1518
A. Poschalko et al. / Tetrahedron 58 (2002) 1513±1518
washed with water (2£50 mL) and brine (1£50 mL), dried
(Na2SO4), ®ltered and evaporated in vacuo to yield (^)-12
as off-white crystals (355 mg, 92%). Mp 158±1618C; H
NMR (CDCl3) d 6.92 (s, 1H), 6.18 (d, J10.2 Hz, 1H),
6.02 (dd, J10.2 Hz, J5.1 Hz, 1H), 4.58 (b, 1H), 4.25±
4.13 (m, 1H), 3.34 (dd, J6.4, 16.5 Hz, 1H), 3.16±2.92 (m,
2H), 2.81±2.60 (m, 2H), 2.41 (s, 3H), 2.48±2.27 (m, 2H),
2.04±1.91 (m, 1H).
Acknowledgements
1
The authors thank Sanochemia AG for ®nancial support and
the donation of chemicals. S. N. thanks the Fonds zur
È
Forderung der Wissenschaftlichen Forschung (FWF) for a
Lise-Meitner-Scholarship (Grant-No.: M-00435).
References
4.1.11. (4aa,6b,8aRp)-4a,5,9,10,11-Hexahydro-3-meth-
oxy-10-methyl-6H-benzofuro[3a,3,2-ef]-[3]benzazepin-
6-ol ((^)-2). Zinc powder (1.00 g) and copper(I)iodide
(1.00 g) in 50% EtOH (50 mL) were sonicated under
argon for 2 h. CaCl2 (722 mg, 6.51 mmol) and (^)-12
(340 mg, 0.93 mmol) were added and re¯uxed for 12 h.
The mixture was ®ltered and concentrated in vacuo. The
residue was partitioned between water (20 mL) and
EtOAc (20 mL). The aqueous layer was extracted with
EtOAc (2£10 mL), the combined organic layers were
washed with water (2£20 mL) and brine (1£30 mL), dried
(Na2SO4), ®ltered and concentrated in vacuo. The residue
was puri®ed by MPLC (SiO2, CHCl3/MeOH97:3) to yield
(^)-2 as colorless crystals (230 mg, 86%). Mp 152±1558C;
1H NMR (CDCl3) d 6.66 (d, J8.2 Hz, 1H), 6.61 (d,
J8.2 Hz, 1H), 6.22 (dd, J10.2, 1.1 Hz, 1H), 6.01 (ddd,
J10.2, 5.2, 1.0 Hz, 1H), 4.57 (b, 1H), 4.22±4.12 (m, 1H),
3.83 (s, 3H), 3.29±3.12 (m, 1H), 3.12±3.01 (m, 1H), 2.80±
2.62 (m, 3H), 2.42 (s, 3H), 2.46±2.26 (m, 2H), 2.04±1.90
(m); 13C NMR (CDCl3) d 145.3 (s), 142.9 (s), 132.7 (s),
130.9 (s), 128.3 (d), 126.5 (d), 121.5 (d), 111.1 (d), 85.6
(d), 66.3 (t), 62.0 (d), 59.1 (t), 55.6 (q), 49.3 (q), 48.9 (s),
34.5 (t), 30.0 (t).
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Ê
rhombic, space group Pbca (No. 61), a14.784(4) A, b
Ê
Ê
Ê 3
10.805(3) A, c19.546(6) A, V3122.3(15) A , Z8, Dx
1.609 g cm23, T295(2) K, F(000)1536, l(Mo Ka)
0.71073 A, m2.65 mm21
,
colorless crystal (0.64£
Ê
0.54£0.28 mm3). Data were collected on a Siemens/Bruker
SMART 3-circle diffractometer with a CCD area detector
and graphite monochromatized Mo Ka radiation by record-
ing 4£606 v-scan frames (Dv0.38, t15 s) covering a
complete sphere of the reciprocal space, umax,30.08.
Corrections for absorption applied. Structure solution by
direct methods, re®nement by full-matrix least-squares on
F2 (SHELX-97);13 N-bonded formyl group disordered with
oxygen O(4) and C(17)-bonded H in two orientations;
data/restraints/parameters4550/0/220; ®nal R10.048,
wR20.080 (all data). CCDC 16/165137.14
10. Chavdarian, C. H. G.; Seeman, J. I.; Wooten, J. B. J. Org.
Chem. 1983, 492±494.
11. Erdik, E. Tetrahedron 1987, 2203±2212.
12. (a) Carroll, P.; Furst, G. T.; Han, S. Y.; Joullie, M. Bull. Soc.
Chim. Fr. 1990, 769±780. (b) Roques, R.; Rossi, J. C.;
Declercq, J. P.; Germain, G. Acta Crystallogr., Sect. B 1980,
B36, 1589±1593. (c) Peeters, O. M.; Blaton, N. M.; De Ranter,
C. J. Acta Crystallogr., Sect. C (Cr. Str. Comm.) 1997, C53,
1284±1286. (d) Matusch, R.; Kreh, M.; Mueller, U. Helv.
Chim. Acta 1994, 77, 1611±1615.
13. Sheldrick, G. M. SHELX97: Program System for Crystal
È È
Structure Determination; University of Gottingen: Gottingen,
Germany, 1997.
Crystal data for (^)-2: C17H21NO3, Mr287.35, triclinic,
14. Complete crystallographic data (excluding structure factors)
have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC
165137±165138. Copies of the data can be obtained, free
of charge, on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ (fax: 144-1223-336033, email:
deposit@ccdc.cam.ac.uk).
Ê
Å
space group P1 (No. 2), a7.991(3) A, b9.634(4),
Ê
10.549(5) A, a92.02(2)8, b106.86(2)8, g107.69(2)8,
V3122.3(15) A , Z8, Dx1.301 g cm23, F(000)308,
Ê 3
l(Mo Ka)0.71073 A, m0.089 mm21
,
T298(2) K,
Ê
colorless crystal (0.7£0.46£0.24 mm3). Data collected on
a Siemens/Bruker SMART diffractometer (given earlier),
u
max,25.08. Corrections for absorption applied. Structure
solution by direct methods, re®nement by full-matrix
least-squares on F2, data/restraints/parameters2580/0/
193; ®nal R10.042, wR20.101 (all data). CCDC 16/
165138.14