这些框架提供独特的理化性质和精确定位的取代基。为了以交叉偶联方式快速访问此类分子，我们描述了烯烃胺 (OLA) 试剂，用于将醛和酮转化为所有三种拓扑类型的双环 N-杂环：桥环、螺环和稠环。OLA 试剂很容易制备，并允许在操作简单的条件下合成复杂的分子框架，可耐受多种官能团。对 Mn 或 Fe 促进的反应途径的研究支持金属氢化物氢原子转移 (MH-HAT) 以生成 C 中心自由基，该自由基与未活化的亚胺加成，导致 N 中心自由基。

更新日期：2019-05-22

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