LETTER
Synthesis of Highly Functionalized Spirobenzofuranols and Spirobenzofuranones
2369
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Table 3 Synthesis of Spirobenzofuranones
Entry R1
R2
H
R3
H
H
H
H
R4
Product Yield (%)a
1
2
3
4
H
Me
Me
Me
Ph
9a
9b
9c
9d
68
67
62
50
OEt
H
H
Br
H
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4737.
OEt
a Isolated yield after column chromatography.
Acknowledgment
(12) (a) Kaye, P. T.; Musa, M. A.; Nocanda, X. W.; Robinson,
R. S. Org. Biomol. Chem. 2003, 1, 1133. (b) Lesch, B.;
Torang, J.; Vanderheiden, S.; Bräse, S. Adv. Synth. Catal.
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(f) Govender, T.; Hojabri, L.; Moghaddam, F. M.;
Arvidsson, P. I. Tetrahedron: Asymmetry 2006, 17, 1763.
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Catal. 2006, 348, 967. (h) Shi, Y.-L.; Shi, M. Chem. Eur. J.
2006, 12, 3374. (i) Guo, Y.-W.; Shi, Y.-L.; Li, H.-B.; Shi,
M. Tetrahedron 2006, 62, 5875. (j) Sundén, H.; Ibrahem, I.;
Zhao, G.-L.; Eriksson, L.; Córdova, A. Chem. Eur. J. 2007,
13, 574. (k) Li, H.; Wang, J.; E-Nunu, T.; Zu, L.; Jiang, W.;
Wei, S.; Wang, W. Chem. Commun. 2007, 507. (l) Dai,
L.-Z.; Shi, Y.-L.; Zhao, G.-L.; Shi, M. Chem. Eur. J. 2007,
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10415.
(13) (a) Lesch, B.; Bräse, S. Angew. Chem. Int. Ed. 2003, 43,
115. (b) Nising, C. F.; Ohhemüller, U. K.; Friedrich, A.;
Lesch, B.; Steiner, J.; Schnöckel, H.; Nieger, M.; Bräse, S.
Chem. Eur. J. 2006, 12, 3647. (c) Ohhemüller, U. K.;
Nising, C. F.; Nieger, M.; Bräse, S. Eur. J. Org. Chem. 2006,
1535. (d) Nising, C. F.; Ohhemüller, U. K.; Bräse, S. Angew.
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Korotaev, V. Y.; Chizhov, D. L.; Kutyashev, I. B.;
Yachevskii, D. S.; Kazheva, O. N.; Dyachenko, O. A.;
Charushin, V. N. J. Org. Chem. 2006, 71, 4538. (f) Kaye,
P. T.; Musa, M. A.; Nocanda, X. W. Synthesis 2003, 531.
(g) Kaye, P. T.; Musa, M. A. Synth. Commun. 2003, 33,
1755. (h) Lee, K. Y.; Kim, J. M.; Kim, J. N. Bull. Korean
Chem. Soc. 2003, 24, 17. (i) Lee, K. Y.; Kim, J. M.; Kim,
J. N. Synlett 2003, 357. (j) Hong, W. P.; Lee, K.-J. Synthesis
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Bráse, S. Synlett 2008, 2702.
One of the authors (K.K.) is thankful to the Council of Scientific and
Industrial Research, New Delhi, India for the research fellowship.
References and Notes
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(14) Experimental Procedure for the Synthesis of Spiroben-
zofuranol 3 and 4:
A mixture of salicylaldehyde 1 (1.62 mmol, 1.2 equiv),
N-substituted maleimide 2 (1.35 mmol, 1.0 equiv) and
DABCO (30 mol%) was stirred at 70 °C under neat
conditions for 1–2 h. The residue was dissolved in EtOAc
(20 mL) and given a dilute HCl wash (1 × 20 mL) and H2O
wash (2 × 20 mL). The EtOAc layer was dried over anhyd
Na2SO4 and removal of solvent under reduced pressure gave
a crude product, which was purified by flash column
chromatography with EtOAc–PE (20:80) as eluent to obtain
spirobenzofuranols 3 and 4.
Spectral Data of Compound 3b: colorless solid; mp 162–
164 °C; Rf 0.33 (50% EtOAc–PE). IR: 3450, 2918, 1785,
1698, 1623, 1441, 1195 cm–1. 1H NMR (500 MHz, DMSO-
d6): d = 1.26 (t, 3 H, J = 6.9 Hz), 2.85 (s, 3 H), 2.88 (d, 1 H,
J = 18.3 Hz), 3.37 (d, 1 H, J = 18.3 Hz), 3.98–4.03 (m, 2 H),
5.19 (d, 1 H, J = 6.9 Hz), 6.17 (d, 1 H, J = 6.9 Hz), 6.87–6.95
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Synlett 2009, No. 14, 2366–2370 © Thieme Stuttgart · New York