Br[C:2]1[CH:3]=[CH:4][C:5]([F:8])=[N:6][CH:7]=1.C([Li])CCC.CN(CCN(C)C)C.[CH2:22]1[O:32][C:25]2([CH2:30][CH2:29][C:28](=[O:31])[CH2:27][CH2:26]2)[O:24][CH2:23]1>CCOCC.C1COCC1>[F:8][C:5]1[N:6]=[CH:7][C:2]([C:28]2([OH:31])[CH2:29][CH2:30][C:25]3([O:32][CH2:22][CH2:23][O:24]3)[CH2:26][CH2:27]2)=[CH:3][CH:4]=1A solution of 5-bromo-2-fluoropyridine (2 g, 0.011 mol) in 50 mL of dry ether under nitrogen was cooled to −78° C. n-butyllithium (7.5 mL, 0.011 mol, 1.6 M solution in hexane) and TMEDA (2.5 g, 0.022 mol) were added dropwise. The orange solution was stirred for an additional 1 h at −78° C. and then treated dropwise over 10 min with a solution of 1,4-cyclohexanedione monoethylene ketal (1.8 g, 0.011 mol) in 20 mL of dry THF. The reaction mixture was stirred for 1 h, allowed to warm to 20° C. and poured into ice water (400 mL). The organic layer was separated, and the aqueous layer was extracted twice with EtOAc (20 mL×2). The combined organic extracts were dried over MgSO4 and evaporated to give 2 g of white solid. Chromatography on silica gel afforded 1.7 g (67% yield) of white crystals: MS: 254 (M+1)+.
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