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Helvetica Chimica Acta Vol. 86 (2003)
1.85! d, J 2.5, irrad. at 2.75 ! d, J 7.8, HexoÀC(6)). 13C-NMR (D2O): 73.49, 70.24 (2d, C(7), C(8)); 73.35
(s, C(4)); 65.00 (t, CH2ÀC(5)); 51.30 (d, C(1)); 41.58 (t, C(3)); 40.53 (d, C(5)); 29.01( t, C(6)). HR-MALDI-
MS: 280.1540 (22, [M C7H7] , C15H22NO4 ; calc. 280.1549), 212.0896 (10, [M Na] , C8H15NNaO4 ; calc.
212.0899), 190.1078 (100, [M H] , C8H16NO4 ; calc. 190.1079). Anal. calc. for C8H15NO4 ¥ 0.5 H2O (198.22):
C 48.48, H 8.14, N 7.07; found: C 48.28, H 7.91, N 6.77. pKHA 8.4.
(1R,2R,6R,7R,10R)- and (1S,2S,6S,7S,10S)-8-Benzyl-10-({[(1S,2S,5R)-(2-isopropyl-5-methylcyclohex-1-
yl)oxy]methoxy}methyl)-1-(methoxymethoxy)-4,4-dimethyl-3,5-dioxa-8-azatricyclo[5.2.2.02.6]undecane (24a/
24b). A soln. of (Æ)-22 (20 mg, 0.055 mmol), iPr2EtN (38 ml, 0.22 mmol) and chloromethyl (1R,3S,4S)-menthyl
ether (35 ml, 0.163 mmol) in CH2Cl2 (1ml) was stirred at 25 8 for 1h and evaporated. FC (hexane/AcOEt 3 :1)
gave 24a/24b 1:1(27 mg, 98%). Colourless oil. Rf (cyclohexane/AcOEt 3 :1) 0.38. IR (CHCl3): 3000m, 2949m,
2923m, 2871m, 1596w, 1494w, 1378w, 1263w, 1147m, 1109m, 1083m, 1039s (br.), 962w, 91 6w, 876w. 1H-NMR
(CDCl3): 7.34 7.25 (m, 4 H); 7.20 (tt, J ꢀ 6.9, 1.9, 1 H); 4.93, 4.89, 4.86, 4.85, 4.79, 4.74, 4.72, 4.72 (8d, J ꢀ 7.1, 2
OCH2O); 4.33 (br. d, J 8.4, 0.5 H), 4.25 (d, J 0.9, 1H), 4.26 ( dd, J 8.4, 2.4, 0.5 H) (CH2ÀC(10)); 3.99
(dd, J 9.0, 3.4, HÀC(6)); 3.96, 3.88 (2d, J 14.0, PhCH2); 3.73 (br. d, J 9.3, HÀC(2)); 3.40, 3.39 (td, J ꢀ 10.8,
4.2, HÀC(1')); 3.36, 3.35 (2s, MeO); 3.06, 3.03 (2dd, J ꢀ 9.4, 1.5, HaÀC(9)); 2.88 (dt, J 3.7, 1.9, HÀC(7)); 2.62,
2.58 (2 br. d, J 9.4, HbÀC(9)); 2.27 (sept.d, J 7.2, 2.4, Me2CH); 2.22 1.92 (m), 1.72 1.46 (m, HÀC(10),
