Chemical synthesis based on the skeletal variation has been prolifically utilized as an attractive approach for modification of molecular properties. Given the ubiquity of unstrained cyclic amines, the ability to directly alter such motifs would grant an efficient platform to access unique chemical space. Here, we report a highly efficient and practical strategy that enables the selective ring-opening functionalization of unstrained cyclic amines. The use of difluorocarbene leads to a wide variety of multifaceted acyclic architectures, which can be further diversified to a range of distinctive homologative cyclic scaffolds. The virtue of this deconstructive strategy is demonstrated by successful modification of several natural products and pharmaceutical analogues.

基于骨架变异的化学合成已被广泛用作修饰分子特性的有吸引力的方法。鉴于无限制的环胺无处不在，直接改变这些基序的能力将提供一个有效的平台来访问独特的化学空间。在这里，我们报告了一种高效实用的策略，可以使无应变的环胺选择性开环功能化。二氟卡宾的使用导致了各种各样的多面无环结构，可以进一步多样化为一系列独特的同系环状支架。几种天然产物和药物类似物的成功修饰证明了这种解构策略的优点。