Scheme 1. S_NAr Chemistry toward Subsite 3 Iodophenol Analogues.

Conditions: (a) NIS, AcOH, 25 °C, 6 h, 86%; (b) K₂CO₃, Me₂SO₄, NMP, 80 °C, 1 h, 68%; (c) heterocycle, Cs₂CO₃, DMSO, 70 °C, 1 h, 45–68%; (d) KF, 1-TIPS-pyrrole derivative, Cs₂CO₃, DMSO, 70 °C, 1 h, 73–80%; (e) BBr₃, CH₂Cl₂, 0 to 25 °C, 24 h, 27–62%; (f) TMSI, CH₂Cl₂, 50 °C, sealed tube, 24 h, 31%; (g) Cs₂CO₃, heterocycle, DMSO, 150 °C, 2 h, 55–58%; (h) CF₃CH₂OH, NaH, DMF, 0 to 150 °C, 20 h, 22%; (i) NBS, THF, −78 to 25 °C, 3 h, 89%; (j) nBuLi, NFSI or NCS, THF, −78 to 25 °C, 1.5 h, 48–50%; (k) I₂, H₅IO₆, Et₂O, 25 °C, 1 h, 86%; (l) nBuLi, NFSI, THF, −78 to 25 °C, then nBuLi, NFSI, THF, −78 to 25 °C, 1 h, 32%; (m) NIS, acetone, −78 to 25 °C, 5 h; (n) TBAF, THF, 25 °C, 1 h; (o) NaH, TsCl, THF, 0 to 25 °C, 1 h, 84% over 3 steps; (p) FSO₂CF₂COOCH₃, CuI, HMPA, DMF, 80 °C, 16 h, 62%; (q) Mg, MeOH, 25 °C, 0.5 h, 73%.