Resin-immobilized aldimines 5, derived from the condensation of amine-functionalized Rink polystyrene resin with aldehydes, react with Grignard reagents, lithium reagents or LiBH4 to afford a wide variety of primary amines in good to excellent yields upon trifluoroacetic acid cleavage. In this amine synthesis, Rink resin functions both as a solid support and as a NH protecting group.