M. Chmielewski et al.
FULL PAPER
glucofuranose (19 and 20): Compounds 19/20 were obtained in a
ratio of ca. 5:1 from 18 by the known procedure.[5,6,13] Chromato-
Resin 24: Resin 24 was obtained according to the Mitsunobu pro-
cedure described above. IR (KBr disk): ν˜ ϭ 3487, 1669, 1599, 1373,
graphic separation on silica gel with a hexane/ethyl acetate mixture 1166, 1079, 692 cmϪ1. calcd. S 2.47; found S 2.08. Elemental ana-
(4:6, v/v) as eluent gave 19/20 (69%). Solid foam. 19: 1H NMR
(500 MHz, CDCl3, selected signals taken from the spectrum of the
mixture): δ ϭ 1.20 (d, J ϭ 7.5 Hz, 3 H, CH3-3Ј), 3.29Ϫ3.35 (m, 1
H, H-3Ј), 3.40 (s, 3 H, CH3OϪ), 3.77 (d, J ϭ 2.6 Hz, 1 H, H-3),
4.57 (d, J ϭ 3.7 Hz, 1 H, H-2), 5.27 (d, J ϭ 4.3 Hz, 1 H, H-4Ј),
lysis indicating 2.08% S corresponds to an 84% yield. Capacity of
24: 0.65 mmol/g.
Resin 25: Resin 25 was obtained according to the general procedure
described above. IR (KBr disk): ν˜ ϭ 3468, 1748, 1600, 1374, 1241,
1025, 827 cmϪ1. calcd. N 0.87; found N 0.99. Elemental analysis
indicating 0.99% N corresponds to a 99% yield. Capacity of 25:
0.65 mmol/g. Compounds 7, 21, and 22 were obtained from the
resin 25 according to the general procedure described above to pro-
vide a mixture in a ratio of about 5:1:9, respectively
1
5.81 (d, J ϭ 3.7 Hz, 1 H, H-1), 6.24 (br. s, 1 H, NH) ppm. 20: H
NMR (500 MHz, CDCl3, selected signals taken from the spectrum
of the mixture): δ ϭ 1.19 (d, J ϭ 7.5 Hz, 3 H, CH3-3Ј), 3.25Ϫ3.28
(m, 1 H, H-3Ј), 3.39 (s, 3 H, CH3OϪ), 3.75 (d, J ϭ 3.0 Hz, 1 H,
H-3), 4.56 (d, J ϭ 3.7 Hz, 1 H, H-2), 5.09 (d, J ϭ 4.4 Hz, 1 H, H-
4Ј), 5.82 (d, J ϭ 3.7 Hz, 1 H, H-1), 6.53 (br. s, 1 H, NH) ppm. IR
(film): ν˜ ϭ 3355, 1761, 1367, 1107 cmϪ1. HRMS (LSIMS): calcd.
for [M ϩ H]ϩ (C25H36O11NS) 558.20091, found 558.20224.
1,2-O-Isopropylidene-5-O-(p-pivaloyloxyphenylsulfonyl)-3-O-(prop-
1Ј-enyl)-α-D-xylofuranose (27): Compound 27 was obtained from
26 according to the procedure described above (93%). Oil. [α]2D2
ϭ
1
Ϫ7.1 (c ϭ 0.61, CH2Cl2). H NMR (200 MHz, CDCl3): δ ϭ 1.30,
1.48 (2 s, 6 H, 2 ϫ Me), 1.44 [s, 9 H, (CH3)3CC(O)Ϫ], 1.47 (dd, 3
H, J ϭ 1.7 Hz and J ϭ 6.9 Hz, CH3-3Ј), 4.15 (d, J ϭ 3.0 Hz, 1 H,
H-3), 4.24 (dd, J ϭ 6.2 Hz, 1 H and J ϭ 10.1 Hz, H-5a), 4.31 (dd,
J ϭ 5.3 Hz, 1 H and J ϭ 10.1 Hz, H-5b), 4.41Ϫ4.59 (m, 3 H, H-
