Asymmetric synthesis of amines by nucleophilic 1,2-addition of organometallic reagents to the CN-double bond

Catalytic asymmetric addition of diorganozinc reagents to N -phosphinoylalkylimines

“…T he synthesis of ␣-chiral amines using the catalytic asymmetric addition of diorganozinc reagents has produced very exciting results in recent years (1)(2)(3). This very important subunit is commonly found in many pharmaceuticals and other biologically important compounds.…”

Synthesis of Chirally Pure Enantiomers by Lipase

“…Asymmetric methods for the preparation of chiral amines have recently been reviewed 63,64 . They are mainly involving 1, 2-addition of nucleophiles to a C N bond of imines.…”

Development of New Synthetic Reactions for Nitrogen-Containing Compounds and Their Application

“…However, the addition of organometallic reagents is frequently plagued by the aza-enolization of the substrates with acidic a-hydrogens, poor electrophilicity of the imino group, and the formation of reductive coupling products. 30) We expected that mild addition of a strictly neutral species such as an uncharged free radical would provide a highly general solution to the fundamental problems that are associated with the strong basicity of organometallic reagents. Among the different types of radical acceptors containing a CϭN bond, the oxime ether and hydrazone are well known to be excellent radical acceptors because of the extra stabilization of the intermediate aminyl radical B provided by the lone pair on the adjacent heteroatom involving three electron p-bonding interactions.…”