Synthesis of ANPs 8, the corresponding phosphorodiamidate
prodrugs 9, and phosphono disphosphates 10. Reagents
and conditions: a) LDA, THF, −20 °C, then oxirane, THF, 10
°C, then TfOCH2P(O)(OiPr)2,
−40 °C; b) XPhos Pd G2, R-B(OH)2,
K3PO4, THF/H2O (4:1), 40 °C, then
TFA, RT, 5 min; c) TMSBr, pyridine, RT, then
(L)-NH2CH(Bn)COOiPr·HCl,
Aldrithiol™, PPh3, Et3N, pyridine, 70 °C; d)
(i) TMSBr, pyridine, RT, (ii) 2M aq. TEAB and TBAH, (iii) CDI,
(Bu3N)2P2O7, DMSO.