CHEMISTRY & BIODIVERSITY – Vol. 10 (2013)
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5 :1!1:1) provided 4 (3.9 g, 59%). Nearly colorless oil. [a]2D7 ¼ ꢀ24 (c¼1.98, CHCl3). IR (neat): 3510,
2957, 1734, 1692, 1455. 1H-NMR: 5.30 (tt, J¼7.0, 1.2, HꢀC(7’)); 4.53 (d, J¼7.0, CH2(8’)); 3.86 (dd, J¼7.3,
5.2, HꢀC(2)); 3.57 (br. s, OH); 3.56 (m, HꢀC(3’)); 3.50 (d, J¼13.7, HaꢀC(10)); 3.42 (d, J¼13.7,
HbꢀC(10)); 3.14 (dq, J¼6.7, 6.7, HꢀC(2’)); 2.23 (m, HaꢀC(5’)); 2.06 (m, HaꢀC(3), HbꢀC(5’)); 2.03 (m,
HbꢀC(3)); 2.00 (s, Me(2’’); 1.86 (m, HaꢀC(5), HaꢀC(6)); 1.81 (m, HꢀC(4)); 1.67 (m, HaꢀC(4’)); 1.65 (s,
Me(9’)); 1.41 (m, HbꢀC(4’)); 1.34 (m, HbꢀC(6)); 1.32 (m, HbꢀC(5)); 1.20 (dd, J¼6.7, 1.7, Me(10’)); 1.14 (s,
Me(8)); 0.94 (s, Me(9)). 13C-NMR: 175.3 (C(1’)); 171.0 (C(1’’)); 141.6 (C(6’)); 118.5 (C(7’)); 75.0 (C(3’));
65.4 (C(2)); 61.2 (C(8’)); 53.1 (C(10)); 48.3 (C(7)); 47.7 (C(1)); 45.1 (C(2’)); 44.7 (C(4)); 38.5 (C(3)); 35.3
(C(5’)); 33.6 (C(4’)); 32.9 (C(6)); 26.4 (C(5)); 21.0 (C(2’’)); 20.8 (C(8)); 19.9 (C(9)); 16.5 (C(9’)); 14.2
(C(10’)). EI-MS: 207 (8), 178 (6), 164 (12), 151 (31), 132 (100), 108 (53). HR-ESI-MS: 464.2078 ([M þ
Na]þ , C22H35NNaO6Sþ ; calc. 464.2077).
(2R)-N-[(aS,2S,5S)-Tetrahydro-a,5-dimethyl-5-vinyl-2-furanacetyl]bornane-10,2-sultam (¼(2S)-2-
[(2S,5S)-5-Ethenyltetrahydro-5-methylfuran-2-yl]-1-[(3aS,6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-
3H-3a,6-methano-2,1-benzisothiazol-1(4H)-yl]propan-1-one; 3). In a sealed Schlenk-type reaction
vessel, 4 (500 mg, 1.13 mmol), [Pd2(dba)3] (101 mg, 0,11 mmol), and (R)-BINAP (280 mg, 0,45 mmol)
in THF (22.6 ml) were stirred at 828 for 48 h under Ar. The deep red soln. was then filtered over Celiteꢃ,
washed with AcOEt, and the solvent was removed in vacuo. The crude product (638 mg) was purified by
FC (hexane/AcOEt 9 :1) to yield 3 (239 mg, 0.63 mmol, 55%) and (5’’R)-product (87 mg, 0.23 mmol,
20%) as white, crystalline solids.
Data of 3. White crystals (CHCl3). M.p. 1448. [a]2D5 ¼ ꢀ 24 (c¼1.22, CHCl3). IR (neat): 2936, 1687,
1455, 1391, 1322, 1312. 1H-NMR: 5.78 (dd, J¼17.3, 10.6, HꢀC(6’’)); 5.10 (dd, J¼17.3, 1.7, HaꢀC(7’’)); 4.91
(dd, J¼10.6, 1.7, HbꢀC(7’’)); 4.13 (m, HꢀC(2’’)); 3.90 (dd, J¼7.7, 4.7, HꢀC(2)); 3.49 (d, J¼13.7,
HaꢀC(10)); 3.41 (d, J¼13.7, HbꢀC(10)); 3.12 (dq, J¼9.1, 6.6 , HꢀC(2’)); 2.15 (m, HaꢀC(3)); 2.03 (m,
HbꢀC(3)); 2.01 (m, HaꢀC(3’’)); 1.88 (m, HaꢀC(6)); 1.84 (m, HaꢀC(5)); 1.81 (m, HꢀC(4)); 1.78 (m,
HbꢀC(4’’)); 1.73 (m, HaꢀC(4’’)); 1.71 (m, HbꢀC(3’’)); 1.36 (m, HbꢀC(6)); 1.33 (m, HbꢀC(5)); 1.24 (s,
Me(8’’)); 1.20 (s, Me(8)); 1.09 (d, J¼6.6, Me(3’)); 0.94 (s, Me(9)). 13C-NMR: 174.9 (C(1’)); 143.8 (C(6’’));
111.1 (C(7’’)); 83.5 (C(5’’)); 82.3 (C(2’’)); 65.3 (C(2)); 53.3 (C(10)); 48.2 (C(7)); 47.7 (C(1)); 46.2 (C(2’));
44.8 (C(4)); 38.3 (C(3)); 36.5 (C(4’’)); 32.9 (C(6)); 29.1 (C(3’’)); 26.8 (C(8’’)); 26.5 (C(5)); 21.1 (C(8));
19.9 (C(9)); 13.6 (C(3’)). EI-MS: 216 (10), 207 (4), 166 (6), 151 (19), 135 (52), 111 (98), 93 (100). HR-
ESI-MS: 404.1864 ([M þ Na]þ , C20H31NNaO4Sþ ; calc. 404.1866).
