Unsubstituted and 6,7-dialkoxy-N-pivaloyl-tetrahydroisoqu~nolines 1-3 are converted to l-bromomagnesium derivatives by sequential treatment with 1-BuLi (-75"/THF) and MgBrz.0Et2. Addition of the metalated tetrahydroisoquinolines to aliphatic or aromatic aldehydes occurs with relative topicity ul (Scheme 2). The I-hydroxyalkylated 2-pivaloyl-tetrahydroisoquinolines a of u-configuration thus obtained (14 examples) can be converted to free aminoalcohols c of either Ior u-configuration (9 examples; Scheme 3). The depivdloylation with retention (+ u-c) is best achieved by heating in EtOH/KOH, the conversion to 1 -aminoalcohols I-c by treatment with CF,COOH/(CF,CO),O (+ I -pivalates I-b), followed by alkaline saponification or by LiAIH4 reduction of the esters. The configuration of the products is assigned by 'H-NMR spectroscopy, by X-ray crystal structure analysis, by chemical correlation, and by comparison of the chemical properties of the Iand the u-isomers. The diastereoselective hydroxybenzylation of the tetrahydroisoquinoline is used for short syntheses of ushinsunine/ oliveroline (Scheme 4 ) , p-hydrastine, and ophiocarpine/epiophiocarpine (Scheme 6: aporphine, phthalide, and protoberberine alkaloids, respectively).