Reagents and conditions. Unbranched Synthesis: (a) Ar–B(OH)2 or Ar–Br, Pd(PPh3)4, Cs2CO3, dioxane/H2O, 90 °C; (b) methoxymethyl triphenylphosphonium chloride, NaOtBu, THF, 0 °C; (c) NaI, TMSCl, MeCN, −20 °C; (d) dimethyl(1-diazo-2-oxopropyl)phosphonate, K2CO3, MeOH; (e) iodoethyl diaminopyrimidine, Pd(PPh3)2Cl2, CuI, KOAc, DMF, 50 °C; (f) TFA, DCM. Asymmetric Synthesis: (a) PdCl2(PPh3)2, 4-methoxycarbonylphenylboronic acid, dioxane/H2O, 90 °C; (b) 10% Pd/C, Et3SiH, DCM; (c) nonaflyl fluoride, P1-t-Bu-tris(tetramethylene) phosphazene base, DMF, −15 °C to rt; (d) iodoethyl diaminopyrimidine, Pd(PPh3)2Cl2, CuI, KOAc, DMF, 50 °C; (e) LiOH, THF·H2O, 32 °C.