(2R,2’S,5’S)-Lilac Alcohol (¼(2R)-2-[(2S,5S)-5-Ethenyltetrahydro-5-methylfuran-2-yl]propan-1-ol;
2). To a soln. of 3 (542 mg, 1.42 mmol) in 30 ml of Et2O/THF 2 :1 was added LiAlH4 (134 mg, 3.55 mmol)
at 08. After 30 min, the mixture was heated to reflux and stirred for 12 h. The reaction was quenched with
conc. HCl at 08, and the aq. phase was extracted with Et2O. The combined org. layers were dried
(Na2SO4), and the solvent was removed in vacuo. FC (hexane/AcOEt, 5–30% AcOEt in 5% steps) of
the crude product gave 2 (173 mg, 1.02 mmol, 72%). Colorless oil. [a]2D5 ¼ ꢀ1.2 (c¼1.0, CHCl3); [7]:
1
[a]2D5 ¼ ꢀ1.4 (c¼2.9, CHCl3). IR (neat): 3421, 2967, 2875, 1456, 1369, 1243, 1085, 1025. H-NMR: 5.82
(dd, J¼17.3, 10.7, HꢀC(6’)); 5.13 (dd, J¼17.3, 1.5, HaꢀC(7’)); 4.95 (dd, J¼10.7, 1.5, HbꢀC(7’)); 3.77 (m,
HꢀC(2’)); 3.58 (dd, J¼11.0, 8.2, HaꢀC(1)); 3.53 (dd, J¼11.0, 4.3, HbꢀC(1)); 3.45 (br. s, OH); 1.97 (m,
HaꢀC(3’)); 1.81 (m, HaꢀC(4’)); 1.71 (m, HꢀC(2); HbꢀC(4’)); 1.66 (m, HbꢀC(3’)); 1.28 (s, Me(8’)); 0.77 (d,
J¼6.9, Me(3)). 13C-NMR: 143.4 (C(6’)); 111.3 (C(7’)); 85.2 (C(2’)); 83.4 (C(5’)); 68.4 (C(1)); 41.0 (C(2));
36.3 (C(4’)); 30.5 (C(3’)); 27.1 (C(8’)); 13.5 (C(3)). EI-MS: 170 (2, Mþ ), 155 (29), 143 (3), 137 (8), 125
(13), 111 (100), 93 (85). HR-ESI-MS: 193.1201 ([M þ Na]þ ; C10H18NaO2þ ; calc. 193.1199).
(2S,2’S,5’S)-Lilac Aldehyde (¼(2S)-2-[(2S,5S)-5-Ethenyltetrahydro-5-methylfuran-2-yl]propanal;
1). A soln. of 2 (173 mg, 1.02 mmol) in 30 ml of CH2Cl2 was cooled to 08, and 535 mg (1.22 mmol) of
DessꢀMartin periodinane were added carefully, followed by the addition of 9 ml (0.5 mmol) of H2O. The
mixture was allowed to warm to r.t. and was stirred for 12 h. The org. phase was successively washed with
10% aq. NaHCO3, 10% aq. Na2S2O3, H2O, and brine. The aq. phases were re-extracted with Et2O. All
org. phases were combined and dried (Na2SO4), and the solvent was evaporated. FC (hexane/AcOEt
7:1) yielded 1 (124 mg, 737 mmol, 72%). Nearly colorless oil. [a]2D5 ¼ þ46 (c¼1.24, CHCl3). IR (neat):
2972, 2927, 1708, 1461, 1413, 1371. 1H-NMR: 9.74 (d, J¼2.4, HꢀC(1)); 5.80 (dd, J¼17.3, 10.7, HꢀC(6’));
5.13 (dd, J¼17.3, 1.5, HaꢀC(7’)); 4.95 (dd, J¼10.7, 1.5, HbꢀC(7’)); 4.10 (mc, HꢀC(2’)); 2.45 (ddq, J¼7.4,
7.0, 2.4, HꢀC(2)); 2.06 (m, HaꢀC(3’)); 1.93 (m, HaꢀC(4’)); 1.78 (m, HbꢀC(4’)); 1.67 (m, HbꢀC(3’)); 1.27 (s,