Helvetica Chimica Acta – Vol. 89 (2006)
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pure AcOEt): 801 mg (92%) of (+)-41. White foam. [a]D = +11.2 (c=1.0, CHCl3). IR (CHCl3): 3604,
3420 (br.), 3006, 2946, 2870, 1725, 1640, 1596, 1579, 1498, 1448, 1374, 1303, 1132, 1120, 1098, 1046,
1
1030, 973. H-NMR (500 MHz; rotamer mixture 5 :2): major component: 7.97 (dm, J=8.3, 1 H); 7.84
(dm, J=9.1, 2 H); 7.52 (s, 1 H); 7.49 (dt, J=8.2, ca. 0.8, 1 H); 7.31 (ddd, J=8.3, 7.3, 1.2, 1 H); 7.23
(ddd, J=7.9, 7.3, 1.0, 1 H); 6.85 (dm, J=9.1, 2 H); 4.68 (dd, J=3.8, 1.8, 1 H); 4.61 (dq, J=10.4, 6.1,
1 H); 3.98 (dt, J=ca. 9.5, ca. 4.5, 1 H); 3.77 (s, 3 H); 3.64 (dd, J=15.9, 1.1, 1 H); 3.56 (dd, J=15.9, 1.4,
1 H); 3.37 (dm, J=10.1, 1 H); 3.21 (dm, J=10.1, 1 H); 2.53 (br. s, 1 H); 2.42 (tdd, J=10.6, 5.6, 1.8,
1 H); 2.071 (s, 3 H); 1.97 (m, 1 H); 1.87 (dt, J=13.6, 2.7, 1 H); 1.85 (dt, J=13.6, ca. 3, 1 H); 1.39 (ddt,
J=13.9, 4.4, 2.2, 1 H); 1.22 (d, J=6.1, 3 H); 1.03 (ddt, J=13.5, 5.5, 2.7, 1 H); minor component: 7.97
(dm, J=8.3, 1 H); 7.82 (dm, J=8.9, 2 H); 7.51 (dt, J=8.3, ca. 0.8, 1 H); 7.46 (s, 1 H); 7.32 (ddd,
J=8.3, 7.2, 1.1, 1 H); 7.24 (ddd, J=7.9, 7.3, 1.0, 1 H); 6.87 (dm, J=9.1, 2 H); 4.74 (dq, J=9.6, 6.1,
1 H); 3.82 (dd, J=3.4, 1.5, 1 H); 3.78 (s, 3 H); 3.68 (m, 1 H); 3.68 (br. d, J=15.9, 1 H); 3.54 (dd,
J=15.7, 1.4, 1 H); 3.37 (dm, J=10.1, 1 H); 3.21 (dm, J=10.1, 1 H); 2.39 (m, 1 H); 2.065 (s, 3 H); 2.05
(m, 1 H); 1.96 (m, 1 H); 1.93 (dt, J=9.6, ca. 3.5, 1 H); 1.79 (br. s, 1 H); 1.34 (dm, J=ca. 13.5, 1 H);
1.26 (d, J=6.1, 3 H); 1.08 (ddt, J=13.3, 7.1, ca. 2.5, 1 H). 13C-NMR (125 MHz; rotamer mixture 5 :2):
major component: 170.8 (s); 169.7 (s); 163.7 (s); 135.0 (s); 130.6 (s); 129.8 (s); 129.2 (2d); 124.8 (d);
124.2 (d); 123.1 (d); 119.6 (d); 115.6 (s); 114.4 (2d); 113.6 (d); 71.2 (d); 66.5 (d); 55.6 (q); 49.2 (t); 46.7
(d); 35.1 (d); 34.1 (t); 30.5 (t); 28.7 (t); 27.1 (d); 21.4 (q); 17.7 (q); minor component: 170.4 (s); 169.3
(s); 163.8 (s); 135.0 (s); 130.4 (s); 129.7 (s); 129.1 (2d); 124.9 (d); 124.0 (d); 123.3 (d); 119.6 (d); 116.1
(s); 114.5 (2d); 113.6 (d); 72.0 (d); 67.5 (d); 55.7 (q); 52.1 (d); 48.1 (t); 35.3 (d); 34.4 (t); 30.4 (t); 28.8
(t); 26.1 (d); 21.6 (q); 17.6 (q). EI-HR-MS: 540.1931 (47, M+, C28H32N2O7S+; calc. 540.1931), 481.1796
(10), 370.1859 (13), 369.1827 (46, C21H25N2Oþ4 ; calc. 369.1814), 327.0577 (11), 309.1607 (31, C19H21N2Oþ2 ;
calc. 309.1603), 301.0743 (14), 300.0704 (52, C16H14NO3S+; calc. 300.0694), 198.1141 (76, C10H16NO3þ ; calc.
