clinic, space group P21/n, Z = 4, a = 9.9458(2), b = 16.1368(4),
Concentration of fraction B (Rf 0.2) afforded hexahydro-
indole15(51mg, 12%)ascolourlessneedles. 1HNMR(300MHz,
CDCl3) δ 7.76 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H),
6.72 (d, J = 7.8 Hz, 1H), 6.56 (d, J = 1.5 Hz, 1H), 6.52 (dd,
J = 7.8 and 1.5 Hz, 1H), 5.94 (s, 2H), 5.04 (br s, 1H), 3.80 (br s,
1H), 3.75 (dd, J = 10.5 and 8.7 Hz, 1H), 3.30 (app t, J = 10.5
Hz, 1H), 3.14 (br s, 1H), 2.58–2.50 (complex m, 1H), 2.45
(s, 3H), 2.04–1.92 (complex m, 2H), 1.90–1.82 (complex m,
1H), 1.60–1.45 (complex m, 2H); 13C NMR (75 MHz, CDCl3)
δ 147.7 (C), 146.6 (C), 143.5 (C), 141.7 (C), 134.7 (C), 132.0 (C),
129.8 (CH), 127.6 (CH), 121.9 (CH), 121.8 (CH), 108.6 (CH),
108.2 (CH), 101.0 (CH2), 59.6 (CH), 54.7 (CH2), 46.8 (CH),
30.1 (CH2), 24.1 (CH2), 21.6 (CH3), 20.1 (CH2); IR (CH2Cl2
solution, NaCl cell) 1503, 1488, 1443, 1346, 1249, 1161, 1092,
1040, 758 cmϪ1; MS (EI) m/z 397.1349 (397.1348 calcd for
c = 12.0708(3) Å, β = 94.2552(13)Њ, V = 1931.94(8) Å3, Dc = 1.37 g cmϪ3
,
4414 unique data (2θmax = 55Њ), 3733 with I > 3σ(I), R = 0.0420,
Rw = 0.0291, S = 1.0315.
Crystal data for 17: C24H27NO6S, M = 457.55, T = 200(1) K, mono-
clinic, space group P21/c, Z = 4, a = 9.51220(10), b = 24.4129(3),
c = 9.93130(10) Å, β = 99.5571(6)Њ, V = 2274.24(4) Å3, Dc = 1.336 g
cmϪ3, 5323 unique data (2θmax = 55Њ), 3319 with I > 3σ(I); R = 0.0688,
Rw = 0.0746, S = 1.0311.
Crystal data for 21: C16H17NO2ؒHClؒ1.5H2O, M = 318.79, T = 200(1)
K, monoclinic, space group C2/c, Z = 8, a = 20.0656(2), b = 13.9995(2),
c = 13.3059(2) Å, β = 124.0651(7)Њ, V = 3096.35(7) Å3, Dc = 1.368 g
cmϪ3, 4507 unique data (2θmax = 60Њ), 1851 with I > 3σ(I); R = 0.0360,
Rw = 0.0230, S = 1.1222.
Images were measured on a Nonius Kappa CCD diffractometer
(MoKα, graphite monochromator, λ = 0.71073 Å) and data extracted
using the DENZO package.23 Structure solution was by direct methods
(SIR92)24 and refinement was by full matrix least-squares on F using
the CRYSTALS program package.25 Atomic coordinates, bond lengths
and angles, and displacement parameters have been deposited at the
Cambridge Crystallographic Data Centre. CCDC reference numbers
crystallographic files in .cif or other electronic format.
+
ؒ
C22H23NO4S, M , 61%), 369 (23), 242 (57), 214 (86), 91 (100).
Anal. calcd for C22H23NO4Sؒ0.5H2O: C, 65.0; H, 6.0; N, 3.4.
Found: C, 64.9; H, 5.8; N, 3.2%.
