Tabey Alexis, Vemuri Pooja Y, Patureau Frederic W
Institute of Organic Chemistry, RWTH Aachen University Landoltweg 1 52074 Aachen Germany
Chem Sci. 2021 Oct 19;12(43):14343-14352. doi: 10.1039/d1sc03851f. eCollection 2021 Nov 10.
The relatively high electronegativity of nitrogen makes N-N bond forming cross-coupling reactions particularly difficult, especially in an intermolecular fashion. The challenge increases even further when considering the case of dehydrogenative N-N coupling reactions, which are advantageous in terms of step and atom economy, but introduce the problem of the oxidant in order to become thermodynamically feasible. Indeed, the oxidizing system must be designed to activate the target N-H bonds, while at the same time avoid undesired N-N homocoupling as well as C-N and C-C coupled side products. Thus, preciously few intermolecular hetero N-N cross-dehydrogenative couplings exist, in spite of the central importance of N-N bonds in organic chemistry. This review aims at analyzing these few rare cases and provides a perspective for future developments.
氮的相对较高电负性使得形成N-N键的交叉偶联反应特别困难，尤其是分子间的反应。当考虑脱氢N-N偶联反应的情况时，挑战进一步增加，这类反应在步骤和原子经济性方面具有优势，但为了使其在热力学上可行而引入了氧化剂的问题。实际上，氧化体系必须设计成既能激活目标N-H键，同时又能避免不希望的N-N自偶联以及C-N和C-C偶联副产物。因此，尽管N-N键在有机化学中至关重要，但分子间杂原子N-N交叉脱氢偶联反应却极为罕见。本综述旨在分析这些少数罕见的案例，并为未来的发展提供一个视角。
