Fokin Andrey A, Reshetylova Olga K, Bakhonsky Vladyslav V, Pashenko Alexander E, Kivernik Alena, Zhuk Tatyana S, Becker Jonathan, Dahl Jeremy E P, Carlson Robert M K, Schreiner Peter R
Department of Organic Chemistry, Igor Sikorsky Kiev Polytechnic Institute, Pr. Pobedy 37, 03056 Kiev, Ukraine.
Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany and Center for Materials Research, Heinrich-Buff-Ring 16, 35392 Giessen, Germany.
Org Lett. 2022 Jul 15;24(27):4845-4849. doi: 10.1021/acs.orglett.2c00982. Epub 2022 May 13.
We present a strategy for the skeletal editing of diamondoid structures to selectively displace methylene for heteroatom moieties in the carbon framework. This constitutes a synthetic approach to doping diamond-like structures with electron donor dopants (O, N, and S). The key steps involve two subsequent retro-Barbier fragmentations followed by cage reconstruction in the presence of a dopant. Remarkably, the incorporation of n-dopants reduces the strain of the diamondoid cage as shown through homodesmotic equations.
我们提出了一种对类金刚石结构进行骨架编辑的策略，以在碳骨架中选择性地用杂原子部分取代亚甲基。这构成了一种用电子供体掺杂剂（O、N和S）对类金刚石结构进行掺杂的合成方法。关键步骤包括两个连续的逆巴比耶碎片化反应，随后在掺杂剂存在下进行笼状结构重建。值得注意的是，如通过同系分解方程所示，n型掺杂剂的掺入降低了类金刚石笼的应变。
