(2S*,3R*)-2-tert-Butyl-3-methyloxetane 68
HOCH2CHCH3) (Found: MHϩ, 141.1280. C9H17O requires
MH, 141.1279).
In the same way as oxetane 3 (Table 1, entry 2), the diol 47 (0.2
g, 1.36 mmol), gave, after column chromatography eluting with
light petroleum–ether (9 : 1) the oxetane 68 (0.15 g, 85%) as an
oil, Rf (light petroleum–ether 9 : 1) 0.35; νmax (film, CDCl3)/cmϪ1
3100 (CH); δH(400 MHz; CDCl3) 4.40 (1 H, dd, J 8.2 and 5.7,
CHAHBO), 4.14 (1 H, br t, J 6.1, CHAHBO), 3.99 (1 H, d, J 6.4,
CHO), 2.73 (1 H, m, CHMe), 1.18 (3 H, d, J 6.8, MeCH) and
2-(1-Phenylsulfonyl-1-methylethyl)-3-methyloxetane 75
In the same way as oxetane 3 (Table 1, entry 3), sulfone 61 (55
mg, 0.21 mmol) gave, after column chromatography eluting
with light petroleum–ether (1 : 1), the oxetane 75 (47 mg, 92%),
Rf (light petroleum–ether 1 : 1) 0.4; νmax(CHCl3)/cmϪ1 3100
(CH); δH(500 MHz; CDCl3) 7.86 (2 H, d, J 7.5, Ph-H), 7.64
(1 H, t, J 7.4, Ph-H), 7.54 (2 H, t, J 7.8, Ph-H), 4.73 (1 H, d,
J 6.4, CHO), 4.47 (1 H, dd, J 8.3 and 5.9, CHAHBO), 4.21 (1 H,
t, J 6.1, CHAHBO), 2.99 (1 H, m, CHMe), 1.35 (3 H, s,
Me), 1.33 (3 H, s, Me) and 1.30 (3 H, d, J 6.8, CHMe); δC(101
MHz; CDCl3) 136.5, 133.7, 130.3, 128.7, 89.1, 75.7, 65.4,
31.9, 18.3, 17.5 and 14.4; m/z 125.0 (30%, PhSOH), 113.1 (100,
M Ϫ PhSOH) and 71.1 (25, M Ϫ C3H6SOPh).
t
0.88 (9 H, s, Bu); δC(101 MHz; CDCl3) 97.4, 74.4, 31.8, 29.0,
t
t
23.8 and 18.7; m/z 84.1 (5%, BuCHCH2), 71.1 (75, M Ϫ Bu)
and 57.1 (100, tBu).
(2S*,3R*)-2-Cyclohexyl-3-methyloxetane 69
In the same way as oxetane 3 (Table 1, entry 2), the diol 48
(0.2 g, 1.16 mmol), gave, after column chromatography eluting
with light petroleum–ether (9 : 1) the oxetane 69 (5.3 mg,
3%) as an oil, Rf (light petroleum–ether 9 : 1) 0.25; νmax (film,
CDCl3)/cmϪ1 3100 (CH). 1H NMR consistent with that
reported previously.38
4-Hydroxy-5-methyl-5-phenylsulfanylhexan-2-one 76
In the same way as ester 13, acetone (0.61 g, 0.8 ml, 10.5 mmol)
and aldehyde 5918b (1.8 g, 10 mmol) gave, after column chrom-
atography eluting with light petroleum–ether (1 : 1), the ketone
76 (2.2 g, 92%) as an oil, Rf (light petroleum–ether 1 : 1) 0.5;
νmax (film, CDCl3)/cmϪ1 3300 (OH) and 1715 (CO); δH(200
MHz; CDCl3) 7.59–7.29 (5 H, m, SPh), 3.72 (1 H, dd, J 9.7 and
2.2, CHOH), 3.25–3.10 (1 H, br s, OH), 2.61 (1 H, double AB
quartet, J 16.4 and 4.4, CHAHB), 2.67 (1 H, double AB quartet,
J 16.4 and 10.9, CHAHB), 2.22 (3 H, s, MeCO), 1.26 (3 H, s, Me)
and 1.20 (3 H, s, Me); δC(51 MHz; CDCl3) 208.6, 137.4, 130.9,
129.1, 128.6, 72.1, 53.0, 44.6, 30.6, 24.5 and 23.9; m/z 238.1
(100%, M), 220.1 (30, M Ϫ H2O) and 151.1 (70, C3H6SPh).
