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P. Šafár et al. / Tetrahedron: Asymmetry 20 (2009) 626–634
634
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cooled and water added cautiously until the lithium complex was
destroyed. The mixture was then diluted with water (20 mL) and
dichloromethane (50 mL). The dichloromethane layer was sepa-
rated and the aqueous layer extracted with dichloromethane
(2 Â 20 mL). The combined extracts were washed with water,
brine, dried over MgSO4, and concentrated in vacuo to give a resi-
due (0.36 g, 94%). Recrystallization from n-heptane gave enantio-
merically pure indolizinol 6a (0.22 g, 64%) as a colorless solid;
TAU-CHEM, Ltd Company and Dr. Pavel Cepec for HPLC and
GC–MS analyses.
References
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mp 110–112 °C; [a]D = +0.9 (c 1.0, MeOH); IR (m
, cmÀ1, KBr):
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3183, 3054, 3027, 2967, 2948, 2933, 2883, 2796, 2785, 2742,
1942, 1599, 1498, 1458, 1450, 1443, 1381, 1347, 1325, 1278,
1236, 1198, 1161, 1147, 1099, 1085, 1041, 1028, 995, 926, 906,
881, 818, 757, 696, 655, 600, 503, 475; UV (kmax, nm (loge)): 205
(2.98); 1H NMR (600 MHz, CD3OD): d 1.61 (ddd, 1H, H6eq; J = 2.6,
6.1 and 12.9 Hz), 1.68–1.82 (m, 3H, 2 Â H2 and H1), 1.87 (ddd,
1H, H1; J = 5.3, 10.5 and 15.3 Hz), 2.10–2.19 (m, 2H, 2 Â H2), 2.20
(dd, 1H, H8a; J = 6.6 and 10.6 Hz), 2.29 (dq, 1H, H6ax; J = 4.1 and
12.8 Hz), 2.69 (td, 1H, H7; J = 2.8 and 12.9 Hz), 3.05 (dt, 1H, H3;
J = 2.1 and 7.9 Hz), 3.17 (ddd, 1H, H5eq; J = 2.4, 3.7 and 10.8 Hz),
3.81 (s, 1H, H8), 7.17 (t, 1H, HpAr; J = 7.3 Hz), 7.27 (t, 2H, HmAr
;
J = 7.6 Hz), 7.33 (d, 2H, HoAr; J = 8.3 Hz); 13C NMR (150 MHz,
CD3OD): d 22.0 (t, C2), 26.1 (t, C1), 26.5 (t, C6), 49.2 (d, C7), 53.5
(t, C5), 55.1 (t, C3), 69.8 (d, C8a), 70.7 (d, C8), 127.2 (d, CpAr), 129.1
and 129.3 (d, Cm+oAr), 145.0 (s, CipsoAr). Anal. Calcd for C14H19NO
(217.31): C, 77.38; H, 8.81; N, 6.45. Found: C, 77.26; H, 8.64; N,
6.22.
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4.13. (7R,8R,8aS)-7-Phenyloctahydroindolizin-8-ol 6c
The product was obtained by reduction of 12c (0.4 g, 1.8 mmol)
with lithium aluminum hydride (0.35 g, 0.95 mmol) in dry THF
(25 mL) at reflux for 12 h. After standard work-up, a residue was
obtained (0.35 g, 98%). Recrystallization from n-heptane gave
enantiomerically pure indolizidinol 6c (0.32 g, 48%) as a white so-
lid; mp 132–134 °C; [a]D = +7.5 (c 1.0, MeOH); IR (m
, cmÀ1, KBr):
ˇ
7. Kadlecíková, K.; Dalla, V.; Marchalín, Š.; Decroix, B.; Baran, P. Tetrahedron 2005,
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1161, 1117, 1100, 1077, 1053, 1016, 996, 924, 900, 870, 846,
ˇ
ˇ
J.; Kadlecˇíková, K.; Šafárˇ, P.; Baran, P.; Dalla, V.; Daïch, A.
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ˇ
ˇ
9. Šafár, P.; Zúziová, J.; Bobošíková, M.; Marchalín, Š.; Prónayová, N.; Dalla, V.;
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763, 702, 578, 546, 515, 443, 418; UV (kmax, nm (loge)): 206
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(2.99); 1H NMR (600 MHz, CD3OD): d 1.61 (ddt, 1H, H1; J = 7.0,
10.6 and 11.8 Hz), 1.76–1.92 (m, 4H, 2 Â H2 and 2 Â H6), 2.00 (dt,
1H, H8a; J = 6.5 and 9.6 Hz), 2.14 (dddd, 1H, H1; J = 3.7, 6.5, 10.0
and 12.6 Hz), 2.19 (dt, 1H, H5ax; J = 3.8 and 11.2 Hz), 2.27 (q, 1H,
H3; J = 9.2 Hz), 2.50 (ddd, 1H, H7; J = 5.3, 10.2 and 11.8 Hz), 3.09
(ddd, 1H, H5eq; J = 2.4, 4.1 and 11.2 Hz), 3.12 (dt, 1H, H3; J = 2.3
and 8.8 Hz), 3.52 (t, 1H, H8, J = 9.5 Hz), 7.19 (tdd, 1H, HpAr; J = 1.8,
6.9 and 7.1 Hz), 7.26–7.32 (m, 4H, Hm+oAr); 13C NMR (150 MHz,
CD3OD): d 21.9 (t, C2), 29.5 (t, C1), 34.7 (t, C6), 52.4 (d, C7), 53.0
(t, C5), 55.2 (t, C3), 71.6 (d, C8a), 77.0 (d, C8), 127.5 (d, CpAr), 129.2
and 129.4 (d, Cm+oAr), 144.5 (s, CipsoAr). Anal. Calcd for C14H19NO
(217.31): C, 77.38; H, 8.81; N, 6.45. Found: C, 77.22; H, 8.68; N,
6.25.
ˇ
Szemes, F.; Kadlecíková, K.; Marchalín, Š.; Bobošíková, M.; Dalla, V.; Daïch, A.
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Acknowledgments
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15. Full crystallographic data have been deposited to the Cambridge
Crystallographic Data Center; CCDC reference number 716573 for product
(7R,8S,8aS)-12a. Copies of the data can be obtained free of charge at the
16. Podea, P. V.; Tosa, M. I.; Paizs, C. P.; Irimie, F. D. Tetrahedron: Asymmetry 2008,
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The authors thank the Grant Agency of Slovak Republic,
Grant No. 1/0161/2008, the Scientific Council of University of
Le Havre (France), and the Slovak Research and Development
Agency under the Contract No. APVV-0210-07 for financial sup-
port for this research program. NMR measurements were per-
formed on the equipment supported by the Slovak State
Program Project No. 2003SP200280203. The authors also thank