An Efficient Synthesis of Substituted (Z)-Allylamines and 7-Membered Nitrogen Heterocycles from (Z)-3-(Tributylstannyl)allylamine

Article abstract of DOI:10.1021/jo00058a026

The reaction of N-(trimethylsilyl)allylamine with 2 mol of n-butyllithium, followed by treatment with chlorotributyltin and subsequent hydrolysis, gave (Z)-3-(tributylstannyl)allylamines in high yields.The N,N-disilylated derivatives, upon transmetalation of the C-Sn bond, led to unstable vinyllithium species.The latter readily underwent a <1,4> nitrogen to carbonyl silyl migration to give a lithium amide.The unprotected (Z)-3-(tributylstannyl)allylamine underwent a palladium-catalyzed cross-coupling reaction with aromatic bromides affording a stereospecific preparation of substituted allylic amines with Z configuration of the carbon-carbon double bond.The reactions of ortho-functionalized aryl bromides offer a one-step preparation of 7-membered nitrogen heterocycles in high yields.