Given the importance of aryl amines in various disciplines, the synthesis of such type of compounds has inspired longstanding interests in synthetic community. While taking a close look at the literature precedents, in almost all cases, anilines were wildly employed precursors for those well established coupling techniques. In this realm, one of the well known C-N coupling strategy should in principle be the Buchwald-Hartwig amination, which was independently established in 1995 by Buchwald's group and Hartwig's group.
Since the startup of my independent career in 2018, we wondered if a more step-economical approach toward the C-N coupling technique could be feasible? As is well known that from a classical synthesis point of view, the anilines is reasonably obtained by the reduction of nitroarenes. We believed that a reductive C-N coupling technique is indeed possible and in high demand, and imagining if the intermediates can be proved to be the in-situ generated anilines, then the corresponding reaction can in principle be named as "reductive Buchwald-Hartwig amination".
Recorded herein is the repertoire for the first reductive Buchwald-Hartwig amination by harnessing synthetically upstream nitroarenes as the coupling precursors. This approach represents a one step foward especially with the consideration of availability and stability of coupling partners, compared with Buchwald-Hartwig amination technique.
https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/ejoc.202300494