614
A. Casaschi et al. / Tetrahedron 57 (2001) 607±615
4.66 (t, 1H, 12-H), 6.80±7.80 (m, 15H, ArH), and 8.0 (s, 1H,
15-H). m/z (%) 544 (M1, 5), 403 (7), 274 (42), and 130
(100).
12q. Colourless oil. (Found: C, 62.05; H, 5.5; N, 7.0; S,
11.0. C30H31N3O5S2 requires: C, 62.35; H, 5.4; N, 7.25; S,
11.1%). d 1.36 (s, 3H, CH3), 2.28, 2.35 (2£d, J14.0 Hz,
2H, CCH2CvC), 2.63, 3.27 (2£t, J7.9 Hz, 4H,
CH2CH2N), 3.35, 3.43 (2£d, J15.8 Hz, 2H, NCH2CvC),
4.12, 4.49 (2£d, J8.8 Hz, 2H, CH2O), 4.76, 4.95 (2£s, 2H,
CH2vC) and 6.72±7.93 (m, 16H, ArH). m/z (%) 577 (M1,
31), 444 (22), 436 (29), 304 (50), 187 (21), 141 (36), 133
(100), 105 (91), 82 (22), 81 (31), 77 (90) and 51 (25).
12j. Pale yellow oil. (HRMS found: 281.1521. C17H19N3O
requires: 281.1528). d 1.37 (s, 3H, 3-CH3), 2.31 (2£d,
J13.7 Hz, 2H, 8-H), 3.18 (s, 3H, 1-NCH3), 3.98, 3.99
(2£d, J15.9 Hz, 2H, 10-H), 4.51, 4.74 (2£s, 2H, 9-CH2),
and 6.60±7.40 (m, 7H, ArH). m/z (%) 281 (M1, 59.51), 160
(100), and 121 (62.69).
12r. Colourless prisms from n-hexane/ether, mp 46±478C.
(Found: C, 60.0; H, 4.75; N, 2.9; S, 14.1. C45H42N2O10S4
requires: C, 60.1; H, 4.7; N, 3.1; S, 14.3%). d 1.20 (s, 3H,
CH3), 2.13, 2.27 (2£d, J14.0 Hz, 2H, CCH2CvC), 2.64 (t,
J7.6 Hz, 2H, CH2CH2N), 3.11 (m, 2H, CH2CH2N), 3.33
(d, J15.0 Hz, 1H, NCH2CvC), 3.45 (d, J10.2 Hz, 1H,
CH2NAr), 3.55 (d, J15.0 Hz, 1H, NCH2CvC), 4.04 (d,
J10.2 Hz, 1H, CH2NAr), 4.64, 4.87 (2£s, 2H, CH2vC)
and 6.95±7.89 (m, 27H, ArH). m/z (%) 898 (M1, 15), 272
(59), 184 (22), 179 (39), 144 (79), 141 (20), 133 (100), 132
(75) and 130 (48).
12k. Pale yellow oil. (HRMS found: 254.1427. C16H18N2O
requires: 254.1419). d 1.41 (s, 3H, 3-CH3), 2.25 (s, 2H,
2-CH2), 3.79, 3.93 (d, J15.8 Hz, 2H, 10-H), 4.17, 4.49
(d, J8.8 Hz, 2H, 2-H), 4.82, 5.00 (2£s, 2H, 9-CH2), and
6.60±7.20 (m, 7H, ArH). m/z (%) 254 (M1, 10), 133 (100),
105 (72).
12l. Colourless prisms from petroleum ether/diethyl ether,
mp 868C. (HRMS found: 308.1524. C19H20N2O2 requires:
308.1525). d 1.43 (s, 3H, 3-CH3), 2.49, 2.74 (2£d, J
13.7 Hz, 2H, 8-H), 3.22 (s, 3H, NCH3), 3.76, 4.44 (2£d,
J15.8 Hz, 2H, 10-H), 4.39, 4.72 (2£s, 2H, 9-CH2), 6.07
(t, 1H, 15-H), 6.50 (d, 1H, 13-H), 6.72 (d, 1H, ArH), 6.82 (d,
1H, ArH), 7.12 (t, 1H, ArH), and 7.20±7.40 (m, 3H, ArH).
m/z (%) 308 (M1, 21), 160 (71), and 148 (100).
12s. Sticky colourless oil. (Found: C, 61.35; H, 4.75; N, 1.6;
S, 12.5. C39H37NO9S3 requires: C, 61.6; H, 4.9; N, 1.85; S,
12.65%). d 1.39 (s, 3H, CH3), 2.29, 2.37 (2£d, J14.0 Hz,
2H, CCH2CvC), 2.64, 3.13 (2£t, J8.2 Hz, 4H,
CH2CH2N), 3.49 (s, 2H, NCH2CvC), 4.15, 4.53 (2£d,
J8.9 Hz, 2H, CH2O), 4.82, 4.95 (2£s, 2H, CH2vC) and
6.75±7.86 (m, 22H, ArH). m/z (%) 759 (M1, 0.2), 224 (31),
141 (23), 133 (100), 105 (55), 78 (17), 77 (67) and 51 (18).
12m. Pale yellow oil. (HRMS found: 281.1425. C18H19NO2
requires: 281.1416). d 1.40 (s, 3H, 3-CH3), 2.36 (s, 2H,
CvCCH2), 3.84 (d, J15.9 Hz, 1H, 2a-H), 4.44 (d, J
8.8 Hz, 1H, 10a-H), 4.26 (d, J15.9 Hz, 1H, 2b-H), 4.52
(d, J8.8 Hz, 1H, 10b-H), 4.57, 4.82 (2£s, 2H, CvCH2),
6.06 (t, 1H, 15-H), 6.51 (d, 1H, 13-H), 6.74 (d, 1H, ArH),
and 6.80±7.25 (m, 5H, ArH). m/z (%) 281 (M1, 7), 148 (83),
133 (90), and 105 (100).
