Synthesis of trifunctional sphingomyelin derivatives TFSM 1 and TFSM 2 . Synthetic route for TFSM 1 : (i) MOM-Cl, DIPEA, DCM, 0 C, 4 h, 85%; (ii) TBAF, THF, 0 C, 2 h, 97%; (iii) beta-bromoethylphosphoryl dichloride, pyridine, DCM, 0 C, 4 h, 82%; (iv) N,N-dimethylpropargylamine, CHCl 3 , MeCN, iPrOH, rt -> 45 C, 2 d, 63%; v) 1. HCl, MeOH, rt, 2 h; 2. 13 , DIPEA, DCM, rt, 18 h, 85% in two steps; vi) TFA, DCM, 0 C, 2 h, quant. Synthetic route for TFSM 2 : (i) MOM-Cl, DIPEA, DCM, 0 C -> rt, 4 h, 74%; (ii) TBAF, THF, 0 C -> rt, 1 h, 78%; (iii) beta-bromoethylphosphoryl dichloride, pyridine, DCM, 0 C, 5 h, 56%; (iv) N,N-dimethylpropargylamine, CHCl 3 , MeCN, iPrOH, rt, 6 d, 69%; (v) 1. HCl, MeOH, rt, 3.5 h; 2. 14 , DIPEA, DCM, rt, 3 d, 85% in two steps; (vi) TFA, DCM, 0 C, 2.5 h, quant.
