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Reagents and reaction conditions: i) 1-Boc-piperazine/NaHB(OAc)3/CH2Cl2; ii) TFA/CH2Cl2; iii) EDCl/R4COOH/DMF or R4CHO/NaHB(OAc)3/CH2Cl2 or R4SO2Cl/TEA/CH2Cl2.