Enantioselective synthesis of 1-aryl tetrahydroisoquinolines by the rhodium-catalyzed reaction of 3,4-dihydroisoquinolinium tetraarylborates

The 1-aryl tetrahydroisoquinolines (1-aryl THIQs) are omnipresent in biologically active molecules. Here we report on the direct asymmetric synthesis of these valuable compounds via the reaction of 3,4-dihydroisoquinolinium tetraarylborates. The dual roles of anionic tetraarylborates, which function as both prenucleophiles and stabilizers of 3,4-dihydroisoquinolinium cations, enable this rhodium(I)-catalyzed protocol to convergently provide enantioenriched 1-aryl THIQs in good yields (≤95%) with ≤97% ee, as demonstrated by the formal synthesis of (−)-solifenacin and the facile synthesis of (−)-Cryptostyline I.