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J. Oyamada, T. Kitamura / Tetrahedron 62 (2006) 6918–6925
157.27, 169.38. MS (EI, m/z): 192 (M+). Anal. Calcd for
C11H12O3: C, 68.74; H, 6.29. Found: C, 68.58; H, 6.31.
(AcOEt). 1H NMR (300 MHz, DMSO-d6): d 3.04 (dd,
J¼5.7, 16.2 Hz, 1H, COCH2), 3.14 (dd, J¼6.9, 16.2 Hz,
1H, COCH2), 4.62 (dd, J¼5.7, 6.9 Hz, 1H, CH), 6.81 (d, J¼
8.4 Hz, 1H, aryl), 6.96 (d, J¼2.4 Hz, 1H, aryl), 7.12 (d,
J¼8.7 Hz, 1H, aryl), 7.25 (d, J¼2.1 Hz, 1H, aryl), 7.28
(dd, J¼2.4, 8.4 Hz, 1H, aryl), 7.50 (dd, J¼2.1, 8.7 Hz, 1H,
aryl). 13C NMR (75.5 MHz, DMSO-d6): d 33.45, 34.79,
110.23, 116.07, 117.65, 118.88, 127.08, 129.45, 130.51,
130.83, 131.26, 131.36, 150.82, 154.41, 167.03. MS (EI,
m/z): 396, 398, 400 (M+). Anal. Calcd for C15H10Br2O3:
C, 45.26; H, 2.53. Found: C, 45.36; H, 2.46.
3.2.26. (2Z)-3-(4-Hydroxy-2,6-dimethylphenyl)cinnamic
acid (4b). Light yellow crystals. Mp 219–221 ꢀC (AcOEt/
hexane). 1H NMR (300 MHz, CD3OD): d 1.97 (s, 6H,
CH3), 6.53 (s, 2H, aryl), 6.64 (s, 1H, vinyl), 7.32 (app s,
5H, phenyl). 13C NMR (75.5 MHz, CD3OD): d 20.20,
115.08, 119.26, 128.00, 129.73, 130.56, 130.86, 137.36,
140.26, 156.35, 157.37, 169.35. MS (EI, m/z): 268 (M+).
Anal. Calcd for C17H16O3: C, 76.10; H, 6.01. Found: C,
75.96; H, 6.00. The stereochemistry of 4b was determined
by NOE experiments.
3.2.31. Ethyl 3-oxooctanoate (6).23 Yellow liquid.
3.2.27. 4-(2-Hydroxy-5-methylphenyl)-6-methyl-3,4-di-
hydrocoumarin (5a). Colorless crystals. Mp 166–168 ꢀC
(CH2Cl2/hexane). H NMR (300 MHz, CDCl3): d 2.15 (s,
1
References and notes
3H, CH3), 2.26 (s, 6H, CH3), 2.95 (dd, J¼6.6, 16.1 Hz,
1H, COCH2), 3.19 (dd, J¼5.7, 16.1 Hz, 1H, COCH2), 4.59
(dd, J¼5.7, 6.6 Hz, 1H, CH), 6.05 (br s, 1H, OH), 6.54 (d,
J¼2.1 Hz, 1H, aryl), 6.61 (d, J¼8.1 Hz, 1H, aryl), 6.85
(dd, J¼2.1, 8.1 Hz, 1H, aryl), 6.86 (d, J¼2.1 Hz, 1H, aryl),
7.01 (d, J¼8.1 Hz, 1H, aryl), 7.09 (dd, J¼2.1, 8.1 Hz, 1H,
aryl). 13C NMR (75.5 MHz, CDCl3): d 20.52, 20.71,
35.17, 35.26, 115.51, 116.66, 124.55, 126.48, 128.76,
129.02, 129.13, 129.97, 134.44, 149.84, 151.03, 169.83,
169.86. MS (EI, m/z): 268 (M+). Anal. Calcd for
C17H16O3: C, 76.10; H, 6.01. Found: C, 75.87; H, 5.97.
The structure of 5a was determined by NOE experiments.
1. Staunton, J. Comprehensive Organic Chemistry; Sammes,
P. G., Ed.; Pergamon: Oxford, 1979; Vol. 4, pp 651–653.
2. Matern, U.; Luer, P.; Kreusch, D. Comprehensive Natural
¨
Products Chemistry; Sankawa, U., Ed.; Pergamon: Oxford,
1999; Vol. 1, pp 623–635.
3. Hepworth, J. D. Comprehensive Heterocyclic Chemistry;
Boulton, A. J., McKillop, A., Eds.; Pergamon: Oxford, 1984;
Vol. 3, pp 799–810.
4. Pd: (a) An, Z.; Catellani, M.; Chuisoli, G. P. J. Organomet.
Chem. 1989, 371, C51–C52; (b) Deshpande, P. P.; Martin,
O. R. Tetrahedron Lett. 1990, 31, 6313–6316; (c) Catellani,
M.; Chiusoli, G. P.; Fagnola, M. C.; Solari, G. Tetrahedron
Lett. 1994, 35, 5919–5922; (d) Catellani, M.; Chiusoli, G. P.;
Fagnola, M. C.; Solari, G. Tetrahedron Lett. 1994, 35, 5923–
5926; (e) Cacchi, S. Pure Appl. Chem. 1996, 68, 45–52; (f)
Catellani, M.; Chiusoli, G. P.; Marzolini, G.; Rossi, E.
J. Organomet. Chem. 1996, 525, 65–69; (g) Arcadi, A.;
Cacchi, S.; Fabrizi, G.; Marinelli, F.; Pace, P. Synlett 1996,
568–570; (h) Cacchi, S.; Fabrizi, G.; Moro, L.; Pace, P.