Compound 2
A solution of sodium naphthalenide was prepared by adding
sodium (400 mg, 17 mmol), in small pieces, to a solution of
naphthalene (2.1 g, 16 mmol) in deoxygenated DME (10 mL)
and by stirring the resulting green mixture at 18 ЊC for 2 h.
This solution was then added, dropwise and via cannula, to
a magnetically stirred solution of compound 14 (170 mg, 0.43
mmol) in DME (4.5 mL), maintained at –78 ЊC under a nitro-
gen atmosphere, until a light-green colour persisted. Saturated
aq. NH4Cl (10 mL) was added to the reaction mixture, which
was then extracted with EtOAc (3 × 25 mL). The organic
phases were combined and extracted with 1 M HCl (3 ×
25 mL), then the combined aqueous phases were basified to
pH 10 by the addition of solid NaOH. The resulting mixture
was extracted with EtOAc (3 × 25 mL) and the combined
organic phases were dried (MgSO4), filtered and concentrated
under reduced pressure. The ensuing residue was treated with
formic acid (2 mL) then paraformaldehyde (700 mg, 2.4 mmol)
and the resulting mixture heated at 80 ЊC for 14 h. The cooled
reaction mixture was partitioned between H2O (10 mL) and
Et2O (20 mL). The separated aqueous phase was washed
with Et2O (20 mL) then basified to pH 10 by the addition of
saturated aq. K2CO3. The basic solution was extracted with
EtOAc (3 × 20 mL) and the combined organic phases dried
(MgSO4) filtered and concentrated under reduced pressure. The
resulting brown oil was subjected to flash chromatography on
silica gel (80 : 19 : 1 v/v/v CHCl3–MeOH–aq. NH3 elution) and
concentration of the appropriate fractions (Rf 0.6) yielded
compound 2 (66 mg, 59%), as a colourless solid, which had
spectroscopic properties identical to those reported6 previously.
1 W. C. Wildman and C. L. Brown, J. Am. Chem. Soc., 1968, 90, 6439.
2 (a) W. C. Wildman and C. J. Kaufman, J. Am. Chem. Soc., 1955,
77, 1248; (b) L. J. Dry, M. E. Poynton, M. E. Thompson and
F. L. Warren, J. Chem. Soc., 1958, 4701; (c) Y. Inubushi, H. M. Fales,
E. W. Warnhoff and W. C. Wildman, J. Org. Chem., 1960, 25, 2153.
3 F. Viladomat, J. Bastida, C. Codina, W. E. Campbell and S. Mathee,
Phytochemistry, 1995, 40, 307.
4 I. W. Southon and J. Buckingham, Dictionary of the Alkaloids,
Chapman and Hall, New York, 1989, pp. 229, 735.
5 (a) H. I. Sanchez, M. I. Larraza, I. Rojas, F. B. Kuri, H. J. Flores
and K. Jankowski, Heterocycles, 1985, 23, 3033; (b) C.-K. Sha,
S.-J. Huang, C.-M. Huang, A.-W. Hong and T.-H. Jeng, Pure Appl.
Chem., 2000, 72, 1773.
6 L. E. Overman and J. Shim, J. Org. Chem., 1993, 58, 4662.
7 (a) M. Ishizaki O. Hoshino and Y. Iitaka, J. Org. Chem., 1992, 57,
7285; (b) M. Ishizaki, K. Kurihara, E. Tanazawa and O. Hoshino,
J. Chem. Soc., Perkin Trans. 1, 1993, 101.
8 J. Jin and S. M. Weinreb, J. Am. Chem. Soc., 1997, 119, 5773.
9 W. H. Pearson and B. W. Lian, Angew. Chem., Int. Ed., 1998, 37,
1724.
10 M. Ikeda, M. Hamada, T. Yamashita, K. Matsui, T. Sato and
H. Ishibashi, J. Chem. Soc., Perkin Trans. 1, 1999, 1949.
11 J. R. Henry, L. R. Marcin, M. C. McIntosh, P. M. Scola,
G. D. Harris and S. M. Weinreb, Tetrahedron Lett., 1989, 30, 5709.
12 G. Revial, S. Lim, B. Viossat, P. Lemoine, A. Tomas, A. F. Duprat
and M. Pfau, J. Org. Chem., 2000, 65, 4593.