198.1130), 180.1023 (19), 172.0156 (10), 171.0124 (100, C7H7SOþ3 ; calc. 171.0116), 156.0433 (11), 154.1238
(79, C9H16NO+; calc. 154.1232), 153.1145 (11), 152.1077 (32, C9H14NO+; calc. 152.1075), 130.0656 (50, C9-
H8N+; calc. 130.0657), 129.0582 (38), 123.045 (15), 108.0733 (20), 107.0516 (48, C7H7O+; calc. 107.0497),
92.0296 (15), 81.0717 (11), 77.0423 (29), 69.0694 (10), 67.0545 (12), 57.07 (11), 55.0541 (17), 43.0425 (10),
43.0065 (54), 41.0233 (13).
(1S,7S)-7-[(1R)-1-(Acetyloxy)ethyl]-2-{{1-[(4-methoxyphenyl)sulfonyl]-1H-indol-3-yl]acetyl}-2-aza-
bicyclo[2.2.2]octan-6-one ((+)-42). To a soln. of oxalyl chloride (160 ml, 1.86 mmol; Fluka, purum) in
CH2Cl2 (7 ml; dist. from P2O5) at ꢀ788 under Ar was added via syringe a soln. of (280 ml, 3.94 mmol;
Fluka, puriss.) in CH2Cl2 (9 ml ), and the mixture was stirred at ꢀ788 for 30 min. Then was added a
soln. of (+)-41 (815 mg, 1.51 mmol) in CH2Cl2 (14 ml) and stirring was continued for 60 min at ꢀ788.
After addition of Et3N (1.1 ml, 7.89 mmol; dist. from CaH2), the mixture was allowed to reach 238 and
then poured onto aq. 1M HCl (30 ml). The aq. phase was extracted with CH2Cl2 (2×30 ml) and the com-
bined org. layer dried (MgSO4) and evaporated. The crude product (815 mg) was employed as such for
the next step. An anal. sample was prepared by FC (silica gel, cyclohexane/AcOEt 2 :1). Colorless foam.
[a]D =+10.1 (c=1.0, CHCl3). IR (CHCl3): 3006, 2946, 2876, 2843, 1736, 1653, 1596, 1579, 1498, 1448,
1415, 1374, 1304, 1263, 1168, 1132, 1121, 1099, 1068, 1030, 973, 834. 1H-NMR (500 MHz; rotamer mixture
2 :1): major component: 7.98 (dt, J=8.3, 0.8, 1 H); 7.85 (dm, J=9.1, 2 H); 7.55 (s, 1 H); 7.49 (dm, Jꢃ8.0, 1
H); 7.31 (ddd, J=8.3, 7.2, 1.2, 1 H); 7.24 (ddd, J=ca. 8, ca. 7, 1.0, 1 H); 6.87 (dm, J=9.1, 2 H); 5.05 (d,
J=2.0, 1 H); 4.70 (dq, J=10.1, 6.1, 1 H); 3.78 (s, 3 H); 3.66 (dd, J=16.1, 1.1, 1 H); 3.62 (dd, J=16.1, 1.2, 1
H); 3.55 (m, 1 H); 3.48 (dt, J=10.1, 2.6, 1 H); 2.43 (m, 1 H); 2.41 (m, 1 H); 2.27 (dm, Jꢃ19, 1 H);
2.23–2.14 (m, 1 H); 2.05 (s, 3 H); 1.89 (ddt, J=ca. 13.5, 11.2, ca. 2.5, 1 H); 1.28–1.23 (m, 1 H); 1.25 (d,
J=6.2, 3 H); minor component: 7.92 (dm, J=8.3, 1 H); 7.86 (dm, J=9.1, 2 H); 7.50 (s, 1 H); 7.45 (dm,
J=7.6, 1 H); 7.29 (ddd, J=8.3, 7.3, 1.2, 1 H); 7.22 (ddd, J=ca. 8, ca. 7, 1.0, 1 H); 6.88 (dm, J=9.1, 2
H); 4.82 (dq, J=9.4, 6.1, 1 H); 4.31 (d, J=1.7, 1 H); 3.78 (s, 3 H); 3.66 (dd, J=16.1, 1.1, 1 H); 3.62
(dd, J=16.1, 1.2, 1 H); 3.55 (m, 1 H); 3.44 (dt, J=12.4, 2.2, 1 H); 2.51 (quint., J=2.8, 1 H); 2.45 (m, 1
H); 2.35 (dt, J=ca. 19, 2.6, 1 H); 2.23–2.14 (m, 1 H); 2.03 (s, 3 H); 1.95 (ddt, J=13.9, 11.1, 3.0, 1 H);
1.34 (ddt, J=13.9, 5.7, 2.8, 1 H); 1.29 (d, J=6.1, 3 H). 13C-NMR (125 MHz; rotamer mixture 2 :1):
major component: 206.0 (s); 170.6 (s); 169.5 (s); 163.7 (s); 135.0 (s); 130.5 (s); 129.8 (s); 129.2 (2d);
124.8 (d); 124.4 (d); 123.2 (d); 119.6 (d); 115.0 (s); 114.5 (2d); 113.6 (d); 69.8 (d); 55.6 (q); 53.3 (d);
49.6 (t); 42.3 (t); 40.9 (d); 30.7 (t); 28.6 (d); 27.6 (t); 21.3 (q); 17.9 (q); minor component: 204.9 (s);