A new method of synthesizingortho‐methylated phenylalanines has been developed. Phenylalanines with at least one freeortho‐position undergo a Pictet—Spengler cyclization with formaldehyde followed by hydro‐genolytic splitting of the endocyclic benzylic C—N bond of 1,2,3,4‐tetrahydroisoquinolines and afford correspondingortho‐methyl derivatives. Repeating this reaction sequence on theortho‐substituted phenylalanines yieldedortho, ortho‐disubstituted derivatives, and pro‐substituted phenylalanines yieldedortho,para‐disubstituted analogs. Our modified method of cyclization preserved the configuration at the chiral center: hydrogenolysis, on the other hand, led to racemization. Incorporation of the methylated phenylalanines into position 2 of oxytocin led to, in the case of the D‐isomers, poten