10.1002/ejoc.201900258
European Journal of Organic Chemistry
FULL PAPER
124.0, 127.2, 127.8, 128.6, 128.9, 129.5, 130.0, 130.5, 132.0, 132.2,
132.8, 134.6, 136.1, 137.1, 161.6, 185.6.
Ethyl 3-oxo-3-phenyl-2-((4-bromophenyl)sulfonyl)propanoate, 3ad.
White solid, mp = 74-76°С, Rf = 0.39 (PE:EA = 5:1). Yield 53%. 1Н NMR
(300.13 MHz, CDCl3, δ, ppm): 1.17 (t, J = 7.1 Hz, 3H), 4.13-4.24 (m, 2H),
6.03 (s, 1H), 7.48-7.53 (m, 2H), 7.63-7.72 (m, 3H), 7.81 (d, J = 8.1 Hz,
2H), 7.97 (d, J = 8.1 Hz, 2H).13C NMR (75.48 MHz, CDCl3, δ, ppm): 13.7,
63.1, 75.2, 129.0, 129.3, 130.2, 131.8, 132.1, 134.7, 135.3, 135.9, 161.4,
Ethyl 3-oxo-2-(phenylsulfonyl)hexanoate, 3ga. Colorless oil. Rf = 0.65
(PE:EA = 2:1). Yield 49%. 1Н NMR (300.13 MHz, DMSO-d6, δ, ppm):
0.82 (t, J = 7.3 Hz, 3H), 1.05 (t, J = 7.1 Hz, 3H), 1.42-1.54 (m, 2H), 2.70
(t, J = 7.1 Hz, 2H), 4.03-4.10 (m, 2H), 6.12 (s, 1H), 7.66 (t, J = 7.3 Hz,
2H), 7.78 (t, J = 7.3 Hz, 1H), 7.90 (d, J = 7.3 Hz, 2H).13C NMR (75.48
MHz, DMSO-d6, δ, ppm): 13.1, 13.5, 16.1, 45.0, 62.2, 77.6, 129.1, 134.6,
137.8, 161.5, 196.1. HRMS (ESI) m/z [M+Na]+: Calculated for
[C14H18NaO5S]+ : 321.0767. Found: 321.0761.
185.8. HRMS (ESI) m/z [M+Na]+: Calculated for [C17H15BrO5SNa]+
:
432.9716. Found: 432.9704.
Ethyl 3-oxo-3-phenyl-2-((4-methoxyphenyl)sulfonyl)propanoate, 3ae.
White solid, mp = 105-106 °С. Rf = 0.49 (PE:EA = 2:1). Yield 43%.1Н
NMR (300.13 MHz, CDCl3, δ, ppm): 1.17 (t, J = 7.0 Hz, 3H), 3.85 (s, 3H),
4.14-4.21 (m, 2H), 5.99 (s, 1H), 6.96 (d, J = 8.8 Hz, 2H), 7.48 (dd, J = 7.3,
8.1 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 7.85 (d, J = 8.8 Hz, 2H), 7.97 (d, J =
8.1 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ, ppm): 13.7, 55.6, 62.9, 75.2,
113.8, 128.2, 128.9, 129.2, 132.8, 134.4, 135.6, 161.7, 164.5, 186.1.
HRMS (ESI) m/z [M+Na]+: Calculated for [C18H18O6SNa]+: 385.0716.
Found: 385.0716.
Methyl 3-oxo-3-phenyl-2-(phenylsulfonyl)propanoate, 3ha. White
solid, mp = 100-102 °С. Rf = 0.45 (PE:EA = 2:1). Yield 69%. 1Н NMR
(300.13 MHz, CDCl3, δ, ppm): 3.70 (s, 3H), 6.05 (s, 1H), 7.46-7.55 (m,
4H), 7.60-7.68 (m, 2H), 7.94-7.95 (m, 4H). 13C NMR (75.48 MHz, CDCl3,
δ, ppm): 53.5, 75.0, 128.6, 128.9, 129.2, 130.4, 134.6, 135.4, 137.0,
162.0, 185.7. HRMS (ESI) m/z [M+Na]+: Calculated for [C16H14NaO5S]+
:
341.0454. Found: 341.0456.
Ethyl 3-oxo-3-phenyl-2-(methylsulfonyl)propanoate, 3ag.
White
solid, mp = 75-76 °С. Rf = 0.65 (PE:EA = 2:1). Yield 43%. 1Н NMR
(300.13 MHz, CDCl3, δ, ppm): 1.25 (t, J = 7.1 Hz, 3H), 3.35 (s, 3H), 4.24-
4.30 (m, 2H), 5.81 (s, 1H), 7.52 (dd, J = 7.3, 8.0 Hz, 2H), 7.66 (t, J = 7.3
Hz, 1H), 8.01 (d, J = 8.0 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ, ppm):
13.8, 40.0, 63.4, 73.6, 129.0, 129.4, 134.9, 135.1, 161.7, 186.5.
