T. Satoh et al. / Tetrahedron 59 (2003) 4327–4336
4333
2.1.8. tert-Butyl 3-(3,4-methylenedioxyphenyl)-4-chloro-
4-(p-tolylsulfinyl)butyrate (7h). Colorless oil (about 1:2
diastereomeric mixture); IR (neat) 2979, 1728 (CO) 1491,
1252, 1150, 1042, 757 cm21; 1H NMR d 1.30 (3H, s), 1.34
(6H, s), 2.42 (3H, s), 2.74–3.07 (2H, m), 4.48 (0.32H, d,
J¼2.8 Hz), 4.63 (0.63H, d, J¼3.1 Hz), 5.94 (0.63H, s), 5.98
(1.25H, s), 6.75–7.64 (7H, m). MS m/z (%) 436 (Mþ, 1.4),
384 (7), 363 (7), 328 (10), 241 (23), 204 (41), 140 (67), 91
(17), 57 (100). Calcd for C22H25ClO5S: M, 436.1111.
Found: m/z 436.1105.
2958, 2931, 1725 (CO), 1597, 1455, 1367, 1149, 1055,
812 cm21; 1H NMR d 0.90 (3H, t, J¼7.0 Hz), 1.44 (9H, s),
1.64–1.67 (1H, m), 1.78–1.80 (1H, m), 2.44 (3H, s), 2.57–
2.63 (1H, m), 2.67–2.73 (1H, m), 2.80–2.82 (2H, m), 4.46
(1H, d, J¼1.9 Hz), 7.1–7.3 (7H, m), 7.65 (2H, d,
J¼8.2 Hz). MS m/z (%) 476 (Mþ, trace), 403 (13), 281
(13), 245 (40), 199 (22), 140 (100), 129 (67), 91 (90), 57
(96). Calcd for C27H37ClO3S: M, 476.2125. Found: m/z
476.2149.
2.1.15. tert-Butyl {[8-(p-tolylsulfinyl)methyl]-1,4-dioxa-
spiro[4.5]dec-8-yl}acetate (9). AIBN (9.8 mg; 0.06 mmol)
was added to a solution of 7a (88.6 mg; 0.2 mmol) and
Bu3SnH (0.083 ml; 0.3 mmol) in 4 ml of dry benzene. The
atmosphere in the flask was replaced with Ar, and the
reaction mixture was stirred and refluxed for 20 min. The
benzene was evaporated, and the residue was purified by
silica gel column chromatography to give 9 (80.4 mg; 98%)
as a colorless oil; IR (neat) 2935, 1716 (CO), 1367, 1246,
1147, 1106, 1043, 813 cm21; 1H NMR d 1.45 (9H, s), 1.5–
2.0 (8H, m), 2.41 (3H, s), 2.64, 2.75 (each 1H, d,
J¼14.8 Hz), 2.96, 3.07 (each 1H, d, J¼13.9 Hz), 3.96
(4H, s), 7.32, 7.57 (each 2H, d, J¼7.0 Hz). MS m/z (%) 408
(Mþ, trace), 392 (13), 335 (24), 213 (100), 151 (23), 123
(22), 99 (38). Calcd for C22H32O5S: M, 408.1986. Found: m/z
408.1978.
2.1.9. tert-Butyl 2-{1-[chloro(p-tolylsulfinyl)methyl]-
cyclodecyl}propionate (8a). Colorless oil; IR (neat) 2926,
1725 (CO), 1484, 1445, 1367, 1148, 1057, 811, 755 cm21
;
1H NMR d 1.34 (3H, d, J¼7.0 Hz), 1.47 (9H, s), 1.5–1.7
(12H, m), 1.8–2.1 (5H, m), 2.15 (1H, m), 2.43 (3H, s), 3.01
(1H, q, J¼7.0 Hz), 4.54 (1H, s), 7.32, 7.70 (each 2H, d,
J¼8.0 Hz). MS m/z (%) 455 ([MþH]þ, trace), 381 (8), 259
(17), 223 (55), 140 (100), 95 (33), 57 (74). Calcd for
C25H40ClO3S: M, 455.2386. Found m/z 455.2400.
2.1.10.tert-Butyl2-{1-[chloro(p-tolylsulfinyl)methyl]cyclo-
decyl}hexanoate (8b). Colorless oil; IR (neat) 2928, 1724
(CO), 1484, 1455, 1367, 1149, 1082, 1056, 811, 756 cm21
;
1H NMR d 0.85–1.92 (24H, m), 0.92 (3H, t, J¼7.3 Hz),
1.49 (9H, s), 2.42 (3H, s), 2.86 (1H, t, J¼ 7.6 Hz), 4.48 (1H,
s), 7.31, 7.70 (each 2H, d, J¼8.0 Hz). MS m/z (%) 497
([MþH]þ, trace), 301 (28), 265 (65), 247 (22), 219 (22), 140
(100), 139 (30), 81 (26), 57 (63). Calcd for C28H46ClO3S:
M, 497.2816. Found: m/z 497.2861.
