Sneddon et al.
were washed with saturated brine (10 mL), dried over MgSO4,
filtered, and concentrated under reduced pressure. Flash column
chromatography (petroleum ether/Et2O, 90:10) afforded 23 (29 mg,
94%) as a clear, colorless oil. [R]2D5 -36 (c 0.075, CHCl3). IR
2.21 (1 H, d, J ) 13.8 Hz), 2.12 (1 H, dd, J ) 14.7, 7.2 Hz), 2.07
(1 H, m), 2.05 (1 H, dd, J ) 14.7, 5.3 Hz), 1.95-1.85 (3 H, m),
1.80 (1 H, t, J ) 12.2 Hz). 13C NMR (150 MHz, CDCl3) δ 138.3,
128.3 (2 C), 127.6 (2 C), 127.5, 96.8, 73.4, 72.5, 69.0, 65.3, 47.7,
46.3, 40.8, 39.8, 30.4, 30.2, 26.4, 26.0, 25.4, 25.0. HRMS (+ESI)
m/z 463.0870 [(M + Na)+; calcd for C21H28O2S4Na 463.0870].
1
(neat) 2929, 1654, 1513, 1248, 1173 cm-1. H NMR (400 MHz,
CDCl3) δ 7.65 (4 H, m), 7.35 (6 H, m), 7.24 (2 H, d, J ) 8.9 Hz),
6.87 (2 H, d, J ) 8.5 Hz), 4.68 (1 H, s), 4.50 (2 H, AB quartet),
4.23 (1 H, m), 3.80 (3 H, s), 3.70 (1 H, dd, J ) 9.6, 5.9 Hz), 3.62-
3.55 (3 H, m), 3.03-2.95 (2 H, m), 2.75 (2 H, m), 2.69 (1 H, d, J
) 13.8 Hz), 2.60 (1 H, m), 2.37 (1 H, m), 2.03 (3 H, m), 1.84 (1
H, m), 1.09 (3 H, d, J ) 7.0 Hz), 1.04 (9 H, s). 13C NMR (100
MHz, CDCl3) δ 159.2, 135.7, 135.6, 134.8, 133.94, 133.93, 130.3,
129.5, 129.3, 127.6, 113.8, 99.6, 73.1, 73.0, 71.4, 66.1, 55.3, 45.3,
40.9, 38.6, 30.3, 27.5, 27.2, 26.9 (3 C), 24.6, 19.3, 14.7. HRMS
(+ESI) m/z 635.2684 [(M - OH)+; calcd for C36H47O4S2Si
634.9655].
(8R,10S,11S)-8-([1,3]Dithian-2-yl)methyl-11-methyl-10-(1-
methyl-allyl)-9-oxa-1,5-dithia-spiro[5.5]undecan-8-ol (31e).21 Com-
pound 31e was prepared using procedure E in 65% yield. [R]D25
+3.8 (c 1.00, CHCl3). IR (neat) 3350, 2900, 1638, 1413, 1019 cm-1
.
1H NMR (600 MHz, CDCl3) δ 6.02 (1 H, ddd, J ) 17.2, 10.4, 7.5
Hz), 5.95 (1 H, s), 5.04 (1 H, d, J ) 17.2 Hz), 4.98 (1 H, d, J )
10.4 Hz), 4.40 (1 H, t, J ) 6.2 Hz), 3.77 (1 H, dd, J ) 10.4, 2.1
Hz), 3.16 (1 H, dt, J ) 14.7, 2.4 Hz), 3.09 (1 H, app. d, J ) 14.6
Hz), 2.93 (2 H, dt, J ) 11.2, 2.5 Hz), 2.80 (3 H, m), 2.68 (1 H, m),
2.40 (1 H, app. t, J ) 7.1 Hz), 2.14 (1 H, m), 2.08 (2 H, m), 2.03
(2 H, app. dq, J ) 14.6, 5.8 Hz), 1.84 (3 H, m), 1.18 (3 H, d, J )
6.8 Hz), 0.99 (3 H, d, J ) 7.0 Hz). 13C NMR (150 MHz, CDCl3)
δ 142.5, 113.5, 95.9, 72.1, 53.4, 47.9, 43.5, 42.0, 41.4, 38.6, 30.7,
30.7, 25.8, 25.7, 25.5, 25.1, 11.9, 11.8. HRMS (+ESI) m/z 429.1026
[(M + Na)+; calcd for C18H30O2S4Na 429.1019].
