V. V. Kouznetsov, D. R. Merchan Arenas / Tetrahedron Letters 50 (2009) 1546–1549
1549
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R. J. Mol. Catal. A: Chem. 2007, 267, 53; (b) Agnihotri, G.; Misra, A. K. Tetrahedron
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Acknowledgment
This work was supported by the Instituto Colombiano Para el
Desarrollo de La Ciencia y La Tecnología ‘Francisco José de Caldas’
(COLCIENCIAS-CENIVAM, Grant No. 432-2004).
References and notes
22. Selected spectral data for 3: r-1-ethyl-5-hydroxy-c-3-(4-hydroxy-5-
methoxyphenyl)-6-methoxy-t-2-methylindane (3): Mp 184–185 °C. IR(KBr):
3487, 2962, 1265 cmÀ1 1H NMR (400 MHz; CDCl3; Me4Si), d (ppm): 0.97 (3H, t,
.
1. Saleem, M.; Kim, H. J.; Ali, M. S.; Lee, Y. S. Nat. Prod. Rep. 2005, 22, 696.
2. MacRae, W. D.; Towers, C. H. N. Phytochemistry 1984, 23, 1207.
3. Ward, R. S. Chem. Soc. Rev. 1982, 11, 75.
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5. Puxeddu, E. Gazz. Chim. Ital. 1909, 131.
6. Bergman, W.; McAleer, W. J. J. Am. Chem. Soc. 1951, 73, 4969.
7. Ko, F. N.; Liao, C. H.; Kuo, Y. H.; Lin, Y. L. Biochim. Biophys. Acta 1995, 1258,
145.
8. Murakami, Y.; Shoji, M.; Hirata, A.; Tanaka, S.; Yokoe, I.; Fujisawa, S. Arch.
Biochem. Biophys. 2005, 434, 326.
9. (a) Atsumi, T.; Murakami, Y.; Shibuya, K.; Tonosaki, K.; Fujisawa, S. Anticancer
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10. Griengl, H.; Foidl, G. Patent US No. 4,256,764, 1981.
11. Lin, C. H.; Kuo, Y. H.; Lin, Y. L.; Teng, C. M. J. Pharm. Pharmacol. 1994, 46,
54.
J = 7.3 Hz, Me), 1.03 (3H, d, J = 6.9 Hz, 2-Me), 1.31–1.44 (1H, m, CH2), 1.65–1.75
(1H, m, CH2), 2.40–2.51 (1H, m, 2-H), 2.85–2.95 (1H, m, 1-H), 3.73 (1H, d,
J = 9.5 Hz, 3-H) 3.80 (3H, s, –OCH3Ar), 3.89 (3H, s, 6-OCH3), 5.51 (1H, s, OHAr),
5.56 (1H, s, 5-OH), 6.48 (1H, s, 4-H), 6.62 (1H, br s, 2-HAr), 6.65 (1H, br d, J = 8.0,
6-HAr), 6.77 (1H, br s, 7-H), 6.83 (1H, d, J = 8.0, 5-HAr); 13C NMR (100 Hz; CDCl3;
Me4Si), d (ppm): 146.4, 145.1, 144.5, 144.1, 139.1, 138.7, 135.8, 121.5, 114.0,
111.0, 110.6, 107.5, 56.7, 56.1, 55.9, 49.2, 48.5, 22.4, 13.8, 12.2. COSY
correlations: 0.97/1.31–1.44 [Me/CH2], 0.97/1.65–1.75 [Me/CH2], 1.03/2.40–
2.51 [2-Me/2-H], 1.31–1.44/0.97 [CH2/Me], 1.31–1.44/1.65–1.75 [CH2/CH2],
1.31–1.44/2.85–2.95 [CH2/1-H], 1.65–1.75/0.97 [CH2/Me], 1.65–1.75/1.31–1.44
[CH2/CH2], 1.65–1.75/2.85–2.95 [CH2/1-H], 2.40–2.51/1.03 [2-H/2-Me], 2.40–