Propyl 3-oxo-3-phenyl-2-(phenylsulfonyl)propanoate, 3ia. White solid,
mp = 47-49 °С. Rf = 0.70 (PE:EA = 2:1). Yield 78%. 1Н NMR (300.13
MHz, CDCl3, δ, ppm): 0.78 (t, J = 7.3 Hz, 3H), 1.48-1.60 (m, 2H), 4.00-
4.13 (m, 2H), 6.02 (s, 1H), 7.45-7.55 (m, 4H), 7.60-7.68 (m, 2H), 7.95 (d,
J = 8.1 Hz, 4H). 13C NMR (75.48 MHz, CDCl3, δ, ppm): 10.0, 21.5, 68.5,
75.3, 128.6, 128.9, 129.2, 130.4, 134.5, 135.5, 137.1, 161.5, 185.8.
HRMS (ESI) m/z [M+Na]+: Calculated for [C18H18NaO5S]+ : 369.0767.
Found: 369.0763.
General procedure for the synthesis of α-sulfonyl esters 4aa, 4ma,
4lb-4lf (Table 3). To a solution of β-ketoester 1a, 1l-1m (300 mg, 1.56-
2.31 mmol) and sodium sulfinate 2a-2f (454-673 mg, 2.77 mmol, molar
ratio 1.2 mmol/mmol 1) in i-PrOH-H2O mixture (15 mL, 2:1),
Fe(ClO4)3·xH2O (1.94-2.88 g, 3.90-5.78 mmol, molar ratio 2.5
mmol/mmol 1) was added while stirring. The reaction mixture was
refluxed for 3 hours. After that it was diluted with EA : diethyl ether
mixture (80 mL, 1:1), phases were separated. Organic layer was washed
with water (3×20 mL), dried over Na2SO4 and filtered. Solvent was
removed under reduced pressure. Target α-sulfonyl esters 4aa, 4ma,
4lb-4lf were isolated by chromatography on SiO2 with elution using PE-
EA in a linear gradient of the latter from 5 to 35 vol %.
Benzyl 3-oxo-3-phenyl-2-(phenylsulfonyl)propanoate, 3ja. White solid,
mp = 91-93 °С. Rf = 0.54 (PE:EA = 2:1). Yield 71%. 1Н NMR (300.13
MHz, CDCl3, δ, ppm): 5.14-5.23 (m, 2H), 6.07 (s, 1H), 7.25-7.34 (m, 5H),
7.49-7.51 (m, 4H), 7.63-7.65 (m, 2H), 7.89-7.98 (m, 4H). 13C NMR (75.48
MHz, CDCl3, δ, ppm): 68.5, 75.4, 128.5, 128.6, 128.6, 128.6, 128.9,
129.2, 130.4, 134.1, 134.5, 134.5, 135.4, 136.9, 161.4, 185.6. HRMS
(ESI) m/z [M+Na]+: Calculated for [C22H18NaO5S]+ : 417.0767. Found:
417.0775.
Phenethyl 3-oxo-3-phenyl-2-(phenylsulfonyl)propanoate, 3ka. White
solid, mp = 66-68 °С. Rf = 0.57 (PE:EA = 2:1). Yield 73%. 1Н NMR
(300.13 MHz, CDCl3, δ, ppm): 2.82-2.86 (m, 2H), 4.30-4.35 (m, 2H), 5.99
(s, 1H), 7.06-7.08 (m, 2H), 7.20-7.25 (m, 3H), 7.48-7.54 (m, 4H), 7.61-
7.66 (m, 2H), 7.91-7.93 (m, 4H). 13C NMR (75.48 MHz, CDCl3, δ, ppm):
34.5, 67.2, 75.2, 126.7, 128.5, 128.6, 128.8, 128.9, 129.2, 130.5, 134.5,
134.6, 135.5, 136.7, 137.0, 161.4, 185.7. HRMS (ESI) m/z [M+Na]+:
Calculated for [C23H20NaO5S]+ : 431.0924. Found: 431.0912.
Ethyl 2-(phenylsulfonyl)acetate, 4aa.
Yellow oil, Rf = 0.56 (PE:EA =
2:1). Yield 69%. 1Н NMR (300.13 MHz, CDCl3, δ, ppm): 1.17 (t, J =7.2 Hz,
3H), 4.10 (s, 2Н), 4.10-4.16 (m, 2Н), 7.57 (dd, J = 8.1, 7.3 Hz, 2H), 7.68
(t, J = 7.3 Hz, 1H), 7.94 (d, J = 8.1 Hz, 2H). 13C NMR (75.48 MHz, CDCl3,
δ, ppm): 13.8, 61.0, 62.4, 128.5, 129.2, 134.2, 138.7, 162.3.
