1583 (SPh); δH(400 MHz; CDCl3) 7.42–7.37 (2 H, m, SPh),
7.31–7.20 (3 H, m, SPh), 4.10–4.03 (1 H, double quintet, J 9.4
and 6.4, OCHMe), 3.82–3.72 (4 H, m, 2 × OCH2eqϩax), 3.41
(1 H, dd, J 10.1 and 7.1, CHSPh), 2.49 (1 H, ddd, J 12.8, 7.0
and 6.0, CHAHB), 1.96 (1 H, ddd, J 13.3, 11.6 and 5.2, CHC-
HDax), 1.8 (1 H, ddd, J 14.7, 11.6 and 4.5, CHCHDax), 1.71 (1 H,
dt, J 12.8 and 10.1, CHAHB), 1.56 (1 H, qd, J 13.3 and 2.4,
CHCHDeq), 1.43 (1 H, qd, J 13.4 and 2.3, CHCHDeq) and 1.28
(3 H, d, J 6.1, Me); δC(100 MHz; CDCl3) 135.6, 131.3, 129.1,
126.9, 80.7, 72.4, 64.7, 64.4, 56.1, 41.4, 36.4, 34.6 and 22.2.
M, 264.1189); m/z (EI) 264 (65%, M), 155 (100, M Ϫ SPh), 110
(90, SPh) and 83 (40, C5H7O).
3-Hydroxy-3-[methoxy(phenylsulfanyl)methyl]thiolane 56
In the same way as alcohol 15; X = O, methoxymethyl phenyl
sulfide (4.75 g, 4.55 ml, 30.9 mmol), n-BuLi (24.9 ml, 1.3 M in
hexanes, 32.4 mmol) and tetrahydrothiophen-3-one 55 (3.0 g,
2.51 ml, 29.4 mmol) in THF (150 ml) gave, after column
chromatography on silica gel eluting with petroleum ether–
ether (9:1), an inseparable diastereomeric mixture (54:46) of
the alcohol 56 (7.1 g, 95%) as a colourless oil; Rf [petroleum
ether–ether (9:1)] 0.1; νmax(film, CDCl3)/cmϪ1 3300 (OH) and
1550 (SPh); δH(200 MHz; CDCl3) 7.55–7.23 (10 H, m, SPhmaj
and SPhmin), 7.75 (1 H, s, CHSPhmaj), 4.74 (1 H, s, CHSPhmin),
3.49 (6 H, s, OMemaj and OMemin), 3.23–2.65 (8 H, m, 2 ×
(2RS,4RS)-2-Methyl-4-phenylsulfanyl-1,8-dioxaspiro[4.5]-
decane anti-51
In the same way as the tetrahydrofuran anti-24; X = O, the diol
anti-46 (50 mg, 0.18 mmol) and toluene-p-sulfonic acid (6.8 mg,
36 µmol) in CH2Cl2 (2.5 ml) gave, the tetrahydrofuran anti-51
(45 mg, 96%) as a colourless oil; Rf [ether] 0.7; νmax(NaCl)/cmϪ1
1583 (SPh); δH(400 MHz; CDCl3) 7.42–7.38 (2 H, m, SPh),
7.31–7.20 (3 H, m, SPh), 4.24 (1 H, sext, J 6.3, OCHMe), 3.82–
3.70 (4 H, m, 2 CH2Oeqϩax), 3.42 (1 H, t, J 7.5, CHSPh), 2.16
(1 H, dt, J 13.0 and 7.2, CHAHB), 2.06 (1 H, ddd, J 13.1, 7.9 and
6.4, CHAHB), 1.94–1.81 (2 H, m, 2 × CHCHDax), 1.60 (1 H, dq,
J 12.5 and 2.5, CHCHDeq), 1.40 (1 H, dq, J 13.3 and 2.5, CHC-
HDeq) and 1.23 (3 H, d, J 6.2, Me); δC(100 MHz; CDCl3)
135.6, 131.3, 131.2, 129.1, 126.8, 81.4, 71.8, 64.8, 64.4, 55.5,
40.5, 37.8, 31.6 and 22.5 (Found Mϩ, 264.1184. C15H20O2S
requires M, 264.1183); m/z (EI) 264 (20%, M), 164 (100) and
110 (60, SPh).