(8R,10R)-10-Benzyloxymethyl-8-ethyl-9-oxa-1,5-dithia-spiro-
[5.5]undecan-8-ol (31a). Compound 31a was prepared using
procedure D in 58% yield. [R]2D5 +18.0 (c 0.31, CHCl3). IR (neat)
1
3381, 2906 cm-1. H NMR (500 MHz, CDCl3) δ 7.31 (5 H, m),
5.47 (1 H, s), 4.58 (2 H, d, J ) 6.2 Hz), 4.28 (1 H, m), 3.58 (1 H,
dd, J ) 10.2, 4.7 Hz), 3.50 (1 H, dd, J ) 10.2, 5.1 Hz), 3.11 (1 H,
ddd, J ) 14.5, 11.6, 2.8 Hz), 2.99 (1 H, ddd, J ) 14.1, 11.5, 2.7
Hz), 2.80 (1 H, m), 2.74 (1 H, m), 2.68 (1 H, dd, J ) 14.3, 2.2
Hz), 2.13 (2 H, m), 1.92 (2 H, m), 1.77 (1 H, dd, J ) 13.5, 2.2
Hz), 1.65 (2 H, q, J ) 7.4 Hz), 0.98 (3 H, t, J ) 7.4 Hz). 13C
NMR (125 MHz, CDCl3) δ 138.2, 128.3, 127.7, 127.6, 97.6, 73.4,
72.6, 64.7, 46.3, 41.7, 40.2, 35.2, 26.3, 25.9, 25.1, 7.3. HRMS
(+ESI) m/z 377.1205 [(M + Na)+; calcd for C18H26O3S2Na
377.1221].
(7R,9R)-9-Benzyloxymethyl-7-ethyl-8-oxa-1,4-dithia-spiro[4.5]-
decan-7-ol (32a). Compound 32a was prepared using procedure
D in 63% yield. [R]2D5 +8.5 (c 0.42, CHCl3). IR (neat) 3422, 2919
cm-1. 1H NMR (500 MHz, CDCl3) δ 7.30 (5 H, m), 4.57 (2 H, s),
4.24 (1 H, m), 3.53 (1 H, dd, J ) 10.3, 5.4), 3.47 (1 H, dd, J )
10.3, 4.5 Hz), 3.31 (4 H, m), 3.21 (1 H, d, J ) 0.9 Hz), 2.28 (1 H,
dd, J ) 14.1, 2.1 Hz), 2.12 (2 H, m), 1.92 (1 H, dd, J ) 13.4, 11.5
Hz), 1.65 (2 H, q, J ) 7.6 Hz), 0.95 (3 H, t, J ) 7.6 Hz). 13C
NMR (125 MHz, CDCl3) δ 138.3, 128.3 (2 C), 127.7 (2 C), 127.6,
97.7, 73.4, 72.7, 69.0, 60.3, 46.4, 44.0, 39.4, 37.6, 35.6, 7.4. HRMS
(+ESI) m/z 363.1035 [(M + Na)+; calcd for C17H24O3S2Na
363.1065].