Ethyl 2-(4-methylphenylsulfonyl)acetate, 4lb.
Yellow oil, Rf = 0.59
(PE:EA = 2:1). Yield 19%. 1Н NMR (300.13 MHz, CDCl3, δ, ppm): 1.16 (t,
J = 7.1 Hz, 3H), 2.42 (s, 3H), 4.06 (s, 2Н), 4.06-4.14 (m, 2Н), 7.33 (d, J =
8.1 Hz, 2H), 7.78 (d, J = 8.1 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ,
ppm): 13.8, 21.6, 61.0, 62.2, 128.4, 129.7, 135.7, 145.3, 162.4.
Ethyl 3-oxo-3-phenyl-2-((4-methylphenyl)sulfonyl)propanoate, 3ab.
White solid, mp = 104-106 °С, Rf =0.64 (PE:EA = 2:1). Yield 62%. 1Н
NMR (300.13 MHz, CDCl3, δ, ppm):1.17 (t, J = 7.0 Hz, 3H), 2.43 (s, 3H),
4.12-4.21 (m, 2H), 5.99 (s, 1H), 7.31 (d, J = 8.1 Hz, 2H), 7.49 (dd, J = 7.3,
8.1 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.81 (d, J = 8.1 Hz, 2H), 7.97 (d, J =
8.1 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ, ppm): 13.8, 21.7, 62.9, 75.4,
128.9, 129.3, 130.5, 134.0, 134.5, 135.6, 145.8, 161.6, 185.9. HRMS
(ESI) m/z [M+Na]+: Calculated for [C18H18O5SNa]+ : 369.0767. Found:
369.0761.
Ethyl 2-(4-chlorophenylsulfonyl)acetate, 4lc.
Colorless oil, Rf =
0.72 (PE:EA = 2:1). Yield 41%. 1Н NMR (300.13 MHz, CDCl3, δ, ppm):
1.19 (t, J = 7.3 Hz, 3H), 4.10 (s, 2Н), 4.10-4.17 (m, 2Н), 7.53 (d, J = 8.7
Hz, 2H), 7.87 (d, J = 8.7 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ, ppm):
13.8, 60.8, 62.5, 129.5, 130.1, 137.1, 141.1, 162.2.
Ethyl 3-oxo-3-phenyl-2-((4-chlorophenyl)sulfonyl)propanoate, 3ac.
White solid, mp = 87-89 °С. Rf = 0.64 (PE:EA = 2:1). Yield 50%.1Н NMR
(300.13 MHz, CDCl3, δ, ppm): 1.18 (t, J = 7.0 Hz, 3H), 4.16-4.24 (m, 2H),
6.02 (s, 1H), 7.49-7.54 (m, 4H), 7.65 (t, J = 7.3 Hz, 1H), 7.89 (d, J = 8.8
Hz, 2H), 7.97 (d, J = 8.1 Hz, 2H). 13C NMR (75.48 MHz, CDCl3, δ, ppm):
13.8, 63.1, 75.3, 128.9, 129.0, 129.3, 132.2, 134.7, 135.3, 135.4, 141.6,
Ethyl 2-(4-bromophenylsulfonyl)acetate, 4ld.
Yellow oil, Rf = 0.79
(PE:EA = 2:1). Yield 16%. 1Н NMR (300.13 MHz, CDCl3, δ, ppm): 1.19 (t,
J = 7.3 Hz, 3H), 4.09 (s, 2Н), 4.09-4.16 (m, 2Н), 7.69 (d, J = 8.8 Hz, 2H),
7.78 (d, J = 8.8 Hz, 2H).13C NMR (75.48 MHz, CDCl3, δ, ppm): 13.8, 60.8,
62.4, 129.7, 130.1, 132.4, 137.6, 162.2.
161.4, 185.8. HRMS (ESI) m/z [M+Na]+: Calculated
[C17H15ClNaO5S]+ : 389.0221. Found: 389.0217.
for
Ethyl 2-(naphthalen-2-ylsulfonyl)acetate, 4lf. [36] White solid, mp = 69-
71 °С. Rf = 0.62 (PE:EA = 2:1). Yield 31%.1Н NMR(300.13 MHz, CDCl3,
δ, ppm): 1.11 (t, J = 7.1 Hz, 3H), 4.10 (q, J = 7.1 Hz, 2Н), 4.18 (s, 2Н),
7.59-7.69 (m, 2H), 7.88-8.01 (m, 4H), 8.51 (s, 1Н). 13C NMR (75.48 MHz,
7
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