12t. Colourless needles from n-hexane/ether, mp 48±498C.
(Found: C, 67.1; H, 5.7; N, 7.05; S, 10.0. C35H35N3O4S2
requires: C, 67.15; H, 5.65; N, 6.7; S, 10.25%). d 1.14 (s,
3H, CH3), 2.12, 2.26 (2£d, J14.2 Hz, 2H, CCH2CvC),
2.84, 3.34 (2£m, 4H, CH2CH2N), 3.41 (d, J15.0 Hz, 1H,
NCH2CvC), 3.45 (d, J10.2 Hz, 1H, CH2NAr), 3.61 (d,
J15.0 Hz, 1H, NCH2CvC), 3.99 (d, J10.2 Hz, 1H,
CH2NAr), 4.61, 4.92 (2£s, 2H, CH2vC), 6.86±7.84 (m,
19H, ArH) and 8.20 (br. s, 1H, NH). m/z (%) 625 (M1, 7),
484 (19), 356 (17), 355 (38), 354 (31), 272 (39), 213 (15),
184 (21), 149 (20), 144 (27), 141 (20), 132 (26), 131 (27),
130 (100), 83 (16), 77 (41), 69 (16), 57 (35), 55 (22), 43 (19)
and 41 (19).
12n. Pale yellow oil. (HRMS found: 332.1890. C22H24N2O
requires: 332.1889). d 1.40 (s, 3H, 3-CH3), 2.58, 2.77 (2£d,
J13.5 Hz, 2H, 8-H), 2.82±3.10 (m, 4H, 12-CH2, 13-CH2),
3.13, 3.18 (2£d, J13.8 Hz, 2H, 10-H), 3.16 (s, 1H, NCH3),
4.74, 4.83 (2£s, 2£1H, 9-CH2), 6.00 (d, 1H, 17-H, ArH),
6.83 (t, 1H, 16-H, ArH), 6.83 (d, 1H, ArH), and 6.90±7.40
(m, 5H, ArH). m/z (%) 332 (M1, 9), 172 (100), and 132 (20).
12o. Pale yellow oil. (HRMS found: 305.1788. C21H23NO
requires: 305.1780). d 1.41 (s, 3H, CCH3), 2.44, 2.53 (2£d,
J13.4 Hz, 2H, 8-H), 2.92 (t, J8.1 Hz, 2H 13-CH2), 3.05±
3.22 (t, 2H, 12-CH2), 3.24 (s, 2H, 10-CH2, 4.20, 4.58 (2£d,
J8.5 Hz, 2H, 2-H), 4.89, 5.13 (2£s, 2H, CvCH2), 6.25 (d,
1H, 17-H, ArH), 6.80 (t, 1H, 16-H, ArH), and 6.80±7.20 (m,
6H, ArH). m/z (%) 305 (M1, 44), 232 (100), 132 (76).
12u. Pale yellow oil. (Found: C, 71.6; H, 6.0; N, 5.9; S, 6.5.
C29H30N2O3S requires: C, 71.6; H, 6.2; N, 5.75; S, 6.6%). d
1.21 (s, 3H, CH3), 2.32, 2.36 (2£d, J14.1 Hz, 2H,
CCH2CvC), 2.87, 3.30 (2£m, 4H, CH2CH2N), 3.45, 3.54
(2£d, J15.5 Hz, 2H, NCH2CvC), 4.12, 4.51 (2£d, J
8.8 Hz, 2H, CH2O), 4.81, 5.03 (2£s, 2H, CH2vC), 6.75±
7.79 (m, 14H, ArH) and 8.10 (br. s, 1H, NH). m/z (%) 486
(M1, 11), 210 (18), 187 (18), 141 (16), 133 (30), 131 (26),
130 (100), 105 (17), 103 (11), 77 (31), 71 (14), 57 (14), 55
(13), 43 (13) and 41 (13).
12p. Colourless prisms from n-hexane/ether, mp 65±678C.
(Found: C, 62.2; H, 5.8; N, 9.4; S, 10.9. C30H32N4O4S2
requires: C, 62.45; H, 5.6; N, 9.7; S, 11.1%). d 1.16 (s,
3H, CH3C), 2.13, 2.25 (2£d, J14.2 Hz, 2H, CCH2CvC),
2.72, 3.27 (2£t, J8.0 Hz, 4H, CH2CH2N), 3.38, 3.47 (2£d,
J15.8 Hz, 2H, NCH2CvC), 3.68, 3.99 (2£d, J10.2 Hz,
2H, CH2NAr), 4.60, 4.88 (2£s, 2H, CH2vC) and 6.72±7.93
(m, 17H, ArH and NH). m/z (%) 576 (M1, 13), 436 (27), 435
(79), 354 (47), 304 (29), 272 (74), 185 (26), 184 (96), 164
(53), 144 (21), 141 (49), 132 (49), 131 (35), 130 (81), 95
(29), 94 (40), 82 (58), 81 (34), 78 (25) and 77 (100).
1.10. Cyclisation-anion capture product 15
A solution of 2a (0.5 mmol) in THF (5 mL) at 2788C was
treated with freshly prepared organocuprate12 (0.5 mmol)
and the mixture stirred at the same temperature for 1 h.
Water was added and the organic phase separated, dried
(Na2SO4) and evaporated in vacuo. The residue was