PAPER
[5+3] Cycloaddition of 3-Oxidopyrylium
327
concentrated under reduced pressure. Purification of the resultant
residue by flash chromatography (silica gel, EtOAc–hexanes, 3:2)
afforded the diketone 20.
(8) (a) Mehta, G.; Singh, V. Chem. Rev. 1999, 99, 881.
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2
2
006, 45, 5740. (d) Deiters, A.; Martin, S. F. Chem. Rev.
004, 104, 2199. (e) McReynolds, M. D.; Dougherty, J. M.;
Yield: 0.098 g (94%); white solid; mp 95 °C.
–
1
IR (CHCl ): 1721 cm .
3
Hanson, P. R. Chem. Rev. 2004, 104, 2239.
1
(9) (a) Wender, P. A.; Ihle, N. C. J. Am. Chem. Soc. 1986, 108,
H NMR (400 MHz, CDCl ): d = 7.39–7.26 (m, 10 H), 5.04 (d,
3
4678. (b) Wender, P. A.; Snapper, M. L. Tetrahedron Lett.
J = 10.8 Hz, 1 H), 4.69 (d, J = 12 Hz, 1 H), 4.52–4.45 (m, 3 H), 4.14
1987, 28, 2221. (c) Wender, P. A.; Ihle, N. C. Tetrahedron
(
t, J = 4.8 Hz, 1 H), 3.89 (d, J = 11.6 Hz, 1 H), 3.78–3.75 (m, 1 H),
Lett. 1987, 28, 2451. (d) Wender, P. A.; Ihle, N. C.; Correia,
C. R. D. J. Am. Chem. Soc. 1988, 110, 5904. (e) Wender, P.
A.; Tebbe, M. J. Synthesis 1991, 1089. (f) Wender, P. A.;
Nuss, J. M.; Smith, D. B.; Suarez-Sobrino, A.; Vagberg, J.;
Decosta, D.; Bordner, J. J. Org. Chem. 1997, 62, 4908; and
references cited therein.
2
8
1
.99–2.92 (m, 1 H), 2.65 (dd, J = 16, 5.6 Hz, 1 H), 2.26 (dd, J = 16,
.8 Hz, 1 H), 2.16–2.10 (m, 1 H), 2.07 (s, 3 H), 1.94–1.80 (m, 2 H),
.48–1.41 (m, 1 H).
1
3
C NMR (100 MHz, CDCl ): d = 206.3, 204.3, 137.3, 137.1, 129.6,
3
1
6
28.8, 128.6, 128.3, 127.9, 127.7, 127.6, 81.8, 79, 74, 71.2, 70.7,
9.8, 44.9, 44.4, 29.7, 26, 22.8.
(
(
(
10) (a) Sieburth, S. M.; McGee, K. F. Jr.; Al-Tel, T. H. J. Am.
Chem. Soc. 1998, 120, 587. (b) Sieburth, S. M.; Cunard, N.
T. Tetrahedron 1996, 52, 6251.
11) (a) Molander, G. A.; Etter, J. B.; Harring, L. S.; Thorel, P.-J.
J. Am. Chem. Soc. 1991, 113, 8036. (b) Molander, G. A.;
Brown, G. A.; deGracia, I. S. J. Org. Chem. 2002, 67, 3459.
12) (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413.
+
HRMS (FAB): m/z [M + Na] calcd for C H NaO : 431.1829;
found: 431.1835.
2
5
28
5
Supporting Information for this article is available online at
http://www.thieme-connect.de/ejournals/toc/synthesis. It contains
the optimized geometries for all the stationary points obtained at the
B3LYP/6-31G* levels of theory, total electronic energies, and IRC
plots of transition states.
(
b) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992, 114,
5426. (c) Fu, G. C.; Grubbs, R. H. J. Am. Chem. Soc. 1992,
114, 7324. (d) Fu, G. C.; Nguyen, S. T.; Grubbs, R. H. J. Am.
Chem. Soc. 1993, 115, 9856. (e) Grubbs, R. H.; Miller, S. J.;
Fu, G. C. Acc. Chem. Res. 1995, 28, 446.
13) (a) Schmalz, H.-G. Angew. Chem., Int. Ed. Engl. 1995, 34,
Acknowledgment
(
(
1
833. (b) Mar tin, S. F.; Chen, H.-J.; Courtney, A. K.; Liao,
Y.; Patzel, M.; Ramser, M. N.; Wagman, A. S. Tetrahedron
996, 52, 7251. (c) Schneider, M. F.; Junga, H.; Blechert, S.
We thank the Department of Science and Technology (New Delhi,
India) for the financial support of this work and the IIT Bombay
computer center for valuable CPU time. We also thank the National
Single Crystal Diffraction facility at IITB for the X-ray data. M.P.
acknowledges CSIR-New Delhi for a Senior Research Fellowship.
1
Tetrahedron 1995, 51, 13003. (d) Furstner, A.; Muller, T.
Synlett 1997, 1010.
