The Chemistry of Vicinal Diamines

Abstract

Especially in the field of enantioselective synthesis, vicinal diamines (1,2-diamines) 1 and compounds easily prepared from them-such as 1,2-bisimines, 1,2-diamides, or imidazolidin-2-ones-are widely used by organic chemists. Various strategies have been developed to produce these compounds selectively. Many natural products and medicinal agents also contain a 1,2-diamino unit.

Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C–C bond formations via the oxidative activation of sp 3 C–H bonds

“…Vicinal diamines are important structural motifs in biologically active natural products and are used as core units of chiral auxiliaries and chiral ligands in asymmetric catalysis (30). An efficient synthetic approach toward such compounds is through the nitro-Mannich (aza-Henry) reaction.…”

Asymmetric organocatalytic Strecker-type reactions of aliphatic N,N-dialkylhydrazones

“…Alternatively, hydrazino nitriles 2a,b were subjected to reduction with lithium aluminum hydride and subsequent condensation with triphosgene leading to imidazolidinones 7a,b in good overall yields and without racemization. These are also valuable products containing an unsymmetrical vicinal diamine moiety, 26 often present in biologically active compounds. 27 Absolute configuration and stereochemical model…”

Diastereoselective imino-pinacol coupling of chiral imines promoted by Mg(0) and a Grignard reagent

“…Several methods that use a variety of metals as reductants have been reported for the reductive homocoupling reaction. 1 Diastereoselective coupling of chiral imines is especially useful for synthesis of chiral 1,2-diamine derivatives; a valuable class of compounds used as ligands of chiral catalysts in asymmetric synthesis 2 and as medicinal products in pharmaceutical chemistry. 3 Although this diastereoselective coupling has been extensively examined in terms of the intramolecular reaction of chiral diimines 4 and the intermolecular reaction employing chiral imines 5 or chiral activators, 6 most studies use costly reducing agents, such as Sm and SmI2, or a large excess of metals and acids.…”