State Key Laboratory of Physical Chemistry of Solid Surfaces, Innovation Center of Chemistry for Energy Materials, Key Laboratory of Chemical Biology of Fujian Province, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, People's Republic of China.
Nat Commun. 2019 Oct 31;10(1):4953. doi: 10.1038/s41467-019-13024-5.
The 1,2-diamine motif is widely present in natural products, pharmaceutical compounds, and catalysts used in asymmetric synthesis. The simultaneous introduction of two amino groups across an alkene feedstock is an appealing yet challenging approach for the synthesis of 1,2-diamines, primarily due to the inhibitory effect of the diamine products to transition metal catalysts and the difficulty in controlling reaction diastereoselectivity and regioselectivity. Herein we report a scalable electrocatalytic 1,2-diamination reaction that can be used to convert stable, easily available aryl alkenes and sulfamides to 1,2-diamines with excellent diastereoselectivity. Monosubstituted sulfamides react in a regioselective manner to afford 1,2-diamines bearing different substituents on the two amino groups. The combination of an organic redox catalyst and electricity not only obviates the use of any transition metal catalyst and oxidizing reagent, but also ensures broad reaction compatibility with a variety of electronically and sterically diverse substrates.
1,2-二胺基结构广泛存在于天然产物、药物化合物和不对称合成中使用的催化剂中。通过烯烃进料物同时引入两个氨基基团是合成 1,2-二胺的一种吸引人但具有挑战性的方法，主要是由于二胺产物对过渡金属催化剂的抑制作用以及难以控制反应的非对映选择性和区域选择性。在此，我们报告了一种可扩展的电催化 1,2-二胺化反应，可用于将稳定、易得的芳基烯烃和磺胺转化为具有优异非对映选择性的 1,2-二胺。单取代磺胺以区域选择性方式反应，在两个氨基上带有不同取代基的 1,2-二胺。有机氧化还原催化剂和电力的结合不仅避免了使用任何过渡金属催化剂和氧化剂，而且还确保了与各种电子和空间位阻不同的底物具有广泛的反应相容性。