(7R,9R)-9-Benzyloxymethyl-7-(2-hydroxy-ethyl)-8-oxa-1,4-
dithia-spiro[4.5]decan-7-ol (32f). Compound 32f was prepared
using procedure D in 90% yield. The â-anomer was formed in trace
amounts, therefore only the R-anomer is reported below. [R]D25
-4.3 (c 0.65, CHCl3). IR (neat) 3393, 2918, 1091 cm-1. 1H NMR
(600 MHz, CDCl3) δ 7.36-7.26 (5 H, m). 4.60 (1 H, s), 4.56 (2
H, m), 4.30 (1 H, m), 3.97 (1 H, m), 3.84 (1 H, m), 3.52 (2 H, dd,
J ) 6.8, 5.4 Hz), 3.33 (4 H, m), 2.64 (1 H, t, J ) 4.9 Hz), 2.33 (1
H, dd, J ) 13.9, 2.0 Hz), 2.19 (1 H, d, J ) 13.9 Hz), 2.14 (1 H,
d, J ) 13.5 Hz), 1.99 (1 H, m), 1.93 (1 H, ddd, J ) 14.5, 8.6, 3.6
Hz, 1 H), 1.83 (1 H, ddd, J ) 14.5, 6.2, 3.0 Hz). 13C NMR (150
MHz, CDCl3) δ 138.1, 128.4 (2 C), 127.68 (2 C), 127.65, 98.0,
73.4, 72.5, 68.9, 62.8, 58.5, 48.0, 43.7, 42.8, 39.4, 37.6. HRMS
(+ESI) m/z 379.1000 [(M + Na)+; calcd for C17H24O4S2Na
379.1014].
(8RS,10R)-10-Benzyloxymethyl-9-oxa-1,5-dithia-spiro[5.5]-
undecan-8-ol (31b). Compound 31b was prepared using procedure
D. The lactol was obtained as an inseparable mixture of anomers
1
(10:7) in 41% yield. IR (neat) 3411, 2907 cm-1. H NMR (500
MHz, CDCl3) δ 7.31 (10 H, m), 5.28 (1 H, m), 5.13 (1 H, ddd, J
) 9.3, 6.1, 2.1 Hz), 4.57 (4 H, m), 4.36 (1 H, tdd, J ) 9.4, 4.6, 2.5
Hz), (1 H, tdd, J ) 7.8, 4.1, 2.1 Hz), 3.51 (4 H, m), 3.19 (1 H, d,
J ) 6.1 Hz), 3.04 (2 H, m), 2.83 (7 H, m), 2.56 (1 H, app. dt, J )
13.4, 2.1), 2.12 (4 H, m), 1.98 (4 H, m), 1.68 (2 H, m), one OH
not observed. 13C NMR (125 MHz, CDCl3) δ 138.0, 137.9,128.41,
128.38,128.2, 127.8, 127.74, 127.67, 92.49, 92.46, 73.6, 73.5, 72.41,
72.39, 70.6, 63.5, 47.4, 45.4, 43.6, 39.9, 39.4, 39.0, 26.4, 26.0,
25.91, 25.86, 25.5, 25.0. HRMS (+ESI) m/z 349.0903 [(M + Na)+;
calcd for C16H22O3S2Na 349.0908].
trans-(2′RS)-[1,3]-Dithian-2-spiro-4′-octahydro-chromen-2′-
ol (31c). Compound 31c was prepared using procedure D. The lactol
was obtained as an inseparable mixture of anomers (10:3.7) in 53%
yield. The structure was confirmed by X-ray crystallography. IR
(neat) 3380, 2929, 2856 cm-1. Mp ) 133-137 °C. 1H NMR (500
MHz, CDCl3) δ 5.88 (1 H, d, J ) 11.5 Hz), 5.20 (1 H, ddd, J )
12.5, 3.9, 1.0 Hz), 5.12 (1 H, ddd, J ) 11.1, 6.6, 1.9 Hz), 3.82 (1
H, app. dt, J ) 10.2, 4.7 Hz), 3.60 (1 H, app. dt, J ) 10.4, 4.3 Hz),
3.45 (1 H, d, J ) 6.6 Hz), 3.13 (3 H, m), 3.04 (3 H, m), 2.81 (1 H,
td, J ) 14.4, 3.6 Hz), 2.66 (1 H, td, J ) 14.4, 7.8 Hz), 2.15 (5 H,
m), 1.97 (2 H, m), 1.80 (7 H, m), 1.60 (1 H, m), 1.32 (9 H, m),
one OH not observed. 13C NMR (125 MHz, CDCl3) δ 92.8, 92.3,
73.0, 66.7, 52.7, 51.2, 51.1, 50.7, 44.4, 40.1, 32.92, 32.90, 25.76,
25.73, 25.67, 25.63, 25.58, 25.49, 25.41, 25.34, 25.14, 24.5, 24.3.
