Bond-Forming Processes Enabled by Silicon-Masked Aryl- and Alkyl-Substituted Diazenes.

Abstract

Aryl- and alkyldiimides (R-N═NH with R = aryl or alkyl) are elusive intermediates of valuable synthetic use, as they are assumed to be transient species in processes involving both carbon (with concomitant loss of N2) and nitrogen nucleophiles (with conservation of the N═N moiety). The actual compounds are fragile and as such not bench stable which is why they have not yet found the attention they deserve. Conversely, early contributions showed that the stability of the parent diimide is significantly increased by replacing the hydrogen atom by a silyl group, but the synthetic applicability of these silicon-protected aryl- and alkyldiazenes has been far less explored, in part due to the absence of general procedures for their preparation. This Perspective provides an overview of the underexplored diazene chemistry that has witnessed considerable progress in recent years and highlights the potential of this motif in a range of synthetically useful (catalytic) transformations. The rediscovered silicon-masked diazenes constitute a versatile platform possessing enhanced stability and tamed reactivity in comparison to the parent hydrogen-substituted diimides. Aryl, diazenyl, and alkyl anionic key intermediates can be selectively generated in situ under Lewis base or transition metal catalysis, giving rise to novel synthetic approaches as viable alternatives to the already existing methodologies.