13 For examples of the Michael addition of 1,3-dicarbonyl compounds
to nitroalkenes, including asymmetric variants, see (a) P. Hrnciar
and I. Culak, Collect. Czech. Chem. Commun., 1984, 49, 1421;
(b) H. Brunner and B. Kimel, Monatsh. Chem., 1996, 127, 1063;
(c) J. Ji, D. M. Barnes, S. A. King, H. E. Morton, F. A. Plagge,
S. J. Wittenberger and J. Zhang, Book of Abstracts, 217th ACS
National Meeting, Anaheim, California, March 21–25, 1999,
ORGN-487; and references cited therein.
Acknowledgements
14 G. B. Ansell, D. W. Moore and A. T. Nielsen, J. Chem. Soc., D, 1970,
1602.
We thank the Institute of Advanced Studies for financial
support including the provision of a IAS post-Doctoral Fellow-
ship to KAJ. Professor Wolfgang Steglich (LMU—München)
and his Department are thanked for allowing MK to carry
out research work leading to the “Diplomhauptprüfung in
Chemie” in the Research School of Chemistry, The Australian
National University.
15 A. L. Gemal and J.-L. Luche, J. Am. Chem. Soc., 1981, 103, 5454.
16 D. H. Lloyd and D. E. Nichols, J. Org. Chem., 1986, 51, 4294.
17 D. Camp and I. D. Jenkins, J. Org. Chem., 1989, 54, 3045.
18 L. Brandsma, S. F. Vasilevsky and H. D. Verkruijsse, Application
of Transition Metal Catalysts in Organic Synthesis, Springer-Verlag,
Berlin, 1998, p. 6.
19 B. M. Trost and E. Keinan, J. Am. Chem. Soc., 1978, 100, 7779.
20 C. H. Heathcock, T. A. Blumenkopf and K. M. Smith, J. Org.
Chem., 1989, 54, 1548.
21 M. D. Rozwadowski, Heterocycles, 1994, 39, 903.
22 F. W. Eastwood, P. Perlmutter and Q. Yang, J. Chem. Soc., Perkin
Trans. 1, 1997, 35.
23 DENZO-SMN. Processing of X-ray diffraction data collected in
oscillation mode: Z. Otwinowski and W. Minor, Methods Enzymol.,
1997, 276, 307.
24 A. Altomare, M. Cascarano, C. Giacovazzo and A. Guagliardi,
J. Appl. Crystallogr., 1993, 26, 343.
25 D. J. Watkin, C. K. Prout, J. R. Carruthers and P. W. Betteridge,
CRYSTALS Issue 10, Chemical Crystallography Laboratory,
Oxford, UK, 1996.
Notes and references
† All new and stable compounds had spectroscopic data (IR, NMR,
mass spectrum) consistent with the assigned structure. Satisfactory
combustion and/or high-resolution mass spectral analytical data were
obtained for new compounds and/or suitable derivatives.
‡ Crystal data for 7: C15H13NO5ؒCH3OH, M = 319.31, T = 200(1) K,
monoclinic, space group P21/n, Z = 4, a = 10.4370(6), b = 11.1112(6),
c = 13.9707(6) Å, β = 108.346(3)Њ, V = 1537.80(14) Å3, Dc = 1.379 g
cmϪ3, 14104 unique data (2θmax = 46Њ), 1743 with I > 3σ(I), R = 0.0415,
Rw = 0.0450, S = 1.0581.
26 D. J. Watkin, C. K. Prout and L. J. Pearce, CAMERON, Chemical
Crystallography Laboratory, Oxford, UK, 1996.
Crystal data for 15: C22H23NO4S, M = 397.49, T = 200(1) K, mono-
1348
J. Chem. Soc., Perkin Trans. 1, 2001, 1345–1348