Synthesis of the hybrid structures. Reagents and conditions: (i) 1% TFA in DCM, 30 min, 3×. (ii) TMS–diazomethane (2 equiv.), 15 min., 85% from Fmoc-Nle-resin. (iii) Hydrazine monohydrate (60 equiv.), MeOH, reflux, 1.5 h, 92%. (iv) (a) HCl (2.8 equiv.), tBuONO (1.1 equiv.), DMF–EtOAc (1: 1, v/v), −25 °C, 4 h. (b) TFA·H-Ra–c (1.1 equiv.), DiPEA (3.8 equiv.), −25 °C to RT, 15 h, Ia 77%, Ib 34%, Ic 63%, IIa 77%, IIb 53%, IIc 66%. (v) HCl·H-Phe-OMe (1 equiv.), BOP (1 equiv.), DiPEA (2.2 equiv.), DCM, 15 h, quant. (vi) TFA/DCM 1: 1 (v/v), 15 min. (vii) 2-(Naphthalen-2-yl)-acetic acid (1 equiv.), BOP (1 equiv.), DiPEA (3.3 equiv.), DCM, 15 h, 68%. (viii) Hydrazine monohydrate (60 equiv.), MeOH, reflux, 2.5 h, 95%.