S. Paul et al. / Tetrahedron Letters 52 (2011) 4051–4055
4055
Karisch, R.; Lautens, M. J. Org. Chem. 2007, 72, 1341; (d) Fuwa, H.; Sasaki, M.
J. Org. Chem. 2009, 74, 212.
Acknowledgments
15. Paul, S. P.; Samanta, S.; Ray, J. K. Tetrahedron Lett. 2010, 51, 5604.
16. (a) Miyaura, N.; Yamada, K.; Suzuki, A. Tetrahedron Lett. 1979, 20, 3437; (b)
Miyaura, N.; Suzuki, A. J. Chem. Soc., Chem. Commun. 1979, 866.
17. (a) Heck, R. F.; Nolley, J. P. J. Org. Chem. 1972, 37, 2320; For recent review on
Heck Reaction see: (b) Le Bras, J.; Muzart, J. Chem. Rev. 2011, 111, 1170.
18. For domino Suzuki/Heck coupling see: (a) Bryan, C. S.; Lautens, M. Org. Lett.
2010, 12, 2754; (b) Wagner, H. A.; Scott, L. T.; de Meijere, A. J. Org. Chem. 2003,
68, 883.
19. General procedure for the synthesis of precursors by Wittig reaction: To a solution
of triphenylphosphoranylidene (1.5 mmol) in 10 ml of solvent (CH2Cl2 or THF)
was added dropwise a solution of the aldehyde (1.0 mmol) in 4 ml of solvent
(CH2Cl2 or THF) at 0 °C under an inert argon atmosphere. The resulting mixture
was stirred at 25 °C until completion of the reaction, which was monitored by
TLC. The solvent was then evaporated under reduced pressure to give the crude
product which was purified by silica gel (60–120 mesh) column chromatography
using petroleum ether/ethyl acetate as the eluent to afford the desired product.
Spectral data of representative compounds:
3-(2-Bromo-3,4-dihydro-naphthalen-1-yl)-acrylic acid ethyl ester (2l):
Yellowish semisolid, Yield 80%, 1H NMR (CDCl3, 200 MHz) d 1.34 (3H, t, J = 7.2),
2.85 (4H, br s), 4.28 (2H, q, J = 7), 6.23 (1H, d, J = 16.2), 7.18–7.22 (3H, m), 7.32–
7.33 (1H, m), 7.80 (1H, d, J = 16.2); 13C NMR (50 MHz, CDCl3) d 14.6, 29.6, 36.3,
60.9, 124.3, 125.7, 126.8, 127.9 (2 ꢀ C), 129.1, 132.9, 133.1, 135.7, 142.0, 167.0.
20. General procedure for the Pd-catalyzed domino Suzuki/Heck coupling: The aryl or
vinyl bromide (1 mmol), 2-bromophenyl boronic acid (1.2 mmol), dry Cs2CO3
(4 mmol) and PPh3 (0.5 mmol) were placed in a two-necked round bottom
flask, flushed with N2 and DMF (6 mL) was added to it. After degasification,
We thank DST, New Delhi for financial support. S.P. thanks CSIR,
New Delhi for senior research fellowship.
Supplementary data
Supplementary data associated with this article can be found, in
References and notes
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Pd(OAc)2 (5 mol %) catalyst was added and the mixture was heated at
a
temperature between 60 and 120 °C (for exact temperature see the
corresponding compound) for 1–1.5 h. The reaction mixture was cooled,
diluted with water and extracted with ethyl acetate (3 ꢀ 15 mL). The solvent
was evaporated after drying (with Na2SO4) to give the crude product which
was purified by silica gel (60–120 mesh) column chromatography using
petroleum ether/ethyl acetate (20:1) as the eluent.
Spectral data of representative compounds:
(5,6-Dihydro-benzo[a]fluoren-11-ylidene)acetic acid ethyl ester (4m)
8. Chernyak, N.; Gevorgyan, V. J. Am. Chem. Soc. 2008, 130, 5636.
ˇ
9. Prashad, M.; Liu, Y.; Mak, X. Y.; Har, D.; Repic, O.; Blacklock, T. J. Tetrahedron
This compound was prepared from the aryl bromide 2l at a temperature of
60 °C over a period of 1–1.5 h to yield the fluorenylidene 4m as an orange
solid; mp 90–91 °C; Yield 56%; 1H NMR (CDCl3, 200 MHz) d 0.90 (3H, t, J = 7),
2.63–2.71 (2H, m), 2.92–2.99 (2H, m), 4.01 (2H, q, J = 7.6), 6.72 (1H, s), 7.07 (1H,
d, J = 7.4), 7.24–7.36 (6H, m), 7.65 (1H, d, J = 7.8); 13C NMR (50 MHz, CDCl3) d
13.3, 21.8, 28.7, 61.2, 115.7, 119.1, 119.6, 125.9, 126.1, 126.4, 126.6, 127.6,
129.4, 132.5, 133.2, 135.7, 139.0, 141.2, 145.3, 149.8, 167.4; Elemental Anal.
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C
21H18O2 requires C, 83.42; H, 6.00. Found: C, 83.40; H, 5.94.
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(11H-benzo[a]fluoren-11-yl)-acetic acid ethyl ester (5m):
This compound was prepared from the aryl bromide 2l at a temperature of
120 °C over a period of 1–1.5 h to yield the fluorenyl 5m as a pale yellow solid;
mp 70–71 °C (lit. Mp21 69.4–70.6); Yield 62%; 1H NMR (CDCl3, 400 MHz) d 1.30
(3H, t, J = 7.2), 2.39 (1H, dd, 10.4, 16.4), 3.42 (1H, dd, J = 3.2, 16.4), 4.23–4.31
(2H, m), 4.84 (1H, dd, J = 3.2, 10.4), 7.31–7.35 (1H, m), 7.42–7.51 (2H, m), 7.57–
7.63 (2H, m), 7.82 (1H, d, J = 7.6), 7.91 (2H, s), 7.96 (1H, d, J = 8), 8.04 (1H, d,
J = 8.4); 13C NMR (50 MHz, CDCl3) d 14.3, 39.2, 43.2, 60.8, 118.7, 119.9, 123.7,
124.5, 125.3, 126.7, 126.9, 127.6, 128.8, 129.5, 129.8, 133.5, 138.4, 141.3, 141.6,
147.9, 172.7; HRMS (ESI, 70 eV): m/z = 303.1376 [M++H] (calcd mass for
C
21H18O2: 303.1385 [M++H]).
21. Orchin, M.; Reggel, L. J. Am. Chem. Soc. 1951, 73, 436.