maj
maj
CH2 and 2 × CH2min) and 2.20–2.08 (4 H, m, CH2 and
CH2min); δC(50 MHz; CDCl3) 134.9 (i-SPhmin), 134.8 (i-SPhmaj),
132.9 (m-SPhmaj and i-SPhmin), 129.4 (o-SPhmaj and o-SPhmin),
127.7 (p-SPhmaj and p-SPhmin), 99.0 (CHSPhmaj and CHSPhmin),
86.2 (COHmin), 86.0 (COHmaj), 57.5 (MeOmaj and MeOmin),
39.8, 39.6, 39.5 and 39.2 (2 × CH2Smaj and 2 × CH2Smin), 29.2
(CH2min) and 29.0 (CH2maj) (Found Mϩ, 256.0588. C12H16O2S2
requires M, 256.0591); m/z 256.1 (40%, M), 147.1 (35,
M Ϫ SPh) and 115.0 (100, M Ϫ SPh Ϫ MeOH).
3-(Phenylsulfanyl)thiolane-3-carboxaldehyde 57
In the same way as aldehyde 17; X=O, the alcohol 56 (6.0 g, 23.4
mmol), Et3N (25.2 g, 34.0 ml, 0.25 mol) and thionyl chloride
(8.36 g, 5.23 ml, 70.3 mmol) in CH2Cl2 (350 ml) gave, after
column chromatography on silica gel eluting with petroleum
ether–ether (9:1), the aldehyde 57 (3.66 g, 70%) as a colourless
oil; Rf [petroleum ether–ether (9:1)] 0.35; νmax(film, CDCl3)/
cmϪ1 1750 (CO) and 1550 (SPh); δH(200 MHz; CDCl3) 9.31
(1 H, s, CHO), 7.49–7.25 (5 H, m, SPh), 3.12 (1 H, AB quartet,
CHAHBS), 3.05–2.97 (1 H, m, CHCHDS), 2.94 (1 H, AB quartet,
CHAHBS), 2.83–2.70 (1 H, m, CHCHDS), 2.55–2.42 (1 H, m,
CHEHF) and 2.15–1.99 (CHEHF); δC(50 MHz; CDCl3) 191.9
(CHO), 136.3 (m-SPh), 129.8 (p-SPh), 129.2 (i-SPh), 129.1
(o-SPh), 66.3 (CSPh), 35.5 (CH2S), 35.3 (CH2S) and 29.0 (CH2)
(Found Mϩ, 224.0327. C11H12OS2 requires M, 224.0329); m/z
224.0 (50%, M), 195.0 (20, M Ϫ CHO), 115.1 (40, M Ϫ SPh),
109.0 (45, SPh) and 87.0 (100, C4H6S ϩ H).
(1SR,2SR)-1-(3,6-Dihydro-(2H)-pyran-4-yl)-2-methyl-3-
phenylsulfanylpropan-1-ol anti-54
Toluene-p-sulfonyl chloride (80 mg, 0.39 mmol) was added to a
stirred solution of the diol anti-31 (0.1 g, 0.35 mmol) in pyridine
(1 ml). The solution was stirred for 12 hours. Ether (20 ml) was
added and the solution was extracted with HCl (10 ml, 3 M)
and evaporated under reduced pressure. The residue was puri-
fied by flash chromatography on silica gel eluting with petrol-
eum ether–ether (1:1) to give the allylic alcohol anti-54 (33 mg,
64%) as a colourless oil; Rf [ether] 0.6; [α]D Ϫ7.5 (c 0.2 in
CHCl3); νmax(NaCl)/cmϪ1 3426 (OH) and 1580 (SPh); δH(400
MHz; CDCl3) 7.37–7.31 (2 H, m, Ph), 7.27–7.24 (2 H, m, Ph),
7.16–7.13 (1 H, m, Ph), 5.68 (1 H, s, CH᎐C), 4.16–4.14 (2 H, m,
᎐
OCH CH᎐), 3.88 (1 H, d, J 7.6, CHOH), 3.80 (1 H, dt, J 10.9
᎐
2
Ethyl 3-[(3Ј-phenylsulfanyl)thiolanyl]propionate 58
and 5.4, CHAHBO), 3.71 (1 H, ddd, J 11.3, 6.9 and 4.5, CHA-
HBO), 3.32 (1 H, dd, J 12.9 and 3.6, CHAHBS), 2.75 (1 H, dd,
J 12.9 and 8.4, CHAHBS), 2.14–2.09 (1 H, m, CHCHD), 1.99–
1.91 (2H, m, CHCHD and CHMe) and 0.98 (3 H, d, J 6.8, Me);
δC(100 MHz; CDCl3) 137.0, 136.7, 129.5, 128.9, 128.8, 125.7,
123.2, 79.3, 65.2, 64.2, 36.7, 36.0, 24.0 and 16.4 (Found Mϩ,
264.1183. C15H22O3S requires M, 264.1183); m/z (EI) 264 (20%,
M), 143 (100) and 109 (30, SPh).
