3138 J . Org. Chem., Vol. 62, No. 10, 1997
Furman et al.
mL) and hexane (20 mL). The organic layer was separated,
dried, and evaporated. The crude product was purified on a
silica gel column using hexane: tert-butyl methyl ether 9.5:
0.5 v/v as eluent to give 15 (0.8 g, 83%): [R]D ) -15.5° (c 0.5,
purified on a silica gel column using hexane:ethyl acetate 4:1
v/v as eluent to afford 33 and 34 (81%): IR (film) 1774, 3282
cm-1; 1H NMR (CDCl3) δ signals due to 33 1.61, 1.74 (2m, 2H),
2.73 (ddd, 1H, J ) 0.7, 1.4, 15.1 Hz), 3.02 (ddd, 1H, J ) 2.7,
4.0, 15.1 Hz), 3.49 (m, 1H), 3.60 (dt, 1H), 3.89 (m, 1H), 3.97
(dd, 1H, J ) 7.4, 10.5 Hz), 4.06 (dd, 1H, J ) 3.0, 10.5 Hz),
4.41, 4.51 (2d, 2H, J ) 11.8 Hz), 5.08 (dd, 1H, J ) 1.4, 4.0
Hz); signals due to 34 inter alia 2.71 (ddd, 1H, J ) 0.6, 1.5,
15.0 Hz), 2.98 (ddd, 1H, J ) 2.7, 4.0, 15.0 Hz), 5.00 (dd, 1H, J
) 1.5, 4.0 Hz); MS (HR, LSIMS) m/ z (M + H)+ calcd
420.148092, obsd 420.148085.
1
CH2Cl2): IR (film) 1632 cm-1; H NMR (CDCl3) δ 1.73-2.05
(m, 2H), 3.45-3.62 (m, 2H), 3.83 (d, 2H), 3.91 (dd, 1H, J )
1.5, 6.5 Hz), 4.07 (m, 1H), 4.25 (dd, 1H, J ) 1.5, 14.1 Hz), 4.45
(s, 2H), 6.31 (dd, 1H, J ) 6.5, 14.1 Hz); MS (HR, LSIMS) m/ z
(M+ + Na) calcd 503.20184, obsd 503.2028. Anal. Calcd for
C31H32O3Si: C, 77.50; H, 6.67. Found: C, 77.28; H, 6.60.
(S)-1-O-(Tr ip h en ylsilyl)-2-O-vin ylp r op a n e-1,2-d iol (17).
Compound 17 was obtained according to the procedure de-
scribed for 15 (80%): [R]D ) +1.8° (c 1.5, CH2Cl2); IR (film)
(3R,4′S)- a n d (3R,4′R)-3-O-(2′-Oxoa zetid in -4′-yl)-1-O-
(tr ip h en ylsilyl)bu ta n e-1,3-d iol (35 a n d 36). A mixture of
compounds 35 and 36 in proportion 1:2.6, respectively, was
obtained by addition of CSI to 16 according to the procedure
1
1638 cm-1; H NMR (CDCl3) δ 1.21 (d, 3H, J ) 6.3 Hz), 3.71
(dd, 1H, J ) 5.2, 10.5 Hz), 3.84 (dd, 1H, J ) 5.8, 10.5 Hz),
3.94 (dd, 1H, J ) 1.5, 6.5 Hz), 4.02 (sext, 1H), 4.23 (dd, 1H, J
) 1.5, 14.1 Hz), 6.31 (dd, 1H, J ) 6.5, 14.1 Hz); MS (HR,
LSIMS) m/ z (M + Na)+ calcd 383.144325, obsd 383.14413.
(S)-1-O-(Tr iisop r op ylsilyl)-2-O-vin ylp r op a n e-1,2-d iol
(18). Compound 18 was obtained according to the procedure
described for 15 (71%): [R]D ) +4.3° (c 0.7, CH2Cl2); IR (film)
described for addition to 13 (25%): IR (film) 1767, 3257 cm-1
;
1H NMR (CDCl3) δ signals due to 35 inter alia 1.15 (d, 1H, J
) 6.5 Hz), 2.78 (ddd, 1H, J ) 0.7, 1.4, 14.9 Hz), 3.04 (ddd, 1H,
J ) 2.7, 3.9, 14.9 Hz), 4.99 (dd, 1H, J ) 1.5, 2.8 Hz); signals
due to 36 inter alia 1.17 (d, 1H, J ) 6.3 Hz), 2.72 (dd, 1H, J )
0.6, 1.5, 15.0 Hz), 2.94 (dd, 1H, J ) 2.9, 4.0, 15.0 Hz), 4.96
(dd, 1H, J ) 1.5, 4.0 Hz). MS (HR, LSIMS) m/ z (M + Na)+
calcd 440.165788, obsd 440.165753.
1
1633 cm-1; H NMR (CDCl3) δ 1.23 (d, 1H, J ) 6.3 Hz), 3.61
(dd, 1H, J ) 5.5, 10.1 Hz), 3.77 (dd, 1H, J ) 5.7, 10.1 Hz),
3.96 (dd, 1H, J ) 1.5, 6.6 Hz), 3.97 (sext, 1H), 4.28 (dd, 1H, J
) 1.5, 14.1 Hz), 6.38 (dd, 1H, J ) 6.6, 14.1 Hz); MS (HR,
LSIMS) m/ z (M + H)+ calcd 259.20933, obsd 259.20934. Anal.
