Recent advances in metal free- and late transition metal-catalysed hydroamination of unactivated alkenes

Abstract

This Perspective article outlines some of the recent advancements in the development of (chiral) metal-free and late transition metal catalysts for hydroamination of unactivated alkenes.

Recent Advances on the Chemistry of POCOP–Nickel Pincer Compounds

“…In general, intramolecular hydroamination proceeds faster than intermolecular reactions both thermodynamically and kinetically. In order to promote the hydroamination of C-C unsaturations, a wide variety of catalysts have been developed [87,88]. In the case of POCOP-Ni complexes, the first reports employing these compounds as catalysts for the hydroamination of unsaturated nitriles were reported in 2007 [89].…”

Hydroaminations of Alkenes: A Radical, Revised, and Expanded Version

“…[1] Among the numerous concepts for forging aC ÀNb ond, the hydroamination of olefins constitutes an especially attractive strategy,w hich relies upon olefins and amines as most basic, widely available, yet diverse families of starting materials. [2] Today,avast arsenal of metal-catalyzed hydroamination methods are available (Scheme 1). Depending on the nature of the employed metal catalyst and substrates,t he reaction mechanism can be based on one of two general activation modes: Thef ormation of active amido or imido complexes is mostly observed with Lewis acidic catalysts (alkaline earth, rare earth, early transition metals).…”

“…employed metal catalyst and substrates,t he reaction mechanism can be based on one of two general activation modes: Thef ormation of active amido or imido complexes is mostly observed with Lewis acidic catalysts (alkaline earth, rare earth, early transition metals). [2] Late transition metals and Group 11 and 12 metals mostly undergo coordinative p-activation of the alkene. [2] Contrary to this,e lectrophilic aminations have been reported with hydroxylamine derivatives.…”

“…[2] Late transition metals and Group 11 and 12 metals mostly undergo coordinative p-activation of the alkene. [2] Contrary to this,e lectrophilic aminations have been reported with hydroxylamine derivatives. [3] These strategies require the employment of ahydride reagent (hydrosilane,alkyl magnesium halide).…”

Intramolecular Alkene Aminocarbonylation Using Concerted Cycloadditions of Amino‐Isocyanates

“…Conversely,m etal-free reactions allowing effective CÀNb ond formation from simple and readily accessible reagents have also attracted significant interest in recent years. [5] In our efforts to develop metal-free alkene amination reactions, we have demonstrated the utility of bifunctionalr eagentsf or the formation of CÀNb onds from alkenes, alkynes and allenesu nder metal-free, thermal conditions. [6,7] In particular,h ydroxylamines provedt ob ee ffective reagents for intraand intermolecularC ope-type (concerted) alkene hydroaminations.…”