Abstract
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.
Highlights
IntroductionNitrogen–nitrogen bond containing molecules are ubiquitously present in natural products[1] and are increasingly used for applications in the eld of organic materials such as organic light-emitting diodes (OLEDs)[2] or covalent organic frameworks (COFs).[3]
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
Nitrogen–nitrogen bond containing molecules are ubiquitously present in natural products[1] and are increasingly used for applications in the eld of organic materials such as organic light-emitting diodes (OLEDs)[2] or covalent organic frameworks (COFs).[3]
Summary
Nitrogen–nitrogen bond containing molecules are ubiquitously present in natural products[1] and are increasingly used for applications in the eld of organic materials such as organic light-emitting diodes (OLEDs)[2] or covalent organic frameworks (COFs).[3]. Because N–H functional groups are o en inherently nucleophilic due to their electronic lone pair as well as their relative so ness, this third option is adapted for the synthesis of intermolecular hetero N–N bonds Side reactions such as N–N homo coupling reactions are thereby avoided due to the philicity control of the (hetero) N–N bond forming nucleophilic substitution process. CDC methods, including N–N bond forming CDCs, must be designed to allow interception of the rst oxidized coupling partner with the second While this may seem challenging, the nature and structure of the oxidants, solvents, and catalysts can be tuned to enable this hetero interception process because these have per design a very intimate relationship with the substrates.
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