2Ј, H-2, H-4), 5.88 (d, J ϭ 3.7 Hz, 1 H, H-1), 5.89 (dq, J ϭ 6.1 Hz,
1 H and J ϭ 1.7 Hz, H-1Ј), 7.23Ϫ7.30, 7.90Ϫ7.98 (2 m, 4 H,
(4S,3ЈR,5ЈS,6ЈR)- and (4S,3ЈR,5ЈR,6ЈS)-4-C-(4Ј-Dethia-6Ј-methyl-
4Ј-oxapenam-3Ј-yl)-1,2-O-isopropylidene-3-O-methoxy-β-L-threo-
furanose (21 and 22): Compounds 21/22 were obtained from the 19/
20 mixture by the procedure described for 8/9. After chromato-
graphic separation with a hexane/ethyl acetate mixture (8.5:1.5, v/
v) as eluent, the pure components were obtained. 21: Oil. [α]2D2
ϭ
Ϫ124.2 (c ϭ 0.49, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ ϭ 1.15
(d, J ϭ 7.6 Hz, 3 H, CH3-6Ј), 1.32, 1.49 (2 s, 6 H, 2 ϫ Me), 2.98
(ddd, 1 H, J ϭ 0.6 Hz, J ϭ 7.2 Hz and J ϭ 12.0 Hz, H-2Јa), 3.39
(ddd, 1 H, J ϭ 0.5 Hz, J ϭ 3.2 Hz and J ϭ 15.0 Hz, H-6Ј), 3.42
(s, 3 H, CH3OϪ), 3.77 (d, J ϭ 3.3 Hz, 1 H, H-3), 3.91 (dd, J ϭ
6.4 Hz, 1 H and J ϭ 12.0 Hz, H-2Јb), 4.30 (dd, J ϭ 3.3 Hz, 1 H
and J ϭ 5.7 Hz, H-4), 4.32Ϫ4.34 (m, 1 H, H-3Ј), 4.55 (d, J ϭ
3.7 Hz, 1 H, H-2), 5.30 (d, J ϭ 3.2 Hz, 1 H, H-5Ј), 5.87 (d, J ϭ
3.7 Hz, 1 H, H-1) ppm. 13C NMR (125 MHz, CDCl3): δ ϭ 7.71,
26.23, 26.86, 47.29, 48.97, 58.09, 78.90, 80.96, 81.71, 84.10, 87.10,
105.28, 111.92, 182.56 ppm. IR (film): ν˜ ϭ 1783 cmϪ1. HRMS (EI):
calcd. for [M]ϩ (C14H21NO6) 299.13689, found 299.13655.
C14H21NO6 (299.33): calcd. C 56.18, H 7.07, N 4.68; found C
phenyl) ppm. IR (CHCl3): ν˜ ϭ 1757, 1670, 1376, 1108, 979 cmϪ1
.
HRMS (LSIMS): calcd. for [M ϩ Na]ϩ (C22H30NaO9S) 493.15082,
found 493.15203. C22H30O9S (470.55): calcd. C 56.16, H 6.43;
found C 56.41, H 6.78
(3ЈS,4ЈR)- and (3ЈR,4ЈS)-1,2-O-Isopropylidene-3-O-(3Ј-methyl-2Ј-
oxoazetidin-4Ј-yl)-5-O-(p-pivaloyloxyphenylsulfonyl)-α-D-xylo-
furanose (28 and 29): A 28/29 mixture in a ratio of ca. 1.7:1 was
obtained from 27 according to the general procedure described
1
earlier above (52%). Oil. 28: H NMR (500 MHz, CDCl3, selected
signals taken from the spectrum of the mixture): δ ϭ 1.16 (d, J ϭ
6.7 Hz, 3 H, CH3-3Ј), 1.31, 1.47 (s, 3 H, 2 ϫ Me), 4.16 (dd, J ϭ
5.5 Hz, 1 H and J ϭ 9.8 Hz, H-5a), 4.28 (dd, J ϭ 7.3 Hz, 1 H and
J ϭ 9.8 Hz, H-5b), 4.57 (d, J ϭ 3.7 Hz, 1 H, H-2), 5.10 (d, J ϭ
4.4 Hz, 1 H, H-4Ј), 5.88 (d, J ϭ 3.7 Hz, 1 H, H-1), 6.43 (br. s, 1
H, NH) ppm. 29: 1H NMR (500 MHz, CDCl3, selected signals