2.51/3.73 [2-H/3-H], 2.85–2.95/1.31–1.44 [1-H/CH2], 2.85–2.95/1.65–1.75 [1-
H/CH2], 2.85–2.95/1.65–1.75 [1-H/CH2], 3.73/2.40–2.51 [3-H/2-H], 3.73/6.48
[3-H/4-H], 3.80/6.62 [OCH3Ar/2-HAr], 3.89/6.77 [6-OCH3/7-H], 6.48/3.73 [4-H/
3-H], 6.62/3.80 [2-HAr/OCH3Ar], 6.77/3.89 [7-H/6-OCH3]. HMQC correlations:
0.96/12.2 [Me/CMe], 1.03/13.8 [2-Me/C2-Me], 1.31–1.44/22.4 [CH2/CCH2], 1.65–
1.75/22.4 [CH2/CCH2], 2.40–2.51/49.2 [2-H/2-C], 2.85–2.95/48.5 [1-H/1-C],
3.73/56.7 [3-H/3-C], 3.80/55.9 [–OCH3Ar/–OCH3Ar], 3.89/55.9 [6-OCH3/6-
OCH3], 6.48/111.0 [4-H/4-C], 6.65/110.6 [2-HAr/2-CAr], 6.65/121.5 [6-HAr/6-
CAr], 6.77/107.5 [7-H/7-C], 6.83/114.0 [5-HAr/5-CAr]. HMBC correlations: 0.96/
22.4/48.5 [Me/CCH2/1-C], 1.03/48.5/49.2/56.7 [2-Me/1-C/2-C/3-C], 1.31–1.44/
12.2/48.5/135.8 [CH2/CMe/1-C/7a-C], 1.65–1.75/12.2/48.5/138.7 [CH2/CMe/1-C/
7a-C], 2.40–2.51/13.8/22.4/48.5/56.7/138.7 [2-H/C2-Me/CCH2/1-C/3-C/7a-C],
2.85–2.95/12.2/22.4/49.2/56.7/107.5/138.7 [1-H/CMe/CCH2/2-C/3-C/7-C/7a-C],
12. Danilova, L. I.; Ivanova, I. Ya.; Kozlova, Z. G.; Kore, S. A.; Livshits, A. G.; Osipova,
V. P.; Tsepalov, V. F.; Shlyapintokh, V. Ya. Patent SU No. 224741, 1968.
13. There are four possible diastereomers for these structures, namely
a
(1,2-cis-
2,3-trans), b (1,2-cis-2,3-cis),
see following figure:
c (1,2-trans-2,3-trans) and d (1,2-trans-2,3-cis),
Me
Me
Me
Me
Me
Me
R
R
R
R
Me
Me
3.73/13.8/49.2/110.6/121.5/135.8/139.1
[3-H/C2-Me/2-C/2-CAr/6-CAr/3a-C/1-
CAr], 3.81/146.7 [CH3OAr/3-CAr], 3.89/146.4/144.5 [6-OCH3/3-C/4-CAr], 5.50/
111.0 [HOAr/4-C], 5.56/114.0/144.5 [5-OH/5-CAr/4-CAr], 6.48/56.7/107.5/121.5/
138.7/145.1 [4-H/3-C/7-C/6-CAr/7a-C/6-C], 6.62/56.7/121.5/135.8/145.1 [2-
HAr/3-C/6-CAr/3a-C/6-C], 6.65/56.7/110.6 [2-HAr/3-C/2-CAr], 6.77/48.5/138.7
[7-H/1-C/7a-C], 6.83/121.5/146.4 [5-HAr/6-CAr/3-C]. MS: m/z (relative
intensity): 328 (M+, 60%), 299 (100), 204 (40), 175 (25). Anal. Calcd for
C20H24O2: C, 81.04; H, 8.16. Found: C, 81.25; H, 8.43.
α
β
δ
γ
R
R
R
R
.
14. (a) Angle, S. R.; Arnaiz, D. O. J. Org. Chem. 1992, 57, 5937;; (b) Alesso, E.; Torviso,
R.; Lantaño, B.; Erlich, M.; Finkielsztein, L. M.; Moltrasio, G.; Aguirre, J. M.;
Brunet, E. Arkivoc 2003, 283; (c) Lantaño, B.; Aguirre, J. M.; Finkielsztein, L. M.;
Alesso, E.; Brunet, E.; Moltrasio, G. Y. Synth. Commun. 2004, 34, 625; (d)
Lantaño, B.; Aguirre, J. M.; Ugliarolo, E. A.; Benegas, M. L.; Moltrasio, G. Y.
