1360
P. Szolcsa´nyi et al. / Tetrahedron Letters 49 (2008) 1357–1360
10. (a) Bunce, R. A.; Herron, D. M.; Lewis, J. R.; Kotturi, S. W. J.
Heterocycl. Chem. 2003, 40, 113–120. Formation of undesired ketone
5 could be explained by a Meerwein–Ponndorf–Verley-type mecha-
nism, see: (b) Kovalev, B. G.; Chusid, A. Ch.; Konyuchov, V. P.;
Nedopekina, C. F.; Neymark, J. L. Zh. Org. Khim. 1975, 11, 1183–
1187.
11. Selected data for toluene-4-sulfonic acid 1-pentyl-hex-5-enyl ester 6:
1H NMR (300 MHz, CDCl3): d = 0.82 (t, 3H, CH3), 1.19–1.44 (m,
8H, H-3, H-20, H-30, H-40), 1.50–1.67 (m, 4H, H-2, H-10), 1.90–2.00
(m, 2H, H-4), 2.44 (s, 3H, CH3Ph), 4.54 (m, 1H, H-1), 4.88–4.98 (m,
2H, H-6), 5.69 (ddt, 1H, H-5), 7.32 (d, 2H, J = 8.1 Hz, CHm-Ph), 7.79
(d, 2H, J = 8.1 Hz, CHo-Ph). 13C NMR (75 MHz, CDCl3): d = 13.9
(q, CH3), 21.6 (q, CH3Ph), 22.4, 23.8, 24.3, 31.4 (4 ꢀ t, C-3, C-20, C-30,
C-40), 33.2, 33.5, 34.0 (3 ꢀ t, C-2, C-4, C-10), 84.3 (d, C-1), 114.8 (t,
C-6), 127.7 (d, CHo-Ph), 129.6 (d, CHm-Ph), 134.6 (s, CH3C), 138.1
(d, C-5), 144.3 (s, CSO2). IR (KBr, m/cmꢁ1): 666, 815, 905, 1097, 1176,
1188, 1362, 2862, 2932, 2954.
12. Selected data for 2-(1-pentyl-hex-5-enylamino)-ethanol 3: 1H NMR
(300 MHz, CDCl3): d = 0.87 (t, 3H, CH3), 1.20–1.45 (m, 12H, H-2,
H-3, H-10, H-20, H-30, H-40), 1.95–2.15 (m, 2H, H-4), 2.43 (br s, 2H,
exchange with D2O, NH, OH), 2.45–2.55 (m, 1H, H-1), 2.74 (t, 2H,
CH2NH), 3.60 (t, 2H, CH2OH), 4.90–5.02 (m, 2H, H-6), 5.79 (ddt,
1H, H-5). 13C NMR (75 MHz, CDCl3): d = 14.0 (q, CH3), 22.6, 24.9,
25.3, 32.1, 33.4, 33.9, 33.9 (7 ꢀ t, C-2, C-3, C-4, C-10, C-20, C-30, C-40),
48.0 (t, CH2NH), 57.1 (d, C-1), 61.0 (t, CH2OH), 114.5 (t, C-6), 138.7
(d, C-5). IR (KBr, m/cmꢁ1): 910, 1062, 1459, 1641, 2858, 2929, 3077,
3313.
14. Typical procedure for the intramolecular Pd(II)-catalysed carbonyl-
ation: A mixture of aminoalkenitol 3 (100 mg, 0.469 mmol), PdCl2
(8 mg, 0.045 mmol, 0.1 equiv), CuCl2 (126 mg, 0.937 mmol, 2 equiv)
and AcONa (77 mg, 0.937 mmol, 2 equiv) in dry dioxane (9 mL) was
stirred under a CO atmosphere (balloon) at 40 °C for 7 h. The
resulting suspension was filtered, the solids were washed with Et2O
(10 mL) and the filtrate was evaporated. The green residue was
suspended in Et2O (20 mL) and washed with 5% aq NH4OH
(2 ꢀ 10 mL). The combined washings were back-extracted with
Et2O (20 mL) and the combined organic extracts were washed with
H2O (10 mL), dried over MgSO4 and evaporated to furnish a
red-brown oil (96 mg). Flash chromatography purification (SiO2,
hexanes/AcOEt/Et3N = 86/14/1) yielded three fractions: oxazolidi-
none 7 as a yellowish oil (5 mg, 4%), calvine rac-1 as a yellowish oil
(45 mg, 38%) and epicalvine rac-2 as a yellowish oil (20 mg, 17%).
15. Selected data for 3-(1-pentyl-hex-5-enyl)-oxazolidin-2-one 7: 1H
NMR (300 MHz, CDCl3): d = 0.86 (t, 3H, J = 6.8 Hz, CH3), 1.20–
1.88 (m, 12H, 7 ꢀ CH2), 1.94–2.16 (m, 2H, CH2CH@CH2), 3.39 (t,
2H, J = 8.1 Hz, CH2N), 3.70–3.86 (m, 1H, CHN), 4.31 (t, 2H,
J = 8.1 Hz, CH2O), 4.92–5.02 (m, 2H, H-6), 5.76 (ddt, 1H, H-5). 13C
NMR (75 MHz, CDCl3): d = 14.0 (q, CH3), 22.6, 25.4, 25.9, 31.6,
31.8, 32.5, 33.4 (7 ꢀ t, 7 ꢀ CH2), 39.5 (t, CH2N), 53.2 (d, CH), 61.9 (t,
CH2O), 115.0 (t, CH2@CH), 138.3 (d, CH2 = CH), 158.5 (s, C@O).
Anal. Calcd for C14H25NO2 (239.21): C, 70.25; H, 10.53; N, 5.85%.
Found: C, 70.20; H, 10.58; N, 5.88%. Preparation of N-substituted
oxazolidinones via Pd(II)-catalysed carbonylation of 1,2-amino-
alcohols is known: Tam, W. J. Org. Chem. 1986, 51, 2977–2981;
Chiarotto, I.; Feroci, M. Tetrahedron Lett. 2001, 42, 3451–3453.
16. Katz, S. J.; Bergmeier, S. C. Tetrahedron Lett. 2002, 43, 557–559.
13. An identical sequence on analogous compounds is reported, see:
Furstner, A.; Langemann, K. Synthesis 1997, 792–803.
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