10.1002/ejoc.201901894
European Journal of Organic Chemistry
FULL PAPER
3.60 (s, 3H), 3.20 (d, J = 15.8 Hz, 1H), 3.17 (s, 3H), 3.01 (d, J = 15.8 Hz,
1H), 2.39 (d, J = 1.3 Hz, 3H); 13C NMR (100 MHz, CDCl3) 167.7, 167.4,
166.0, 160.8, 142.4, 124.0, 122.6, 107.4, 52.0, 51.7, 50.3, 41.7, 16.3; IR
(film) max 2954, 2845, 1773, 1742, 1723, 1602, 1438, 1312, 1240, 1174,
1113, 1032, 930, 867 cm–1; HRMS (ESI) calcd. for C13H16O7Na [M+Na]+
307.0794, found 307.0797.
Keywords: Transtaganolides • Basiliolides • Coumarins • Pyran-
2-ones • Oxidative cleavage
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Reduction of muconolactone 45 with Zn/AcOH. Zinc powder (111 mg,
1.7 mmol, 8.5 equiv) was added to a solution of muconolactone 45 (46
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Na2SO4, and concentrated under reduced pressure to afford an
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inseparable
3:1
mixture
of
(E)-
and
(Z)-5-methoxy-5-
methoxycarbonylmethyl-4-(1-methoxycarbonylpropan-2-ylidene)-3H-
dihydrofuran-2-one (46) as yellowish oil (45 mg, 97% yield): (E
diastereomer) 1H NMR (400 MHz, CDCl3) 3.67 (s, 3H), 3.627 (s, 3H),
3.45 (dq, J = 23.5, 1.8 Hz, 1H), 3.25–3.18 (m, 1H), 3.23 (s, 3H), 3.12–
3.10 (m, 2H), 3.05 (d, J = 15.4 Hz, 1H), 2.96 (d, J = 15.4 Hz, 1H), 1.84 (t,
J = 2.2 Hz, 3H); 13C NMR (100 MHz, CDCl3) 172.36, 170.3, 169.0,
129.0, 128.4, 108.4, 52.04, 51.8, 49.66, 42.9, 41.7, 35.7, 18.0; (Z
diastereomer) 1H NMR (400 MHz, CDCl3) 3.66 (s, 3H), 3.630 (s, 3H),
3.48 (dq, J = 22.2, 1.6 Hz, 1H), 3.38 (dt, J = 15.5, 1.2 Hz, 1H), 3.188 (s,
3H), 3.187 (dq, J = 22.4, 1.5 Hz, 1H), 3.12–3.10 (m, 2H), 3.09 (dt, J =
15.3, 1.3 Hz, 1H), 1.77 (t, J = 1.7 Hz, 3H); 13C NMR (100 MHz, CDCl3)
172.44, 170.5, 169.1, 128.5, 128.1, 108.1, 52.01, 51.7, 49.74, 43.7, 37.9,
36.0, 20.8; IR (film) max 3002, 2955, 2918, 2849, 1792, 1736, 1438,
1360, 1269, 1171, 1130, 991, 930, 734 cm–1; HRMS (ESI) calcd. for
C13H19O7 [M+H]+ 287.1131, found 287.1107.
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J. J. Rubal, F. J. Moreno-Dorado, F. M. Guerra, Z. D. Jorge, A. Saouf,
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Synthesis of pyran-2-one 47. 37% aqueous HCl (700 L) and MeOH
(450 L) were added to a solution of furan-2-one 46 (50 mg, 0.2 mmol) in
CH2Cl2 (5.5 mL). The biphasic system was stirred vigorously until the
disappearance of starting material, 10 d. The mixture was poured into
water (20 mL), and extracted with EtOAc (3×20 mL). The combined
organic phases were washed with brine (40 mL), dried over anhydrous
Na2SO4, and concentrated under reduced pressure. The obtaining
reaction crude was methylated in accordance to general described
methylation method: concentrated H2SO4 (3 drops) in MeOH (8 mL) at rt
for 4 d, and workup consisting of pouring into water (20 mL), extraction
with EtOAc (3×20 mL), and combined organic phases washed with brine
(40 mL). The methylated reaction crude was purified by silica column
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chromatography (EtOAc/hexane
=
1:10 to 1:0) to afford 5,6-
bis(methoxycarbonylmethyl)-2H-pyran-2-one (47) as yellowish oil (11 mg,
25% yield for two steps): 1H NMR (400 MHz, CDCl3) 6.12 (q, J = 1.2 Hz,
1H), 3.72 (s, 3H), 3.71 (s, 3H), 3.61 (s, 2H), 3.39 (s, 2H), 2.17 (d, J = 1.2
Hz, 3H); 13C NMR (100 MHz, CDCl3) 170.2, 168.0, 161.2, 156.1, 154.8,
113.7, 112.2, 52.7, 52.5, 37.4, 32.2, 20.3; IR (film) max 2956, 2850, 1735,
1644, 1556, 1437, 1405, 1343, 1258, 1168, 1011, 854 cm–1; HRMS (ESI)
calcd. for C12H15O6 [M+H]+ 255.0869, found 255.0861.
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Acknowledgements
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We are grateful to the Ministry of Economy and Competitiveness
of Spain (Project AGL2013-42238-R) and the Junta de Analucía
(FQM-169) for the financial support. J.M.A. acknowledges the
Spanish Ministry of Education, Culture and Sport for a fellowship.
The authors are thankfull to the Servicios Centrales de
Investigación Científica
University of Cádiz.
y Tecnológica (SC-ICYT) of the
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13
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