taken from the spectrum of the mixture): δ ϭ 1.14 (d, J ϭ 6.7 Hz,
3 H, CH3Ϫ3Ј), 1.32, 1.48 (s, 3 H, 2 ϫ Me), 4.15 (dd, J ϭ 5.2 Hz,
1 H and J ϭ 9.7 Hz, H-5a), 4.29 (dd, J ϭ 7.7 Hz, 1 H and J ϭ
9.7 Hz, H-5b), 4.51 (d, J ϭ 3.6 Hz, 1 H, H-2), 5.13 (d, J ϭ 4.2 Hz,
1 H, H-4Ј), 5.87 (d, J ϭ 3.6 Hz, 1 H, H-1), 6.57 (br. s, 1 H, NH)
ppm. IR (film): ν˜ ϭ 3341, 1761 cmϪ1. HRMS (LSIMS): calcd. for
55.92, H 6.97, N 4.62. 22: White solid. M.p. 68Ϫ71 °C. [α]2D2
ϭ
ϩ42.9 (c ϭ 0.43, CH2Cl2). 1H NMR (500 MHz, CDCl3): δ ϭ 1.19
(d, J ϭ 7.6 Hz, 3 H, CH3-6Ј), 1.32, 1.48 (2 s, 6 H, 2 ϫ Me), 3.11
(ddd, 1 H, J ϭ 0.7 Hz, J ϭ 7.2 Hz and J ϭ 11.6 Hz, H-2Јa),
3.37Ϫ3.42 (m, 1 H, H-6Ј), 3.43 (s, 3 H, CH3OϪ), 3.75 (d, J ϭ
3.2 Hz, 1 H, H-3), 3.83 (dd, J ϭ 5.4 Hz, 1 H and J ϭ 11.6 Hz, H-
2Јb), 4.09 (dd, J ϭ 3.3 Hz, 1 H and J ϭ 7.1 Hz, H-4), 4.52Ϫ4.56
(m, 1 H, H-3Ј), 4.54 (d, J ϭ 3.7 Hz, 1 H, H-2), 5.17 (d, J ϭ 3.0 Hz,
1 H, H-5Ј), 5.87 (d, J ϭ 3.7 Hz, 1 H, H-1) ppm. 13C NMR
(125 MHz, CDCl3): δ ϭ 7.74, 26.34, 26.86, 47.90, 48.27, 58.02,
79.84, 81.19, 81.66, 83.97, 87.42, 105.15, 111.99, 181.69 ppm. IR
[M
ϩ
H]ϩ (C23H32NO10S) 514.17469, found 514.17593.
C23H31NO10S (513.58): calcd. C 53.79, H 6.08, N 2.73; found C
53.40, H 6.57, N 2.58.
(CH2Cl2): ν˜
ϭ .
1780 cmϪ1 HRMS (EI): calcd. for [M]ϩ
(C14H21NO6) 299.13689, found 299.13661. C14H21NO6 (299.33):
calcd. C 56.18, H 7.07, N 4.68; found C 56.24, H 7.21, N 4.52.
(3aR,4aR,7S,7aR,8aS,8bR)- and (3aR,4aR,7R,7aS,8aS,8bR)-2,2-
Dimethyl-hexahydro-1,3,4,8-tetraoxa-5a-aza-cyclobuta[f]indeno-
[b]cyclopentan-6-one[21] (31 and 32): A mixture of 31 and 32 was
obtained from the 28/29 mixture according to the procedure
described above. Chromatographic separation on silica gel with a
hexane/ethyl acetate mixture (3:7, v/v) as eluent gave compounds
31 and 32, with spectral and analytical data identical to those re-
ported in the literature.[6]
6-O-(p-Hydroxyphenylsulfonyl)-1,2-O-isopropylidene-3-O-methyl-5-
O-(prop-1Ј-enyl)-α-D-glucofuranose (23): Compound 23 was ob-
tained from 18 by the procedure described above (86%). Oil. [α]2D2
ϭ
1
Ϫ25.5 (c ϭ 0.4, CH2Cl2). H NMR (500 MHz, CDCl3): δ ϭ 1.31,
1.48 (2 s, 6 H, 2 ϫ Me), 1.52 (dd, 3 H, J ϭ 1.6 Hz and J ϭ 6.8 Hz,
CH3Ϫ3Ј), 1.64 (br. s, 1 H, ϪOH), 3.36 (s, 3 H, CH3OϪ), 3.72 (d,
J ