Reagents and conditions: (a)
Cu, quinoline, 2 h, 150 °C, 81%; (b) Br2, CHCl3, 30 h, 60 °C, 93%; (c) NCS, TMPMgCl·LiCl, THF,
toluene, −75 °C, 80%; (d) RaNi, H2, EtOH, rt,
96%; (e) 24, p-TsOH·H2O, DMF, 15 h, 80 °C, 66%; (f) 20, Na2CO3 2 M aq, Pd(amphos)Cl2, MeCN, 30 min, 80
°C, 25%; (g) 22, Na2CO3 2
M aq, PdCl2(dppf)·DCM, DME, 80 °C, 68%; (h) NaNO2, KI, HCl 4 M, H2O, MeCN, 5 °C to rt, 36%;
(i) Bis(pinacolato)diboron, KOAc, PdCl2(dppf)·DCM,
dioxane, 10 h, 110 °C, 49%; (j) Bis(pinacolato)diboron, KOAc,
PdCl2(dppf)·DCM, dioxane, 3 h, 100 °C, 80%; (k)
Boc2O, DMAP, DCM, rt, 98%.