In the same way as ester anti-20; X = O, diisopropylamine (0.94
g, 1.26 ml, 9.29 mmol), n-BuLi (5.61 ml, 1.3 M in hexanes, 7.3
mmol), ethyl acetate (0.61 g, 0.68 ml, 6.97 mmol) and aldehyde
57 (1.5 g, 6.63 mmol) in THF (150 ml) gave, after HPLC eluting
with petroleum ether–ether (1:1), an inseparable diastereo-
meric mixture (50:50) of the ester 58 (1.88 g, 90%) as a colour-
less oil; Rf [petroleum ether–ether (1:1)] 0.35; νmax(film, CDCl3)/
cmϪ1 3300 (OH) and 1700 (CO); δH(200 MHz; CDCl3) 7.68–
7.31 (10 H, m, 2 × SPh), 4.35–4.11 (6 H, m, 2 × CH2 and
2 × OH), 3.31–3.05 (8 H, m, 4 × CH2S), 2.99–2.85 (4 H, m,
2 × CH2CO2), 2.42–1.89 (4 H, m, 2 × CH2) and 1.29 (6 H, t,
J 7.2, 2 × Me); δC(50 MHz; CDCl3) 172.5 and 172.4 (2 × CO),
138.9 (2 × o-SPh), 138.4 (2 × o-SPh), 131.3 and 131.3 (2 ×
i-SPh), 129.7 (2 × p-SPh), 71.0 and 71.0 (2 × CHOH), 67.8 and
67.8 (2 × CH2O), 61.0 (2 × CSPh), 38.9 and 38.9 (2 × CH2CO2),
37.3, 37.2 and 37.1 (4 × CH2S), 29.6 and 29.5 (2 × CH2) and
14.2 (2 × Me) (Found Mϩ, 312.0846. C15H20O3S2 requires M,
312.0853); m/z 312.1 (30, M), 267.0 (20, M Ϫ OEt), 202.1 (65,
M Ϫ PhSH), 185.1 (100, M Ϫ SPh Ϫ H2O), 110.0 (55, PhSH),
87.0 (70, C4H7S) and 77.0 (20, Ph).
(1SR,2SR)-1-(3,6-Dihydro-(2H)-pyran-4-yl)-2-methyl-3-phenyl-
sulfanylpropan-1-ol syn-54
In the same way as the allylic alcohol anti-54, the diol syn-31
(100 mg, 0.35 mmol) and toluene-p-sulfonyl chloride (80 mg,
0.39 mmol) in pyridine (1 ml) gave, after flash column chroma-
tography on silica gel eluting with petroleum ether–ether (3:1)
the allylic alcohol syn-54 (76 mg, 82%), as a colourless oil; Rf
[ether] 0.6; [α]D Ϫ10.2 (c 0.82 in CHCl3); νmax(NaCl)/cmϪ1 3426
(OH) and 1580 (SPh); δH(400 MHz; CDCl3) 7.36–7.15 (5 H, m,
Ph), 5.69 (1 H, br s, CH᎐C), 4.16–4.15 (3 H, m, OCH CH᎐C
᎐
᎐
2
and CHOH), 3.80–3.70 (2 H, m, CH2O), 3.05 (1 H, dd, J 13.0
and 6.7, CHAHBS), 2.79 (1 H, dd, J 13.0 and 6.9, CHAHBS),
2.06–1.99 (1 H, m, CHCHD), 1.94–1.80 (2 H, m, CHCHD and
CHMe) and 0.99 (3 H, d, J 6.7, Me); δC(100 MHz; CDCl3)
136.6, 136.5, 129.0, 129.7, 126.1, 121.3, 76.1, 65.4, 64.1, 38.0,
35.6, 25.1 and 13.5 (Found Mϩ, 264.1184. C15H20O2S requires
3-[(3Ј-Phenylsulfanyl)thiolanyl]propan-1,3-diol 59
In the same way as diol anti-22, the ester 58 (1.8 g, 5.76 mmol)
and LiAlH4 (0.65 g, 17.3 mmol) in ether (20 ml) gave, after
J. Chem. Soc., Perkin Trans. 1, 2000, 1903–1914
1913