Synthesis of the Norspermidine/Norspermine series.
Reagents: a. Boc2O (excess), MeOH, rt, 12 h. b. NaH (excess), C16H33I, DMF, − 15°C-r.t., 24 h. c. TFA, r.t, 45 min d. (i) CF3COOEt, MeOH, −78 °C to 0 °C, 1h; (ii) Boc2O (excess), MeOH, r.t, 12 h; (iii) LiOH,THF, r.t. e. 3-bromopropan-1-ol, K2CO3, DMF, 60°C (ii) Boc2O (excess), MeOH, r.t, 12h. f. (i) MeOH, Pd(OH)2/C, H2, 60 psi; (ii) Boc2O (excess), MeOH, r.t, 12h. g. PCC, DCM, r.t. h. (i)C16H33NH2, NaCNBH3, glacial AcOH (5 drops), anhyd. MeOH, r.t, 24h (ii) Boc2O (excess), MeOH, r.t, 12h. i. i) CH2CHCN, MeOH, r.t, 6 h; ii) Boc2O (excess), MeOH, rt, 12 h. j. i) Pd(OH)2/C, Glacial acetic acid, H2, 60 psi; ii) Boc2O (excess), MeOH, rt, 12 h.