Abstract
The addition reaction of benzophenone with lithium (2‐pyridylmethyl)(tert‐butyldimethylsilyl)amide yields dimeric1‐lithoxy‐1,1‐diphenyl‐2‐(2‐pyridyl)‐2‐(trialkylsilylamino)ethane (1) with formation of a C–C bond. C‐Functionalized 2‐(pyridylmethyl)amines are accessible via the reaction of N‐(2‐pyridylmethylidene)phenylamine with diethylmalonate giving 2,2‐bis(ethoxycarbonyl)‐1‐(phenylamino)‐1‐(2‐pyridyl)ethane (2) which eliminates aniline upon heating yielding diethyl 2‐(2‐pyridylmethylidene)malonate (3). The addition of piperidine leads to the formation of the Michael type adduct 2,2‐bis(ethoxycarbonyl)‐1‐piperidyl‐1‐(2‐pyridyl)ethane (4) which can be deprotonated with metal‐organic reagents such as Zn[N(SiMe~3~)~2~]~2~, Zn[CH(SiMe~3~)~2~]~2~, LiN(SiMe~3~)~2~, and NaN(SiMe~3~)~2~ leading to 2,2‐bis(ethoxycarbonyl)‐1‐piperidyl‐1‐(2‐pyridyl)ethane‐2‐yl complexes of zinc (5 and 6), lithium (7), and sodium (8). N‐Functionalization can be achieved via the reaction of (2‐pyridylmethyl)(trialkylsilyl)amine with benzoyl chloride giving N‐(2‐pyridylmethyl)benzoylamine (9). Lithiation and subsequent salt metathesis reaction with another equivalent of benzoyl chloride yields N‐(2‐pyridylmethyl)dibenzoylamine (10). The addition reaction of ZnCl~2~ with N‐(2‐pyridylmethyl)(diphenylmethylidene)amine (11) forms colorless crystalline [(Py–CH~2~N=CPh~2~)ZnCl~2~] (12). The addition of benzoyl chloride leads to N‐(diphenylchloromethyl)‐N‐(2‐pyridylmethyl)benzoylamine (13). Addition of ZnCl~2~ leads to the formation of solvent‐separated [(2‐pyridylmethyl)(benzoylamino)diphenylcarbonium] [(tetrahydrofuran)trichlorozincate] (14). The X‐ray crystal structures of 1, 4 to 7, 9, 12, and 14 are discussed.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)