Copper‐Promoted and Copper‐Catalyzed Intermolecular Alkene Diamination

Abstract

Einfach Kupfer: In vicinaler Stellung befinden sich zwei unterschiedlich funktionalisierte Amine nach einer Kupfer(II)‐vermittelten intra‐ und intermolekularen Olefindiaminierung, bei der noch zusätzlich ein Kohlenstoffstereozentrum eingeführt wird. Ausgehend von chiralen Alkenen wurden hohe Diastereoselektivitäten erzielt.

Catalytic Enantioselective Alkene Aminohalogenation/Cyclization Involving Atom Transfer

“…[12] These reactions occur through a cis aminocupration followed by homolysis of the C–Cu II bond, thereby generating a primary carbon radical. [10c] The fate of the carbon radical is influenced by the substrate structure and reaction components, and both determine which difunctionalized product is formed.…”

“…In recent years, our group has developed a family of Cucatalyzed enantioselective alkene amination reactions, including carboamination, [10] aminooxygenation, [11] and diamination. [12] These reactions occur through a cis aminocupration followed by homolysis of the CÀCu II bond, thereby generating a primary carbon radical. [10c] The fate of the carbon radical is influenced by the substrate structure and reaction components, and both determine which difunctionalized product is formed.…”

Acyclic and Cyclic Ureas (Update 2013)

“…In an alternative approach, N-allylureas can also be cyclized to give imidazolidin-2-ones (Scheme 56). [162] The initial intermediates formed in this reaction are trapped intermolecularly by an aromatic amine and the underlying reaction therefore also represents a 1,2-diamination. It requires the presence of a transition-metal complex, in this case copper(II) 2-ethylhexanoate, but in contrast to the other diaminations described above, this complex also serves as an oxidant and therefore has to be present in excess (3 equivalents).…”

Diastereoselective Synthesis of Vicinal Diamines by Aza‐Michael Addition of Chiral Phenethylamine to Nitroalkenes

“…However, in contrast to their important applications, relatively few general methods are known for the diastereo‐ or enantioselective synthesis of vicinal diamines from readily available starting materials . Most of these synthesis methods are focused on the transition‐metal‐mediated reductive coupling imines, the transformation of chiral alcohols via the corresponding azides, or transition‐metal‐catalyzed diaminations of olefins . Some other methods are referred to sigmatropic rearrangements method, demetalation of corresponding Zn(II) complex method, etc.…”