(2S*,3S*)-3-Methyl-2-phenyloxetane 70
In the same way as oxetane 63, method A; diol 53 (0.1 g, 0.60
mmol) gave oxetane 70 (10 mg, 11%). In the same way as
oxetane 63, method B; diol 53 (50 mg, 0.30 mmol) gave oxetane
70 (22.4 mg, 50%) as a colourless oil, Rf (light petroleum–ether
4 : 1) 0.28; νmax(CHCl3)/cmϪ1 1600 (C᎐C), 980 and 920 (C-O).
᎐
1H NMR consistent with that reported previously.30
(2S*,3S*)-2-Butyl-3-methyloxetane 71
In the same way as oxetane 63, method B; diol 54 (100 mg, 0.69
mmol) gave oxetane 71 (30 mg, 34%) as a colourless oil, Rf (light
petroleum–ether 9 : 1) 0.25; νmax(CHCl3)/cmϪ1 970 and 920
(C-O); δH(500 MHz; CDCl3) 4.80 (1 H, td, J 7.9 and 5.5,
RCHO), 4.75 (1 H, dd, J 7.4 and 5.8, CHAHBO), 4.05 (1 H, t,
J 5.6, CHAHBO), 2.99 (1 H, sept, J 7.0, CHMe), 1.77–1.17 (6 H,
m, CH2), 1.16 (3 H, d, J 7.2, CHMe) and 0.89 (3 H, t, J 7.2,
Me); δC(101 MHz; CDCl3) 85.0, 75.6, 32.0, 31.5, 29.7, 26.9, 14.0
and 13.5; m/z(ϩCI) 111.1 (100%, MH Ϫ OH2), 69.1 (35, CH3-
CH2CH2CH2C) and 58.1 (40, OCH2CHCH3) [Found: (MH Ϫ
OH2)ϩ, 111.1177. C8H15 requires MH Ϫ OH2, 111.1174].
5-Methyl-5-phenylsulfanylhexan-2,4-diols 77 and 78
In the same way as diol 16, ketone 76 (0.1 g, 0.42 mmol) gave,
after column chromatography eluting with light petroleum–
ether (1 : 1), the diol 77 (62 mg, 61%) as an oil, Rf (light
petroleum–ether 1 : 1) 0.2; νmax (film, CDCl3)/cmϪ1 3500–3300
(OH); δH(200 MHz; CDCl3) 7.54–7.25 (5 H, m, SPh), 4.03–3.87
(1 H, m, CHMe), 3.87–3.50 (2 H, br s, 2 × OH), 3.54 (1 H, dd,
J 9.8 and 2.9, CHOH), 1.68–1.39 (2 H, m, CH2), 1.27 (3 H, s,
Me), 1.18 (3 H, s, Me) and 1.16 (3 H, d, J 6.0, MeCH); δC(51
MHz; CDCl3) 137.4, 130.1, 129.2, 128.8, 76.0, 66.4, 54.7, 38.1,
25.4, 23.6 and 21.9; m/z 240.1 (35%, M), 151.1 (100, C3H6SPh),
110.0 (60, PhSH) and 71.1 (45, C4H7O) (Found: Mϩ, 240.1178.
C13H20O2S requires M, 240.1183) and the diol 78 (31 mg, 30%)
as an oil, Rf (light petroleum–ether 1 : 1) 0.1; νmax (film, CDCl3)/
cmϪ1 3450–3300 (OH); δH(200 MHz; CDCl3) 7.58–7.34 (5 H, m,
SPh), 4.20–4.05 (1 H, m, CHMe), 3.67 (1 H, dd, J 9.8 and 3.0,
CHOH), 3.29–3.17 (1 H, br s, OH), 2.55–2.20 (1 H, br s, OH),
1.74–1.45 (2 H, m, CH2), 1.24 (3 H, s, Me), 1.22 (3 H, d, J 6.4,
MeCH) and 1.18 (3 H, s, Me); δC(51 MHz; CDCl3) 137.4, 130.1,
129.2, 128.7, 71.7, 65.5, 55.1, 38.2, 25.6, 23.3 and 22.4; m/z
240.1 (5%, M), 151.1 (100, C3H6SPh), 110.0 (65, PhSH) and
71.1 (50, C4H7O) (Found: Mϩ, 240.1185. C13H20O2S requires M,
240.1183).