Synlett 1997, 1367–1370; (i) Kadnikov, D. V.; Larock, R. C.
Org. Lett. 2000, 2, 3643–3646; (j) Hesse, S.; Kirsch, G.
Tetrahedron Lett. 2002, 43, 1213–1215; (k) Kadnikov, D. V.;
Larock, R. C. J. Org. Chem. 2003, 68, 9423–9432; (l)
Kadnikov, D. V.; Larock, R. C. J. Organomet. Chem. 2003,
687, 425–435; (m) Palencia, H.; Garcia-Jimenez, F.; Takacs,
J. M. Tetrahedron Lett. 2004, 45, 3849–3853; (n) Battistuzzi,
G.; Cacchi, S.; Salve, I. D.; Fabrizi, G.; Parisi, L. M. Adv.
Synth. Catal. 2005, 347, 308–312; (o) Aoki, S.; Oyamada, J.;
Kitamura, T. Bull. Chem. Soc. Jpn. 2005, 78, 468–472.
5. Ru: Chatterjee, A. K.; Toste, F. D.; Goldberg, S. D.; Grubbs,
R. H. Pure Appl. Chem. 2003, 75, 421–425.
6. Rh: (a) Yoneda, E.; Sugioka, T.; Hirao, K.; Zhang, S.-W.;
Takahashi, S. J. Chem. Soc., Perkin Trans. 1 1998, 477–483;
(b) Tollari, S.; Palmisano, G.; Cenini, S.; Cravotto, G.;
Giovenzana, G. B.; Penoni, A. Synthesis 2001, 735–740.
7. Rh and Co: Park, K. H.; Jung, I. G.; Chung, Y. K. Synlett 2004,
2541–2544.
8. Ni: Rayabarapu, D. K.; Shukla, P.; Cheng, C.-H. Org. Lett.
2003, 5, 4903–4906.
9. (a) Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 1996, 118,
6305–6306; (b) Trost, B. M.; Toste, F. D.; Greenman, K.
J. Am. Chem. Soc. 2003, 125, 4518–4526.
3.2.28. 6,60-Dimethyl-3,4-dihydro-[4,80]bichromenyl-
2,20-dione(5b). Colorless crystals. Mp 244–246 ꢀC (CH2Cl2/
hexane). 1H NMR (300 MHz, CDCl3): d 2.27 (s, 3H, CH3),
2.30 (s, 3H, CH3), 3.08 (dd, J¼6.0, 15.9 Hz, 1H, COCH2),
3.14 (dd, J¼4.5, 15.9 Hz, 1H, COCH2), 4.98 (dd, J¼4.5,
6.0 Hz, 1H, CH), 6.45 (d, J¼9.6 Hz, 1H, vinyl), 6.77 (d,
J¼1.8 Hz, 1H, aryl), 6.92 (d, J¼1.8 Hz, 1H, aryl), 7.08 (d,
J¼8.1 Hz, 1H, aryl), 7.16 (dd, J¼1.8, 8.1 Hz, 1H, aryl),
7.19 (d, J¼1.8 Hz, 1H, aryl), 7.68 (d, J¼9.6 Hz, 1H, vinyl).
13C NMR (75.5 MHz, CDCl3): d 20.74, 20.84, 33.69, 35.80,
116.66, 117.05, 118.93, 123.44, 127.34, 128.49, 128.84,
129.81, 131.26, 134.51, 134.72, 143.75, 149.23, 150.19,
160.36, 167.53. MS (EI, m/z): 320 (M+). Anal. Calcd for
C20H16O4: C, 74.99; H, 5.03. Found: C, 74.74; H, 5.05.
3.2.29. 4-(4-Hydroxy-2-methylphenyl)-7-methyl-3,4-di-
hydrocoumarin (5c). Colorless crystals. Mp 183–185 ꢀC
(AcOEt). H NMR (300 MHz, DMSO-d6): d 2.27 (s, 3H,
1
CH3), 2.30 (s, 3H, CH3), 2.88 (dd, J¼7.2, 15.9 Hz, 1H,
COCH2), 2.99 (dd, J¼5.7, 15.9 Hz, 1H, COCH2), 4.51 (dd,
J¼5.7, 7.2 Hz, 1H, CH), 6.48 (dd, J¼2.1, 8.4 Hz, 1H, aryl),
6.54 (d, J¼8.4 Hz, 1H, aryl), 6.63 (d, J¼2.1 Hz, 1H,
aryl), 6.78 (d, J¼7.8 Hz, 1H, aryl), 6.91 (d, J¼7.8 Hz, 1H,
aryl), 7.00 (s, 1H, aryl), 9.26 (s, 1H, OH). 13C NMR
(75.5 MHz, DMSO-d6): d 19.15, 20.55, 34.78, 35.82,
113.16, 116.74, 117.39, 123.58, 125.16, 127.46, 127.86,
129.29, 137.02, 138.12, 151.58, 156.08, 167.94. MS (EI,
m/z): 268 (M+). Anal. Calcd for C17H16O3: C, 76.10; H,
6.01. Found: C, 75.98; H, 6.01. The structure of 5c was deter-
mined by NOE experiments.
10. Au: Shi, Z.; He, C. J. Org. Chem. 2004, 69, 3669–3671.
11. (a) Jia, C.; Piao, D.; Kitamura, T.; Fujiwara, Y. J. Org. Chem.
2000, 65, 7516–7522; (b) Oyamada, J.; Jia, C.; Fujiwara, Y.;
3.2.30. 4-(5-Bromo-2-hydroxyphenyl)-6-bromo-3,4-dihy-
drocoumarin (5d). Colorless crystals. Mp 237.5–238.5 ꢀC