HendoÀC(11), HeqÀC(3'), HeqÀC(4'), HeqÀC(6')); 1.92 (dt, J ꢀ 14.0, 3.3, HexoÀC(11)); 1.66, 1.36 (2s, Me2C(4));
1.46 1.35 (m, HÀC(5')); 1.25 (br. t, J ꢀ 11.7, HÀC(2')); 1.16 0.85 (m, HaxÀC(3'), HaxÀC(5'), HaxÀC(6'));
0.93, 0.91, 0.91, 0.89 (4d, J ꢀ 6.6, Me2CH); 0.79 (br. d, J 7.0, MeÀC(5')). 13C-NMR (CDCl3): 141.34, 139.29
(2s); 128.13 (2d); 127.61 (4d); 126.10 (d); 109.45 (s, C(4)); 94.39, 94.15, 91.69, 91.69 (4t, 2 OCH2O); 78.14, 77.02
(2d, C(2), C(6)); 77.00 (s, C(1)); 69.87, 69.67 (2t , CH2ÀC(10)); 60.73 (t, PhCH2); 55.55 (q, MeO); 55.55, 55.09
(2d, C(1')); 51.07 (d, C(7)); 48.07 (t, C(9)); 48.07 (d, C(2')); 41.50, 41.27 (2t, C(6')); 36.20, 35.34 (2d, C(10));
33.04 (t, C(4')); 31.18 (d, C(5')); 25.78, 23.94 (2q, Me2C(4)); 25.07, 24.99 (2d, Me2CH); 22.74 (t, C(11), C(3'));
21.99, 20.86 (2q, Me2CH); 15.56 (q, MeÀC(5')). HR-MALDI-MS: 554.3456 (10, [M Na] , C31H49NNaO6
;
calc. 554.3458), 532.2640 (100, [M H] , C31H50NO6 ; calc. 532.3638), 332 (22, [M À menthylOCH2OCH2] ).
Anal. calc. for C31H49NO6 (531.73): C 70.02, H 9.29, N 2.63; found: C 69.84, H 9.27, N 2.75.
(1R,2R,6R,7R,10R)- and (1S,2S,6S,7S,10S)-8-Benzyl-1-(methoxymethoxy)-4,4-dimethyl-3,5-dioxa-8-azatri-
cyclo[5.2.2.02.6]undecane-10-methyl (1S,4R)-4,7,7-Trimethyl-3-oxo-2-oxabicyclo[2.2.1]heptane-1-carboxylate
(25a/25b). A soln. of (Æ)-22 (20 mg, 0.055 mmol), 4-(dimethylamino)pyridine (DMAP; 1.5 mg, 0.013 mmol),
iPr2EtN (15 ml, 0.088 mmol) and (1S,4R)-camphanoyl chloride (134 mg, 0.062 mmol) in CH2Cl2 (2 ml) was
stirred at 258 for 30 min and evaporated. FC (hexane/AcOEt 3 :1) yielded 25a/25b 1:1 (30 mg, > 98%).
Colourless foam. Rf (cyclohexane/AcOEt 1:1) 0.59. IR (CHCl 3): 2995w, 2931m, 2906m, 1785s, 1730s (br.),
1602w, 1493w, 1451m, 1398m, 1377m, 1352m, 1316m, 1264s, 1166s, 1106s, 1060s, 1044s, 994m, 91 0s, 875m.