Calcd for C14H30O2Si: C, 65.12; H, 11.63. Found: C, 64.86;
H, 11.60.
(2S,4′S)- a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-1-O-
(tr ip h en ylsilyl)p r op a n e-1,2-d iol (41 a n d 42). A mixture
of compounds 41 and 42 in proportion of 6.7:1, respectively,
was obtained by addition of CSI to 17 according to the
procedure described for addition to 13 (25%): IR (film) 1769,
3269 cm-1; 1H NMR (CDCl3) δ signals due to 41 inter alia 1.15
(d, 1H, J ) 6.2 Hz), 2.77 (ddd, 1H, J ) 0.5, 1.5, 15.1 Hz), 2.96
(ddd, 1H, J ) 2.9, 3.9, 15.1 Hz), 5.21 (dd, 1H, J ) 1.5, 3.9 Hz);
signals due to 42 inter alia 1.10 (d, 1H, J ) 6.4 Hz), 2.79 (ddd,
1H, J ) 0.7, 1.5, 15.0 Hz), 3.05 (ddd, 1H, J ) 2.8, 4.0, 15.0
Hz), 5.11 (dd, 1H, J ) 1.5, 4.0 Hz). MS (HR, LSIMS) m/ z (M
+ H)+ calcd 404.168194, obsd 404.167923.
(2S,4′S) a n d (2S,4′R) 2-O-(2′-Oxoa zetid in -4′-yl)-1-O-ben -
zyl-4-O-(tr iisop r op ylben zen esu lfon yl)bu ta n e-1,2,4-tr iol
(25 a n d 26). To a solution of CSI (61 µL, 0.7 mmol) in toluene
(1 mL) was added anhydrous Na2CO3 (0.08 g). The mixture
was cooled to -78 °C and upon stirring was treated dropwise
with vinyl ether 13 (0.24 g, 0.5 mmol) in toluene (1 mL).
Stirring and cooling were maintained for 1.5 h. The mixture
was diluted with toluene (5 mL) and treated at -78 °C with 1
M Red-Al in toluene. After 30 min the mixture was allowed
to come to rt, and water (0.4 mL) was added. The mixture
was stirred for an additional 30 min, was filtered through
Celite and evaporated. Chromatography of on a silica gel
column using hexane:ethyl acetate 7:3 v/v as eluent gave a
1:1 mixture of 25 and 26 (0.13 g, 50%): IR (CHCl3) 1769, 3412
cm-1; 1H NMR (CDCl3) δ signals due to 25 inter alia 2.83 (ddd,
1H, J ) 0.7, 1.4, 15.0 Hz), 3.08 (ddd, 1H, J ) 2.8, 3.9, 15.0
Hz), 5.26 (dd, 1H, J ) 1.4, 3.9 Hz); signals due to 26 inter alia
2.76 (ddd, 1H, J ) 0.9, 1.5, 15.0 Hz), 3.06 (ddd, 1H, J ) 2.7,
4.1, 15.0 Hz), 5.04 (dd, 1H, J ) 1.5, 4.1 Hz). MS (HR, LSIMS)
m/ z (M+ + H) calcd 532.27328, obsd 532.27306.
(2S,4′S)- a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-4-O-
b en zyl-1-O-(t r iisop r op ylb en zen esu lfon yl)b u t a n e-1,2,4-
tr iol (27 a n d 28). A mixture of 27 and 28 in a ratio of 7:3,
respectively, was obtained from 14 according to the procedure
described above (58%). IR (CHCl3) 1772, 3409 cm-1; 1H NMR
(CDCl3) δ signals due to 27 inter alia 2.79 (ddd, 1H, J ) 0.7,
1.5, 15.2 Hz), 3.05 (ddd, 1H, J ) 2.6, 4.0, 15.2 Hz), 5.14 (dd,
1H, J ) 1.5, 4.0 Hz); signals due to 28 inter alia 2.74 (ddd,
1H, J ) 0.9, 1.5, 15.0 Hz), 5.05 (dd, 1H, J ) 1.5, 3.9 Hz); MS
(EI, HR) m/ z (M+) calcd 531.26545, obsd 531.26540.
(2S,4′S)- a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-1-O-
(tr iisop r op ylsilyl)p r op a n e-1,2-d iol (43 a n d 44). A mixture
of compounds 43 and 44 in proportion 5.5:1, respectively, was
obtained by addition of CSI to 18 according to the procedure
described for addition to 13 (27%): IR (film) 1771, 3263 cm-1
;
1H NMR (CDCl3) δ signals due to 43, inter alia 2.87 (ddd, 1H,
J ) 0.6, 1.5, 15.0 Hz), 3.11 (ddd, 1H, J ) 2.7, 3.9, 15.0 Hz),
5.34 (dd, 1H, J ) 1.5, 3.9 Hz); signals due to 44, inter alia
2.83 (ddd, 1H, J ) 0.9, 1.5, 15.0 Hz), 5.18 (dd, 1H, J ) 1.5, 4.0
Hz). MS (HR, LSIMS) m/ z (M + H)+ calcd 302.215147, obsd
302.213864.
