Unravelling nitrene chemistry from acyclic precursors: recent advances and challenges

Abstract

Recent advances in nitrene chemistry from acyclic precursors is reviewed in this paper. Early developments on nitrene chemistry predominantly focused on exploiting new nitrene precursors and inventing new types of...

Catalytic synthesis of azoarenes via metal-mediated nitrene coupling

“…[32][33][34] Of the different nitrene precursors that had been developed over the years, organoazides are most commonly used due to their ease of synthesis and their sustainable nature, as they produce only N 2 as a by-product. [35][36][37] The reaction is formally an oxidation of the metal center, thus generally requiring formally reduced metal precursors. Upon formation, a reactive metal-imido can undergo a nitrene-transfer reaction with substrates such as alkenes, alkynes, isocyanides, CO, and C-H bonds to form the corresponding products and to restore the formally reduced metal catalyst as shown in Fig.…”

Intermolecular amination of allenes via twofold photocatalytic nitrene transfer reactions

“…1,2 The introduction of an amine functional group -an amination reaction -is commonly achieved by textbook SN type reactions or by cross-coupling reactions in the presence of precious metal catalysts that often requires pre-functionalized building blocks, forcing reaction conditions and careful separation of trace impurities of the metal catalyst. The direct amination reaction at room temperature with reactive nitrogen-based intermediates, such as nitrogen-based radicals 3,4 or nitrenes, [5][6][7][8][9] is one of the main strategies to overcome these fundamental challenges. However, the basic nature of amines comprises one of the main drawbacks in the development of such reactions and can easily lead to complexation of metal catalysts resulting in reduced catalytic efficiency or even catalyst poisoning.…”

Hypervalent iodine (III) reagents and ammonia as useful combination for highly chemoselective N-transfer to low-valent organosulfur compounds and amines

“…Nitrenebased transformations mainly include C-H amination/amidation, aziridination, addition to unsaturated bonds, sulfimidation, etc. 2 Recent studies have extended the scope of nitrene chemistry exploiting the corresponding metal-nitrenes species obtained from iminoiodinanes as N-donors. These methodologies typically require Nprotected iminoiodinane species, easily generated from an hypervalent iodine (III) reagent and a suitable R-NH2 partner.…”