HETEROCYCLES, Vol. 80, No. 2, 2010
1397
(2S,4R)-1-Benzyl-4-(tert-butyldimethylsilyloxy)-2-[(4-methoxymethoxy)but-1-enyl]-2-pentyl-
pyrrolidine (28). Wittig reaction of 8 (3.58 g, 9.20 mmol) with 3-(methoxymethoxy)-
propyltriphenylphosphonium bromide (5.32 g, 12.0 mmol) and n-BuLi (1.54 M in n-hexane, 7.20 mL, 7.2
mmol) was carried out by the same procedure as for the preparation of 10 to give the olefin (28) (3.6 g,
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83%) as a colorless oil; []D -13.5 (c 1.2, CHCl3); IR (thin film): 3086, 3062, 2953, 2929, 2857, 2822,
2797, 1470, 1378, 1254, 1149, 1112, 1037, 918, 836, 775, 732, 698 cm-1; 1H NMR : 7.34-7.27 (m, 4H),
7.23-7.19 (m, 1H), 5.58 (d, J = 12.1 Hz, 1H), 5.46-5.39 (m, 1H), 4.64 (s, 2H), 4.36-4.31 (m, 1H), 3.73 (d,
J = 13.5 Hz, 1H), 3.62 (d, J = 13.5 Hz, 1H), 3.57 (t, J = 6.9 Hz, 2H), 3.38 (s, 3H), 2.91 (dd, J = 7.1, 9.8
Hz, 1H), 2.65-2.52 (m, 3H), 2.24 (dd, J = 7.6, 13.0 Hz, 1H), 1.96 (dd, J = 3.7, 13.0 Hz, 1H), 1.77-1.60 (m,
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2H), 1.51-1.28 (m, 6H), 0.91 (t, J = 6.8 Hz, 3H), 0.87 (s, 9H), 0.01 (s, 3H), -0.02 (s, 3H); C NMR :
140.7, 135.1, 128.3, 128.1, 127.6, 126.4, 96.4, 70.1, 67.5, 66.8, 59.5, 55.2, 52.4, 46.0, 34.9, 32.8, 29.4,
25.8, 24.7, 22.8, 18.0, 14.1, -4.8; MS (m/z): 475 (M+); HRMS m/z calcd (EI) for C28H49NO3Si(M+):
475.3482, found: 475.3459.
(3R,5S)-1-Benzyl-5-[(4-methoxymethoxy)but-1-enyl]-5-pentylpyrrolidin-3-ol (30). Desilylation of 28
(2.18 g, 4.60 mmol) with TBAF (1.0 M in THF, 6.9 mL, 6.9 mmol) in THF (6.9 mL) was carried out by
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the same procedure as described for the preparation of 22 to give 30 (1.6g, 95%) as a colorless oil; []D
+20.4 (c 1.0, CHCl3); IR (thin film): 3425, 3084, 3061, 2952, 2931, 2870, 2822, 2797, 1495, 1454, 1379,
1364, 1208, 1149, 1112, 1033, 919, 832, 735, 699 cm-1; 1H NMR : 7.32-7.27 (m, 4H), 7.23-7.19 (m, 1H),
5.63 (d, J = 12.2 Hz, 1H), 5.48-5.44 (m, 1H), 4.63 (s, 2H), 4.23-4.20 (m, 1H), 3.80 (d, J = 13.3 Hz, 1H),
3.56 (t, J = 6.8 Hz, 2H), 3.44 (d, J = 13.3 Hz, 1H), 3.36 (s, 3H), 2.69 (dd, J = 5.3, 10.2 Hz, 1H), 2.63 (dd,
J = 1.9, 10.2 Hz, 1H), 2.51-2.45 (m, 2H), 2.41 (dd, J = 7.3, 13.8 Hz, 1H), 2.09 (br s, 1H), 1.94 (dd, J = 2.9,
13.8 Hz, 1H), 1.78-1.64 (m, 2H), 1.55-1.23 (m, 6H), 0.90 (t, J = 7.0 Hz, 3H); 13C NMR : 140.2, 134.2,
128.4, 128.3, 127.9, 126.7, 96.4, 69.7, 67.4, 66.6, 59.2, 55.2, 52.0, 46.6, 37.0, 32.5, 29.6, 24.2, 22.7, 14.1;
MS (m/z): 362 (M++1); HRMS m/z (CI) calcd for C22H36NO3(M++1): 362.2695, found: 362.2673.
(3R,5S)-1-Benzyl-5-[(4-methoxymethoxy)butyl]-5-pentylpyrrolidin-3-ol (32). Catalytic reduction of
30 (1.88 g, 5.21 mmol) over PtO2 (59.1 mg, 0.26 mmol) was carried out by the same procedure as
described for the preparation of 12 to give 32 (1.2 g, 61%) as a colorless oil; []D23 +14.6 (c 1.0, CHCl3);
IR (thin film): 3437, 3085, 3061, 3027, 2932, 2870, 2822, 2794, 1495, 1454, 1364, 1212, 1151, 1112,
1044, 920, 772, 736, 698 cm-1; 1H NMR : 7.30-7.27 (m, 4H), 7.20-7.25 (m, 1H), 4.63 (s, 2H), 4.20-4.11
(m, 1H), 3.75 (d, J = 13.3 Hz, 1H), 3.55 (t, J = 6.5 Hz, 2H), 3.46 (d, J = 13.3 Hz, 1H), 3.37 (s, 3H), 2.77
(dd, J = 5.0, 9.9 Hz, 1H), 2.63 (dd, J = 1.8, 9.9 Hz, 1H), 2.07 (dd, J = 7.1, 14.0 Hz, 1H), 1.86 (br s, 1H),
1.71 (dd, J = 2.2, 14.1 Hz, 1H), 1.68-1.47 (m, 6H), 1.46-1.26 (m, 8H), 0.91 (t, J = 7.0 Hz, 3H); 13C NMR