Synthesis of Amido-N-imidazolium Salts and their Applications as Ligands
Synthesis from 18 and 13b: 4-[(2-Butyl-4-oxo-1,3-diaza-
spiro[4.4]non-1-en-3-yl)methyl]phenylboronic acid (18)
(1.00 g, 3.05 mmol), 2-chlorobenzonitrile (13b) (420 mg,
3.05 mmol), NaOH (183 mg, 4.57 mmol), Pd(OAc)2
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(20.5 mg, 0.09 mmol) and 4bc (55.8 mg, 0.09 mmol) were
added to a flask containing 9.0 mL of a mixture of NMP and
H2O (v/v 4/1). The resulting mixture was heated to 1308C
for 12 h. After cooling, the mixture was poured into ethyl
acetate (20.0 mL) and washed with water (2ꢁ10.0 mL),
brine (2ꢁ10.0 mL), and then dried over Na2SO4, followed
by evaporation of the solvent under reduced pressure. The
crude residue was purified by column chromatography (hex-
ane:EtOAc, 7:3) to afford the final product 19 as an off-
white solid; yield: 857 mg, (2.22 mmol, 73%); mp 97–1008C.
1H NMR (300 MHz, CD3OD): d=7.82 (dd, J=7.8, 1.8 Hz,
1H), 7.72 (dt, J=7.8, 1.8 Hz, 1H), 7.59–7.49 (m, 4H), 7.34
(d, J=8.4 Hz, 2H), 4.84 (s, 2H), 2.44 (t, J=7.6, 2H), 2.02–
1.81 (m, 8H), 1.54–1.49 (m, 2H), 1.35–1.28 (m, 2H), 0.84 (t,
J=7.2 Hz, 3H); 13C NMR (75 MHz, CD3OD): d=188.0,
165.4, 146.2, 139.5, 138.8, 135.0, 134.5, 131.4, 130.7, 129.4,
128.3, 119.6, 112.3, 77.7, 44.3, 38.6, 29.6, 28.9, 27.2, 23.4, 14.1.
Synthesis of Irbesartan[19] (20)
In a vial equipped with a magnetic stirrer, TBAF (170 mg,
0.65 mmol), 4’-[(2-butyl-4-oxo-1,3-diazaspiroACTHUNRTGNEUNG[4.4]non-1-en-3-
yl)methyl]biphenyl-2-carbonitrile (19) (500 mg, 1.30 mmol),
TMSiN3 (300 mg, 2.60 mmol) and 5.0 mL of the mixture of
DMF and H2O (v/v 4.5/0.5) were added. The resulting mix-
ture was heated to 1208C for 36 h. After cooling, the mix-
ture was poured into ethyl acetate (20.0 mL) and TBAF was
removed by washing the organic phase with a 1M aqueous
HCl solution (2ꢁ5.0 mL) then dried over Na2SO4. After
evaporation of the solvent under reduced pressure, the
crude residue was recrystallized from ethyl acetate to fur-
nish pure irbesartan (20) as an off-white solid; yield: 495 mg
(1.16 mmol, 89%); mp 180–1838C. 1H NMR (300 MHz,
CD3OD): d=7.55–7.40 (m, 4H), 7.12 (d, J=8.1 Hz, 2H),
7.03 (d, J=8.4 Hz, 2H), 4.70 (s, 2H), 2.38 (t, J=7.8 Hz,
2H), 1.98–1.77 (m, 8H), 1.56–1.46 (m, 2H), 1.38–1.2 (m,
2H), 0.86 (t, J=7.2 Hz„ 3H); 13C NMR (300 MHz,
CD3OD): d=188.0, 165.5, 162.6 , 142.8, 142.3, 136.4, 132.0,
131.4, 131.0, 130.9, 130.3, 128.4,127.5, 77.6, 44.3, 38.5, 28.8,
27.2, 23.3, 14.2.
Acknowledgements
This work was supported by a National Research Foundation
of Korea Grant funded by the Korean Government (2009-
0077677).
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