14) (a) Achamatowicz, O. Jr.; Bukowski, P.; Szechner, B.;
Swiezchowska, Z.; Zamojski, A. Tetrahedron 1971, 27,
1973. (b) Georgiadis, M. P.; Couladouros, E. A. J. Org.
Chem. 1986, 51, 2725. For recent reports from our group,
see: (c) Krishna, U. M.; Srikanth, G. S. C.; Trivedi, G. K.;
Deodhar, K. D. Synlett 2003, 2383. (d) Krishna, U. M.;
Trivedi, G. K. Tetrahedron Lett. 2004, 45, 257. (e)Krishna,
U. M.; Deodhar, K. D.; Trivedi, G. K. Tetrahedron 2004, 60,
References
(
1) (a) Oishi, T.; Ohtsuks, Y. In Studies in Natural Products
Synthesis, Vol. 3; Atta-ur-Rahman, Ed.; Elsevier:
Amsterdam, 1989, 73. (b) Rigby, J. H. In Studies in Natural
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4829. (f) Krishna, U. M.; Srikanth, G. S. C.; Trivedi, G. K.
(
(
(
2) Illuminati, G.; Mandoline, L. Acc. Chem. Res. 1981, 14, 95.
3) Molander, G. A. Acc. Chem. Res. 1998, 31, 603.
4) For reviews on oxidopyrylium cycloadditions, see:
Tetrahedron Lett. 2003, 44, 8227.
(
15) CCDC 232578 (8), 232579 (11), and 735916 (17) contain
the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via
(a) Singh, V.; Krishna, U. M.; Vikrant; Trivedi, G. K.
Tetrahedron 2008, 64, 3405. (b) Sammes, P. G. Gazz. Chim.
Ital. 1986, 51, 1573. (c) Wender, P. A.; Love, J. A. In
Advances in Cycloaddition, Vol. 5; Harmata, M., Ed.; JAI
Press: Stamford CT, 1999, 1. (d) Mascarenas, J. L. In
Advances in Cycloaddition, Vol. 6; Harmata, M., Ed.; JAI
Press: Stamford CT, 1999, 1.
www.ccdc.cam.ac.uk/data_request/cif.
X-ray crystallographic data for 8: CCDC 232578, empirical
formula C H O , formula weight 240.25, T = 293(2) K,
1
2
16
5
l = 0.70930 Å, crystal system monoclinic, space group
P21/n, unit cell dimensions a = 7.4888(5) Å, a = 90.000°,
(
5) Krishna, U. M.; Deodhar, K. D.; Trivedi, G. K.; Mobin, S.
M. J. Org. Chem. 2004, 69, 967.
b = 15.2345(11) Å, b = 98.888(5)°, c = 10.0221(5) Å,
3
g = 90.000°, V = 1129.67(12) Å , Z = 4, D
= 1.413 Mg/
calcd
(6) (a) Hendrickson, J. B.; Farina, J. S. J. Org. Chem. 1980, 45,
3
–1
m , absorption coefficient 0.110 mm , F(000) = 512, crystal
size 0.35 × 0.30 × 0.20 mm, data collection q range 2.45–
3361. (b) Sammes, P. G.; Street, L. J. J. Chem. Soc., Perkin
Trans. 1 1983, 1261. (c) Lee, H.-Y.; Kim, H. Y.; Kim, B. G.;
Kee, J. M. Synthesis 2007, 2360.
7) For other methods utilizing 3-oxidopyrylium in
cyclooctanoid synthesis, see: (a) Magnus, P.; Booth, J.;
Diorazio, L.; Donohoe, T.; Lynch, V.; Magnus, N.;
Mendoza, J.; Pye, P.; Tarrant, J. Tetrahedron 1996, 52,
2
5.01°, index ranges 0 £ h £ 8, 0 £ k £ 18, –11 £ l £ 11,
reflections collected 1875, unique 1875 [R(int) = 0.0000],
refinement method full-matrix least-squares on F2, data/
(
2
restraints/parameters 1875/0/220, goodness-of-fit on F
1
.134, final Rindices [I > 2s(I)] R1 = 0.0539, wR2 = 0.1481,
R indices (all data) R1 = 0.0571, wR2 = 0.1524, largest diff.
peak and hole 0.249 and –0.394 e·Å .
14103. (b) Delgado, A.; Castedo, L.; Mascarenas, J. L. Org.
–3
Lett. 2002, 4, 3091. (c) Radhakrishnan, K. V.;
Syam Krishnan, K.; Bhadbhade, M. M.; Bhosekar, G. V.
Tetrahedron Lett. 2005, 46, 4785.
X-ray crystallographic data for 11: CCDC 232579, empirical
formula C H O , formula weight 282.28, T = 293(2) K,
1
4
18
6
l = 0.70930 Å, crystal system: monoclinic, space group
P21/n, unit cell dimensions a = 10.5020(13) Å,
Synthesis 2010, No. 2, 320–328 © Thieme Stuttgart · New York