[4+2] Cycloaddition of 2-Substituted 1,2-Dihydropyridines with Nitrosobenzene: Asymmetric Synthesis of <i>trans</i>-2-Substituted 3-Amino-1,2,3,6-tetrahydropyridines

Abstract

[reaction: see text] A new methodology for the stereoselective synthesis of trans-2-substituted 3-amino-1,2,3,6-tetrahydropyridines is reported. The preparation of these 3-aminopiperidines is achieved by cycloaddition of nitrosobenzene with 2-substituted 1,2-dihydropyridines followed by chemoselective reduction of the cycloadducts. Enantioenriched 1,2-dihydropyridine derivatives are easily prepared from pyridine and a chiral amide following a previous report from our laboratories. Moreover, the in situ hydrogenation of these cycloadducts over palladium in a solution of hydrogen chloride in methanol led to tetrahydropyrroloimidazoles.