1H-NMR (CDCl3): 7.33 7.26 (m, 4 H); 7.21( tt, J ꢀ 6.4, 2.2, 1H); 4.90, 4.90, 4.83, 4.82 (4 d, J 7.2, 2 OCH2O);
4.70, 4.68 (2dd, J 10.3, 4.0, HÀC(6)); 4.43, 4.39 (br. d, J 10.3, HÀC(2)); 4.30 (br. d, J ꢀ 8.5), 4.26 (dd, J 8.4,
2.2) (CH2ÀC(10)); 3.97, 3.88 (2d, J ꢀ 13.6, PhCH2); 3.37 (s, MeO); 3.10, 2.63 (2 br. d, J 9.3, HÀC(9)); 2.92
(q, J ꢀ 2.1, HÀC(7)); 2.45 (ddd, J 13.4, 10.5, 4.4, 1 H), 2.05 (ddd, J 13.7, 9.4, 4.7, irrad. at 2.45 ! dd, J ꢀ 13.5,
4.5, 1H), 1.93 ( ddd, J ꢀ 13.1, 10.9, 4.6, irrad. at 2.45 ! dd, J ꢀ 13.5, 9.5, 1 H), 1.70 (ddd, J 13.4, 9.0, 4.0, irrad. at
2.45 ! dd, J 10.7, 3.8, 1 H) (2 HÀC(5'), 2 HÀC(6')); 1.85, 1.83 (2dt, J ꢀ 14.3, 4.2, HexoÀC(11)); 1.66, 1.36
(2s, Me2C(4)); 1.59 (br. dd, J ꢀ 13.4, 10.1, HendoÀC(7)); 1.12 (s, MeÀC(6')); 1.08, 1.06, 0.98, 0.97
(4s, 2 MeÀC(7')). 13C-NMR (CDCl3): 177.92, 167.46 (2s, 2 CO); 139.42 (s); 128.17 (2d); 128.06 (2d); 126.61
(d); 109.99 (s, C(4)); 92.26 (t, OCH2O); 91.19 (s, C(1')); 78.43, 77.18 (2d, C(2), C(6)); 76.12 (s, C(1)); 67.76
(t, CH2ÀC(10)); 60.69 (t, PhCH2); 56.09 (q, MeO); 54.77, 54.18 (2s, C(4'), C(7')); 51.50 (d, C(7)); 48.40
(t, C(9)); 35.09, 35.04 (2d, C(10)); 30.70, 29.00 (2t, C(5'), C(6')); 27.55 (t, C(11)); 26.13, 24.28 (2q, Me2C(4));
16.87, 16.87, (2q, Me2C(7')); 9.82 (q, MeÀC(4')). HR-MALDI-MS: 566.2719 (4, [M Na] , C30H41NNaO8 ; calc.
566.2730), 544.2900 (100, [M H] , C30H42NO8 ; calc. 544.2910).
3-[(tert-Butyl)dimethylsilyloxy]-1-[(naphthalen-2-yl)sulfonyl]-1H-pyridin-2-one (6.57 g, 71%) was ob-
tained from 3-[(tert-butyl)dimethylsilyloxy]-1H-pyridin-2-one (5.00 g, 22.2 mmol) and (naphthalen-2-yl)sul-
fonyl chloride (4.90 g, 23.0 mmol) in analogous way as described for the synthesis of 3-[(tert-butyl)dimethylsi-
lyloxy]-1H-pyridin-2-one. Rf (cyclohexane/AcOEt 3 :2) 0.80. M.p. 109 1108. IR (CHCl3): 3122w, 3061w, 2955m,
2931m, 2859m, 1675s, 1620s, 1472w, 1464w, 1418w, 1365s, 1292s, 1177s, 1117s, 1073m, 954m, 944m, 838s. 1H-NMR
(CDCl3): 8.78 (br. s, HÀC(1')); 8.04, 7.91(2 br. d, J ꢀ 8.2, HÀC(5'), HÀC(8')); 7.94 (br. d, J ꢀ 1.4, HÀC(3'),
HÀC(4')); 7.82 (dd, J 7.5, 1.7, HÀC(6)); 7.69 (ddd, J 8.4, 6.9, 1.6), 7.63 (ddd, J 8.4, 7.2, 1.4) (HÀC(6'),
HÀC(7')); 6.68 (dd, J 7.2, 1.9, HÀC(4)); 6.14 (t, J ꢀ 7.3, HÀC(5)); 0.86 (s, t-Bu); 0.05 (s, Me2Si). 13C-NMR
(CDCl3): 157.99 (s, C(2)); 147.67 (s, C(3)); 135.77 (s, C(2')); 133.49, 131.80 (2s, C(9'), C(10')); 132.57 (d), 129.85
(2d), 129.08 (d), 127.96 (d), 127.75 (d), 123.98 (d), 123.33 (d) 122.53 (d), (C(4), C(6), 7 naphthalene d); 105.65