Tetrahedron 2008, 64, 4090.
15. (a) MacMillan, J.; Martin, I. L.; Morris, G. J. Tetrahedron 1969, 25, 905; (b) Alesso,
E. N.; Tombari, D. G.; Moltrasio, G. Y.; Aguirre, J. M. Can. J. Chem. 1987, 65, 2568;
(c) Müller, A.; Meszaros, M.; Lempert-Sreter, M.; Szara, I. J. Org. Chem. 1951, 16,
1003; (d) del Rosario Torviso, M.; Alesso, E. N.; Moltrasio, G. Y.; Vásquez, P. G.;
Pizzio, L. P.; Cáceres, C. V.; Blanco, M. N. Appl. Catal. A: Gen. 2006, 301, 25.
16. (a) Al-Farhan, E.; Keehn, P. M.; Stevenson, R. J. Chem. Res., Synop. 1992, 36; (b)
Zarubin, M. Ya.; Kromina, L. V.; Zakharov, V. I. Zh. Org. Khim. 1975, 11, 632.
17. Chen, J.; Spear, S. K.; Huddleston, J. G.; Rogers, R. D. Green Chem. 2005, 7, 64.
18. Andrade, C. K. Z.; Alves, L. M. Curr. Org. Chem. 2005, 9, 195.
19. For recent examples of the use of PEG in organic synthesis, see: (a) Li, J.-H.; Liu,
W.-J.; Xie, Y.-X. J. Org. Chem. 2005, 70, 5409; (b) Chandrasekhar, S.;
Shyamsunder, T.; Chandrashekar, G.; Narsihmulu, C. Synlett 2004, 522; (c)
Zhang, Z.-H.; Yin, L.; Wang, Y.-M.; Liu, J.-Y.; Li, Y. Green Chem. 2004, 6, 563; (d)
Smith, C. B.; Raston, C. L.; Sobolev, A. N. Green Chem. 2005, 7, 650; (e) van den
Ancker, T. R.; Cave, G. W. V.; Raston, C. L. Green Chem. 2006, 8, 50; (f) Jain, S. L.;
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23. General experimental procedure for synthesis of cyclodimer 3 using PEG-400
as a reaction medium: To a trans-isoeugenol (4.62 mmol) in PEG-400 (5 mL),
BF3ÁOEt2 (10 mol %) was added at 0 °C. The reaction mixture was kept slowly to
room temperature and continuously stirring. The resulting mixture was stirred
at 70 °C for 5 h. After completion of the reaction, as indicated by TLC, a crude
product was purified by column chromatography (ethyl acetate–petroleum
ether, 1:5) to obtain the respective r-1-ethyl-5-hydroxy-t-3-(4-hydroxy-5-
methoxyphenyl)-6-methoxy-t-2-methyl-indane 3. When MeCN was used, the
reaction mixture was treated with
a saturated solution of Na2CO3, and
extracted with ethyl acetate (2 Â 30 mL), the organic layers were dried over
Na2SO4. The crude product was purified by column chromatography to obtain
the respective cyclodimer 3.
24. General experimental procedure for synthesis of cyclodimer 3 using SiO2–
OSO3H/MeCN as a recoverable heterogeneous system prepared from silica gel
and chlorosulfonic acid.20c,b To
a stirred solution of trans-isoeugenol
(4.62 mmol) in MeCN (30 mL) at rt was added SiO2–OSO3H (25% W/W). The
mixture was stirred at rt until reaction was completed as indicated by TLC.The
catalyst was filtered off and washed three times with acetone. The filtrate was
concentrated under vacuum to obtain a crude product and was purified by
column chromatography (ethyl acetate–petroleum ether, 1:5).
25. Trans-isohomogenol (yellowish liquid) was prepared by methylation (MeI/
NaOH/Me2CO) of trans-isoeugenol.
26. O-benzylated isoeugenol (Mp 51–52 °C) was prepared by benzylation (BnBr/
K2CO3/Me2CO) of trans-isoeugenol.