(2S*,3S*)-2-Benzyloxymethyl-3-methyloxetane 72
In the same way as oxetane 63, method A, diol 55 (100 mg, 0.49
mmol) gave oxetane 72 (33 mg, <35%) inseparable from impur-
ities. In the same way as oxetane 63, method B, diol 55 (102 mg,
0.49 mmol) gave oxetane 72 (30 mg, 32%) as a colourless oil,
Rf (light petroleum–ether 4 : 1) 0.10; νmax(CHCl3)/cmϪ1 1644
(C᎐C), 964 (ring CO) and 907 (ring CO); δ (400 MHz; CDCl )
᎐
H
3
7.37–7.24 (5 H, m, Ph), 4.95 (1 H, td, J 11.8 and 3.8, CHO),
4.75 (1 H, dd, J 7.9 and 5.6, ring-CHAHBO), 4.58 (1 H, d, J 10.1,
PhHAHBO), 4.53 (1 H, d, J 10.1, PhHAHBO), 4.19 (1 H, t, J 6.0,
ring CHAHBO), 3.72 (2 H, d, J 5.8, OCH2CHO), 3.14 (1 H, sept,
J 7.1, CHMe) and 1.16 (3 H, d, J 7.1, CHMe); δC(101 MHz;
CDCl3) 138.2, 128.6, 127.8, 127.7, 83.0, 76.8, 73.5, 72.8, 31.3
and 13.4; m/z(ϩCI) 193.1 (33%, MHϩ), 108.1 (23, PhCH2OH),
91.1 (100, PhCH2) and 85.1 (73, C4H7O) (Found: MHϩ,
193.1218. C12H17O2 requires MH, 193.1228).
(3R*,5R*)-3-Phenylsulfanyl-2,2,5-trimethyltetrahydrofuran 79
In the same way as oxetane 3 (Table 1, entry 3), diol 77 (40 mg,
0.16 mmol) gave, after column chromatography eluting with
light petroleum–ether (9 : 1), the THF 79 (37 mg, 99%), Rf (light
petroleum–ether 9 : 1) 0.25; νmax(CHCl3)/cmϪ1 1550 (SPh);
δH(500 MHz; CDCl3) 7.45–7.20 (5 H, m, SPh), 4.05 (1 H, d
quintet, J 9.9 and 6.0, CHMe), 3.47 (1 H, dd, J 11.1 and 6.8,
CHSPh), 2.45 (1 H, quintet, J 5.6, CHAHB), 1.74 (1 H, ddd,
J 9.9, 6.5 and 5.5, CHAHB), 1.27 (6 H, s, 2 Me) and 1.26 (3 H, d,
J 6.1, CHMe); δC(101 MHz; CDCl3) 135.9, 131.3, 129.0, 126.9,
82.3, 72.1, 56.3, 42.3, 28.1, 25.6 and 22.1; m/z 207.1 (55%, M Ϫ
Me), 164.1 (15, M Ϫ C3H6O) and 110.0 (20, PhSH) [Found:
(M Ϫ Me)ϩ, 207.0842. C12H15OS requires M Ϫ Me, 207.0430].
3-Methyl-1-oxaspiro[3.5]nonane 74
In the same way as oxetane 63, method B, diol 57 (104 mg, 0.72
mmol) gave oxetane 74 (30 mg, 33%) as a colourless oil, Rf (light
petroleum–ether 9 : 1) 0.25; νmax(CHCl3)/cmϪ1 970 and 920
(C-O); δH(400 MHz; CDCl3) 4.56 (1 H, dd, J 5.9 and 8.1,
CHAHBO), 4.01 (1 H, t, J 6.3, CHAHBO), 2.62 (1 H, sex, J 7.1,
CHMe), 1.84–1.26 (10 H, m, CH2) and 1.13 (3 H, d, J 5.1
CHMe); δC(101 MHz; CDCl3) 87.8, 72.4, 39.8, 38.1, 32.6,
25.4, 22.3, 22.2 and 13.7; m/z(ϩCI) 141.1 (13%, MHϩ), 123.0
(27, MH Ϫ OH2), 84.2 (18, c-hexyl Ϫ 2 × H) and 59.1 (22,
J. Chem. Soc., Perkin Trans. 1, 2001, 2983–2996
2995