SYNTHESIS OF [14C]ABT-770
889
cooled to 08C under a nitrogen atmosphere. A solution of 95%
diisopropyl azodicarboxylate (0.318 g, 1.5 mmol) was slowly added over
10 min. The reaction was stirred at room temperature for 3.5 h. HPLC
analysis (Zorbax SB C8 column, 4.6 ꢀ 250 mm, 5 mm, UV at 230 nm,
flow rate=1 ml/min, at 308C, 20% CH3CN/0.1% H3PO4 to 60%
CH3CN/0.1% H3PO4 over 15 min, hold at this concentration for
10 min, RT=8.3 min) at this time showed complete consumption of 5.
The product was used directly in the next step.
3-{2-[(3R)-3-(4-Methoxyphenyl)(1,2-oxaziridin-2-yl)(2 S)-3-(4-bromophe-
noxy) propyl-5,5-dimethyl-1,3-diazolidine-2,4-dione [bromophenyl-UL-14C]
ð7Þ
The reaction mixture containing 6 from the previous step was cooled to
–78oC and to this was added a solution of mCPBA (0.703 g, 4.0 mmol)
in THF (1.5 ml). The reaction mixture was warmed to 08C and stirred at
that temperature for 1.5 h. The reaction progress was monitored by
HPLC (Zorbax SB C8 column, 4.6 ꢀ 250 mm, 5 mm, UV at 230 nm, flow
rate=1 ml/min, at 308C, 20% CH3CN/0.1% H3PO4 to 60% CH3CN/
0.1% H3PO4 over 50 min, hold at this concentration for 10 min
RT=20.8, 21.9, 22.7 min). Reactant 6 was completely consumed, and
three new peaks appeared, suggesting formation of a mixture of
diastereomers of the desired product. The crude product was used
directly in the next step.
3-[(2S)-3-(4-Bromophenoxy)-2-(hydroxyamino)propyl]-5,5-dimethyl-
1,3-diazolidine-2,4-dione [bromophenyl-UL-14C] ð8Þ
The mixture containing 7 from the previous step was cooled to 0oC and
aqueous solution (1.5 ml) of hydroxylamine hydrochloride (0.73 g,
10.6 mmol) was added. The reaction mixture was warmed to room
temperature and was stirred at that temperature for 15 h. HPLC
analysis (Zorbax SB C8 column, 4.6 ꢀ 250 mm, 5 mm, UV at 230 nm,
flow rate=1 ml/min, at 308C, 20% CH3CN/0.1% H3PO4 to 60%
CH3CN/0.1% H3PO4 over 50 min, hold at this concentration for
10 min, RT=10.5 min) of the organic layer showed complete disap-
pearance of the three peaks of 7. After cooling the reaction mixture to
08C, a saturated solution of K2CO3 was added until pH 8.0 (5 ml), and
the solution was extracted with EtOAc (2 ꢀ 40 ml). The combined
organic layers were washed with saturated NaHCO3 (10 ml) and a brine
solution (25 ml). The solvent was evaporated using a rotary evaporator,
Copyright # 2003 John Wiley & Sons, Ltd.
J Label Compd Radiopharm 2003; 46: 883–892