(3R,4′S)- a n d (3R,4′R)-3-O-(2′-Oxoa zetid in -4′-yl)-1-O-
tosylbu ta n e-1,3-d iol (39 a n d 40). A mixture of compounds
39 and 40 (1:2.7) was obtained from the mixture of 35 and 36
according to the procedure described for 33 and 34 (65%): IR
1
(film) 1770, 3279 cm-1; H NMR (CDCl3) δ signals due to 39
inter alia 2.78 (ddd, 1H, J ) 0.6, 1.5, 14.9 Hz), 3.11 (ddd, 1H,
J ) 2.7, 4.0, 14.9 Hz), 4.01 (dt, 1H, J ) 4.5, 4.5, 9.9 Hz), 4.26
(dt, 1H, J ) 3.5, 9.9, 10.0 Hz), 5.08 (dd, 1H, J ) 1.5, 4.0 Hz);
signals due to 40 inter alia 1.19 (d, 1H, J ) 6.2 Hz), 2.46 (s,
1H), 2.74 (ddd, 1H, J ) 0.3, 1.5, 15.1 Hz), 3.05 (ddd, 1H, J )
2.9, 4.0, 15.1 Hz), 4.07 (dt, 1H, J ) 5.0, 5.0, 9.9 Hz), 4.17 (ddd,
1H, J ) 4.6, 9.0, 9.9 Hz), 5.03 (dd, J ) 1.5, 4.0 Hz); MS (HR,
EI) m/ z (M+) calcd 313.098395, obsd 313.098016.
(2S,4′S)- a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-4-O-
ben zyl-1-O-(tr ip h en ylsilyl)bu ta n e-1,2,4-tr iol (29 a n d 30).
A mixture of 29 and 30 in a ratio of 4.7:1, respectively, was
obtained from 15 according to the procedure described above
(2S,4′S)- a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-1-O-
tosylp r op a n e-1,2-d iol (47 a n d 48). A mixture of compounds
47 and 48 (6.7:1) was obtained from the mixture of 41 and 42
according to the procedure described for 33 and 34 (73%): IR
1
(56%): IR (film) 1770, 3267 cm-1; H NMR (CDCl3) δ signals
1
due to 29 inter alia 2.74 (ddd, 1H, J ) 0.8, 1.5, 15.0 Hz), 2.90
(ddd, 1H, J ) 2.6, 4.0, 15.0 Hz), 5.14 (dd, 1H, J ) 1.5, 4.0 Hz);
signals 30 inter alia 2.95 (ddd, 1H, J ) 2.5, 4.0, 15.0 Hz), 5.03
(dd, 1H, J ) 1.5, 4.0 Hz); MS (HR, LSIMS) m/ z (M + H)+
calcd 524.226192, obsd 524.2257.
(film) 1772, 3266, 3349 cm-1; H NMR (CDCl3) δ signals due
to 47 inter alia 1.18 (d, 3H, J ) 6.3 Hz), 2.46 (s, 3H), 2.77
(ddd, 1H, J ) 0.4, 1.5, 15.1 Hz), 3.07 (ddd, 1H, J ) 2.9, 3.9,
15.1 Hz), 3.88 (m, 1H), 3.94 (dd, 1H, J ) 7.1, 10.5 Hz), 4.00
(dd, 1H, J ) 3.5, 10.5 Hz), 5.16 (dd, 1H, J ) 1.5, 3.9 Hz);
signals due to 48 inter alia 1.17 (d, 3H, J ) 6.4 Hz), 2.79 (ddd,
1H, J ) 0.5, 1.5, 15.1 Hz), 3.10 (ddd, 1H, J ) 2.8, 4.0, 15.1
Hz), 5.11 (dd, 1H, J ) 1.5, 4.0 Hz); MS (HR, LSIMS) m/ z (M
+ H)+ calcd 300.090565, obsd 300.091288.
(2S,4′S) a n d (2S,4′R)-2-O-(2′-Oxoa zet id in -4′-yl)-4-O-
ben zyl-1-O-tosylbu ta n e-1,2,4-tr iol (33 a n d 34). A solution
of a 5:1 mixture of 29 and 30 (0.10 g, 0.20 mmol) in pyridine
(1 mL) was treated with HF-pyridine complex (0.026 g, 0.26
mmol). After 2 h tosyl chloride (0.10 g, 0.5 mmol) was added,
and the mixture was left overnight in a refrigerator, poured
into water, and extracted with tert-butyl methyl ether. The
extract was dried and evaporated. The crude product was
(2S,6R)- a n d (2S,6S)-2-[(Ben zyloxy)m eth yl]-1-oxa cep h -
a m s (49 a n d 50). A mixture of 49 and 50 in a ratio 1:1 was
obtained from a mixture of 25 and 26 according to the
procedure described earlier (82%).4,5 Compounds 49 and 50