Formation, Structures, and Reactions of Selected α'-Lithioallyl Amides

Article abstract of DOI:10.1021/jo00263a037

Lithiations of the selected allyl amides 6, 10, 14, and 17 give the α'-lithioallyl amides 7, 11, 15, and 18.The structures of 7, 11, and 18 are characterized by their NMR spectra.Electrophilic substitutions of these reagents are usually regioselective at γ'-position, but there are exceptions.In situ lithiation-electrophilic substitutions are effective for 10 and 17 with LiTMP-(CH3)3SiCl, n-BuLi-C6H5CH2Cl, and n-BuLi-Cl(CH2)4Cl.Hydrogen-deuterium isotope effects are consistent with diastereoselective removal of a pseudoequatorial proton from 17.The lithiations are suggested to occur in an amide-organolithium complex and most readily in systems that can achieve a Z conformation.