Department of Chemistry, University of Michigan, Ann Arbor, Michigan 48109, United States.
J Am Chem Soc. 2021 Dec 22;143(50):21223-21228. doi: 10.1021/jacs.1c10541. Epub 2021 Dec 13.
Amines containing bridged bicyclic carbon skeletons are desirable building blocks for medicinal chemistry. Herein, we report the conversion of bicyclo[1.1.1]pentan-1-amines to a wide range of polysubstituted bicyclo[3.1.1]heptan-1-amines through a photochemical, formal (4 + 2)-cycloaddition of an intermediate imine diradical. To our knowledge, this is the first reported method to convert the bicyclo[1.1.1]pentane skeleton to the bicyclo[3.1.1]heptane skeleton. Hydrolysis of the imine products gives complex, sp-rich primary amine building blocks.
含桥环双环碳骨架的胺类是药物化学中理想的构建模块。在此，我们报告了通过光化学方法，将双环[1.1.1]戊-1-胺转化为一系列多取代的双环[3.1.1]庚-1-胺，其中涉及到一个中间亚胺自由基的[4+2]-环加成反应。据我们所知，这是首次报道的将双环[1.1.1]戊烷骨架转化为双环[3.1.1]庚烷骨架的方法。亚胺产物的水解得到复杂的、富含 sp 杂化的伯胺构建模块。