2.1.16. tert-Butyl (8-methyl-1,4-dioxaspiro[4.5]dec-8-
yl)acetate (10). A solution of 9 (71 mg; 0.17 mmol) and
excess of Raney-Ni in 8 ml of EtOH was stirred and refluxed
for 15 min. The Raney Ni was filtered off, and the filtrate
was evaporated to give a residue, which was purified by
silica gel column chromatography to afford 10 (37.0 mg;
74%) as a colorless oil; IR (neat) 2951, 1727 (CO), 1366,
1257, 1159, 1107 cm21; 1H NMR d 1.06 (3H, s), 1.44 (9H,
s), 1.5–1.7 (8H, m), 2.17 (2H, s), 3.93 (4H, s). MS m/z (%)
270 (Mþ, 1.7), 197 (8), 99 (100), 86 (13), 57 (5). Calcd for
C15H26O4: M, 270.1829. Found: m/z 270.1836.
2.1.11.tert-Butyl2-{1-[chloro(p-tolylsulfinyl)methyl]cyclo-
pentadecyl}propionate (8c). Colorless oil; IR (neat) 2929,
1727 (CO), 1459, 1369, 1241, 1150, 1059 cm21; 1H NMR d
1.37 (3H, d, J¼7.1 Hz), 1.2–1.4 (28H, m), 1.47 (9H, s), 2.43
(3H, s), 3.03 (1H, q, J¼7.1 Hz), 4.60 (1H, s), 7.35, 7.71
(each 2H, d, J¼8.3 Hz). MS m/z (%) 525 ([MþH]þ, 1), 451
(24), 329 (80), 293 (100), 275 (43), 219 (100), 140 (100), 95
(40), 57 (100). Calcd for C30H50ClO3S: M, 525.3169.
Found: m/z 525.3185.
2.1.17. tert-Butyl {1-[(p-tolylsulfinyl)methyl]cyclopenta-
decyl}acetate (11). Colorless oil; IR (neat) 2932, 1718
(CO), 1143, 1042 cm21; 1H NMR d 1.2–1.4 (28H, m), 1.45
(9H, s), 2.40 (3H, s), 2.57, 2.67 (each 1H, d, J¼15.0 Hz).
2.90, 3.02 (each 1H, d, J¼14.0 Hz), 7.31, 7.60 (each 2H, d,
J¼7.9 Hz). MS m/z (%) 476 (Mþ, 2), 281 (100), 140 (70),
57 (40). Calcd for C29H48O3S: M, 476.3324. Found: m/z
476.3313.
2.1.12. tert-Butyl 2-{1-[chloro(p-tolylsulfinyl)methyl]-
cyclopentadecyl}hexanoate (8d). Colorless oil; IR (neat)
2929, 1727 (CO), 1462, 1367, 1148, 1059 cm21; 1H NMR d
0.93 (3H, t, J¼7.3 Hz), 1.2–1.5 (28H, m), 1.48 (9H, s), 1.67
(2H, d, J¼10 Hz), 1.7–1.9 (4H, m), 2.10 (1H, m), 2.43
(3H, s), 4.53 (1H, s), 7.31, 7.71 (each 2H, d, J¼8.0 Hz). MS
m/z (%) 567 ([MþH]þ, trace), 493 (21), 371 (69), 335 (100),
289 (45), 267 (19), 219 (100), 140 (100), 57 (100).
2.1.18. tert-Butyl (1-methylcyclopentadecyl)acetate (12).
Colorless oil; IR (neat) 2930, 1727 (CO), 1461, 1367, 1258,
1140 cm21; 1H NMR d 0.97 (3H, s), 1.2–1.3 (28H, m), 1.44
(9H, s), 2.07 (2H, s). MS m/z (%) 338 (Mþ, 4), 282 (20), 222
(100), 57 (42). Calcd for C22H42O2: M, 338.3185. Found: m/z
338.3194.
2.1.13. tert-Butyl 3-[chloro(p-tolylsulfinyl)methyl]-2-
methyl-5-phenylpentanoate (8e). Colorless oil; IR (neat)
2977, 2934, 1726 (CO), 1597, 1454, 1367, 1149, 1055, 812,
753 cm21; 1H NMR d 1.42 (3H, d, J¼7.0 Hz), 1.45 (9H, s),
2.0–2.1 (2H, m), 2.47 (3H, s), 2.73 (2H, t, J¼7.4 Hz), 2.84
(1H, m), 2.91 (1H, quint, J¼7.1 Hz), 4.56 (1H, d,
J¼3.1 Hz), 7.2–7.3 (7H, m), 7.62 (2H, d, J¼8.3 Hz). MS
m/z (%) 434 (Mþ, trace), 361 (15), 203 (23), 157 (26), 140
(100), 129 (53), 91 (68). Calcd for C24H31ClO3S: M,
434.1682. Found: m/z 434.1686.
2.1.19. 1-(p-Tolylsulfanyl)-2-oxaspiro[4.14]nonadecan-3-
one (13a). TFAA (0.66 ml; 3.35 mmol) was added dropwise
with stirring to a suspension of 7c (344.2 mg; 0.67 mmol)
and NaI (508 mg; 3.35 mmol) in 5 ml of dry acetone at
2558C. The reaction mixture turned from yellow to black-
green in color. The reaction mixture was stirred at 2558C
for 5 min and the reaction was quenched by sat. aq.
NaHCO3 and sat. aq. Na2SO3. The whole was extracted with
2.1.14. tert-Butyl 2-{1-[Chloro(p-tolylsulfinyl)methyl]-3-
phenylpropyl}hexanoate (8f). Colorless oil; IR (neat)