A. Rosales et al. / Tetrahedron 67 (2011) 3071e3075
3075
0.071 mmol, 55%) and its 3-epimer (2R
*
,3S
*
,4S
*
)-methyl 4-hydroxy-
a ‘Juan de la Cierva’ contract to A.R., and to Universidad de Almería
2-phenylchromane-3-carboxylate (15b) (8 mg, 0.019 mmol, 15%).
for a scholarship to C.L.
4.7.1. Compound 15a. White solid, mp 167e169 ꢀC; IR (film) nmax
References and notes
3358, 1731, 1581, 1483, 1429, 1232, 1189, 1008, 759, 697 cmꢁ1 1H
;
1. Gansauer, A.; Rinker, B.; Pierobon, M.; Grimme, S.; Gerenkamp, M.; Muck-
Lichtenfeld, C. Angew. Chem., Int. Ed. 2003, 42, 3687e3690.
NMR (CDCl3, 300 MHz)
d
7.57 (1H, br d, J¼7.7 Hz), 7.42 (5H, m), 7.24
(1H, br d, J¼7.7 Hz), 7.05 (1H, dt, J¼0.8, 7.3 Hz), 6.92 (1H, d,
J¼8.1 Hz), 5.36 (1H, dd, J¼10.0, 8.5 Hz, H-3), 5.16 (1H, d, J¼10.5 Hz,
H-2), 3.48 (3H, s), 3.11 (1H, dd, J¼10.5, 10.0 Hz, H-4), 2.39 (1H, d,
2. Gansaeuer, A.; Rinker, B.; Ndene-Schiffer, N.; Pierobon, M.; Grimme, S.; Ger-
enkamp, M.; Mueck-Lichtenfeld, C. Eur. J. Org. Chem. 2004, 2337e2351.
ꢀ
ꢀ
ꢀ
~
3. Jimenez-Gonzalez, L.; Alvarez-Corral, M.; Munoz-Dorado, M.; Rodríguez-García,
J¼8.5 Hz, OH); 13C NMR (CDCl3, 75 MHz)
d 171.89 (C), 153.70 (C),
I. Chem.dEur. J. 2006, 12, 8762e8769.
4. Jimenez-Gonzalez, L.; García-Munoz, S.; Alvarez-Corral, M.; Munoz-Dorado, M.;
ꢀ
ꢀ
ꢀ
~
~
137.41 (C), 129.33 (CH), 128.97 (CH), 128.58 (CH), 126.95 (CH),
126.80 (CH), 124.35 (C), 121.42 (CH), 116.51 (CH), 78.75 (CH), 68.42
Rodríguez-García, I. Chem.dEur. J. 2007, 13, 557e568.
ꢀ
ꢀ
ꢀ
~
5. Jimenez-Gonzalez, L.; Alvarez-Corral, M.; Munoz-Dorado, M.; Rodríguez-García,
I. Chem. Commun. 2005, 2689e2691.
6. Grigg, R.; Liu, A.; Shaw, D.; Suganthan, S.; Woodall, D. E.; Yoganathan, G. Tet-
rahedron Lett. 2000, 41, 7125e7128.
(CH), 55.20 (CH)
*
, 52.01 (CH3)
*
*
. May be interchanged. HREIMS (m/
z) calcd for C17H16O4 284.1049 [M]þ, found 284.1040.
7. Doyle, M. P.; Duffy, R.; Ratnikov, M.; Zhou, L. Chem. Rev. 2010, 110, 704e724.
8. Slattery, C. N.; Ford, A.; Maguire, A. R. Tetrahedron 2010, 66, 6681e6705.
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10. Saito, H.; Oishi, H.; Kitagaki, S.; Nakamura, S.; Anada, M.; Hashimoto, S. Org. Lett.
2002, 4, 3887e3890.