HRMS (+ESI) m/z 283.0799 [(M + Na)+; calcd for C12H20O2S2-
Na 283.0802].
(9R)-9-Benzyloxymethyl-8-oxa-1,4-dithia-spiro[4.5]decan-7-
ol (32b). Compound 32b was prepared using procedure D. The
lactol was obtained as a mixture of anomers (10:6.5) in 64% yield.
1
IR (neat) 3402, 2919, 2862 cm-1. H NMR (500 MHz, CDCl3) δ
7.31 (10 H, m), 5.34 (1 H, m), 4.88 (1 H, ddd, J ) 9.3, 6.0, 2.0
Hz), 4.57 (4 H, m), 4.32 (1 H, m), 3.88 (1 H, m), 3.50 (4 H, m),
3.32 (8 H, m), 2.99 (1 H, d, J ) 6.0 Hz), 2.36 (4 H, m), 2.01 (4 H,
m), one OH not observed. 13C NMR (125 MHz, CDCl3) δ 138.0,
137.9, 128.40, 128.38, 127.83, 127.77, 127.72, 127.67, 95.2, 92.0,
73.8, 73.5, 73.4, 72.5, 72.3, 67.7, 64.0, 61.8, 48.1, 43.9, 43.7, 43.5,
39.6, 39.5, 38.0, 37.8. HRMS (+ESI) m/z 335.0744 [(M + Na)+;
calcd for C15H20O3S2Na 335.0752].
(10R)-10-Benzyloxymethyl-8-([1,3]dithian-2-yl)methyl-9-oxa-
1,5-dithia-spiro[5.5]undec-7-ene (31d). Compound 31d was pre-
pared using procedure E in 91% yield. [R]2D5 +16.3 (c 1.035,
trans-(2′RS)-[1,3]-Dithiolan-2-spiro-4′-octahydro-chromen-2′-
ol (32c). Compound 32c was prepared using procedure D. The lactol
was obtained as a mixture of anomers (10:4) in 58% yield. The
structure was confirmed by X-ray crystallography. IR (neat) 3384,
2929, 2857 cm-1. Mp ) 109-111 °C. 1H NMR (500 MHz, CDCl3)
δ 5.25 (1 H, m), 4.86 (1 H, m), 4.08 (1 H, m), 3.70 (1 H, app. td
J ) 10.2, 4.4 Hz), 3.24 (9 H, m), 2.46 (3 H, m), 2.14 (2 H, m),
2.03 (1 H, dd, J ) 13.0, 9.3 Hz), 1.96 (2 H, m), 1.92 (1 H, m),
1
CHCl3). IR (neat) 3346, 2901, 1421, 1091, 1020 cm-1. H NMR
(600 MHz, CDCl3) δ 7.34 (4 H, m), 7.28 (1 H, m), 5.63 (1 H, s),
4.81 (2 H, AB quartet), 4.39 (1 H, dd, J ) 6.9, 5.4 Hz), 4.33 (1 H,
m), 3.60 (1 H, dd, J ) 10.3, 4.7 Hz), 3.53 (1 H, dd, J ) 10.3, 4.9
Hz), 3.06 (1 H, ddd, J ) 13.8, 10.8, 2.5 Hz), 2.98-2.76 (7 H, m),
2722 J. Org. Chem., Vol. 71, No. 7, 2006