4172
K. Kuramochi et al. / Bioorg. Med. Chem. 19 (2011) 4162–4172
128.0, 86.8, 79.2, 55.1, 49.6, 19.8. HRMS (ESI): calcd for C12H15NO3-
NaS ([M+Na]+) 276.0665, found 276.0665.
was extracted with EtOAc. The combined organic layer was washed
with brine, dried (Na2SO4) and concentrated. The residue was puri-
fied by preparative TLC (hexane/EtOAc = 1:3) to give 4d (3.6 mg,
21%).
5.12.5. (3R⁄,4R⁄,5R⁄)-4-Hydroxy-5-methyl-3,5-
bis(phenylsulfanyl)-2-pyrrolidinone (16)
To a solution of 12 (13.0 mg, 54.3
lmol) and thiophenol (7.0
lL,
References and notes
68.4 mol) in MeOH/H2O (1:1, 4 mL) was added NaHCO3 (18.3 mg,
l
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0.22 mmol) at room temperature, and the mixture was stirred at
room temperature for 24 h. The reaction was quenched by the
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with EtOAc. The layers were separated, the aqueous layer was ex-
tracted with EtOAc. The combined organic layer was washed with
brine, dried (Na2SO4) and concentrated. The residue was purified
by preparative TLC (hexane/EtOAc = 1:3) to give 16 (8.0 mg, 44%)
as amorphous solid and recovered 12 (3.3 mg, 25%). According to
the same procedure, compound 16 was obtained from 14 or 15.
16: IR (film): 3406, 3068, 3016, 2927, 1709, 1581, 1475, 1437,
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1387, 1336, 1176, 1078, 1037, 924 cmꢁ1 1H NMR (270 MHz,
.
DMSO-d6): d = 8.73 (1H, s), 7.58ꢁ7.16 (10H, m), 6.42 (1H, d,
J = 5.7 Hz), 3.90 (1H, dd, J = 10.0 Hz, 5.7 Hz), 3.36 (1H, d,
J = 10.0 Hz), 1.46 (3H, s). 13C NMR (68 MHz, CDCl3): d = 169.9,
137.7 (ꢂ2), 134.7, 130.7, 130.1 (ꢂ2), 129.1, 128.90 (ꢂ2), 128.87
(ꢂ2), 126.7, 79.6, 74.6, 54.0, 26.7. HRMS (ESI): calcd for C17H17NO2-
NaS2 ([M+Na]+) 354.0593, found 354.0592.
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To solution of 7b (50.0 mg, 0.21 mmol) and methyl glyoxal
(41 mg, 40% solution in water, 0.23 mmol) in THF/MeOH/H2O
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temperature. The mixture was stirred at room temperature under
a nitrogen atmosphere for 24.5 h. The reaction was quenched by
the addition of 1 M HCl aqueous solution, and the mixture was di-
luted with EtOAc. The layers were separated, the aqueous layer
was extracted with EtOAc. The combined organic layer was washed
with brine, dried (Na2SO4) and concentrated. The residue was puri-
fied by preparative TLC (hexane/EtOAc = 1:3) to give 17 (7.4 mg,
12%) as colorless oil and recovered 7b (8.9 mg, 18%). 17: IR (film):
3298, 2954, 2925, 2854, 1711, 1618, 1466, 1412, 1379, 1136, 1119,
17. Mizushina, Y.; Kobayashi, S.; Kuramochi, K.; Nagata, S.; Sugawara, F.;
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943, 667 cmꢁ1 1H NMR (270 MHz, DMSO-d6): d = 8.66, (1H, br s),
.
7.52 (1H, d, J = 1.6 Hz), 6.01 (1H, s), 2.80 (2H, t, J = 7.0 Hz), 1.48
(2H, m), 1.41 (3H, s), 1.24 (16H, m), 0.86 (3H, t, J = 6.2 Hz). 13C
NMR (68 MHz, DMSO-d6): d = 197.0, 167.1, 156.5, 134.0, 83.8,
41.2, 31.5, 29.2 (2C), 29.1, 29.0, 28.9, 28.7, 25.0, 23.2, 22.3, 14.2.
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318.2039.
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NaHCO3 aqueous solution (Scheme 10)
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To solution of 7d (22.6 mg, 0.14 mmol) and methyl glyoxal
(29.7 mg, 40% solution in water, 0.16 mmol) in MeOH (1.0 mL)
was added 0.5 M aqueous solution of NaHCO3 (1.0 mL) at room
temperature. The mixture was stirred at room temperature under
a nitrogen atmosphere for 22.5 h. The reaction was quenched by
the addition of 1 M HCl aqueous solution, and the mixture was di-
luted with EtOAc. The layers were separated, the aqueous layer