4.7.2. Compound 15b. White solid, mp 199e201 ꢀC; IR (film) nmax
3433, 1730, 1483, 1168, 752 cmꢁ1; 1H NMR (CDCl3, 300 MHz)
d 7.61
(1H, br d, J¼7.7 Hz), 7.42 (4H, m), 7.37 (1H, m), 7.25 (1H, br d,
J¼7.7 Hz), 7.07 (1H, dt, J¼1.2, 7.7 Hz), 6.97 (1H, br d, J¼8.1 Hz), 5.43
(1H, d, J¼2.4 Hz), 5.30 (1H, dd, J¼10.5, 6.1 Hz), 3.54 (1H, dd, J¼6.1,
2.4 Hz), 3.46 (3H, s), 2.80 (1H, d, J¼10.5 Hz, OH); 13C NMR (CDCl3,
11. Davies, H. M. L.; Beckwith, R. E. J. Chem. Rev. 2003, 103, 2861e2903.
ꢀ
~
12. Garcia-Munoz, S.; Alvarez-Corral, M.; Jimenez-Gonzalez, L.; Lopez-Sanchez, C.;
~
Rosales, A.; Munoz-Dorado, M.; Rodriguez-Garcia, I. Tetrahedron 2006, 62,
12182e12190.
13. McKervey, M. A.; Ye, T. J. Chem. Soc., Chem. Commun. 1992, 823e824.
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15. McCarthy, N.; McKervey, M. A.; Ye, T.; McCann, M.; Murphy, E.; Doyle, M. P.
Tetrahedron Lett. 1992, 33, 5983e5986.
75 MHz)
d 170.02 (C), 154.13 (C), 138.32 (C), 129.03 (CH), 128.27
(CH), 127.95 (CH), 127.13 (CH), 125.40 (CH), 124.58 (C), 121.69 (CH),
116.28 (CH), 77.19 (CH), 66.64 (CH), 51.41 (CH3)
*
, 50.87 (CH)
*
. May
*
be interchanged. HREIMS (m/z) calcd for C17H16O4 284.1049 [M]þ,
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4705e4708.
found 284.1062.
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4.8. Methyl 2-phenyl-2H-chromene-3-carboxylate (5)
Compounds 15a (16 mg, 0.05 mmol) and 15b (6 mg,
0.019 mmol) were dissolved in toluene (2.5 mL), and p-TsOH (6 mg,
0.03 mmol) was added. The mixture was refluxed for 50 min, then
diluted with Et2O and washed with brine. The dried (Na2SO4) ex-
tract was concentrated in vacuo and purified by chromatography
over silica gel, eluting with hexane/Et2O 9:1, to give compound 5
(16 mg, 0.054 mmol, 79%): white solid, mp¼82e84 ꢀC; IR (film)
nmax 3029, 2949, 1709, 1637, 1602, 1434, 1289, 1255, 1210, 1118, 997,
758, 695 cmꢁ1 1H NMR (CDCl3, 300 MHz)
; d 7.70 (1H, s), 7.40 (2H,
m), 7.29 (3H, m), 7.21 (2H, d, J¼7.3 Hz), 6.92 (1H, dt, J¼7.7, 1.2 Hz),
6.82 (1H, dd, J¼7.7, 0.8 Hz), 6.31 (1H, s), 3.79 (3H, s); 13C NMR
(CDCl3, 75 MHz)
d 165.24 (C), 153.60 (C), 139.08 (C), 133.34 (CH),
132.28 (CH), 128.80 (CH), 128.57 (CH), 128.45 (CH), 127.12 (CH),
124.23 (C), 121.49 (CH), 120.30 (C), 116.80 (CH), 75.17 (CH), 51.93
(CH3). HREIMS (m/z) calcd for C17H14O3 266.0943 [M]þ, found
266.0952.
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4.9. Flavanone (6)
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A mixture of 14 (40 mg, 0.13 mmol), NaCl (10 mg, 0.16 mmol)
and water (0.1 mL) in DMSO (2 mL) was heated at 155e165 ꢀC for
4 h, cooled, poured into water (15 mL), and extracted with hexane/
Et2O (1:1). The organic layer was washed with water and brine,
dried (Na2SO4) and evaporated. Flash chromatography (Et2O) of the
residue gave flavanone 6 (32 mg, 0.12 mmol, 89%).35
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Acknowledgements
We wish to acknowledge the Spanish Ministerio de Ciencia e
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ꢀ
Innovacion for financial support (Project CTQ2010-17115), for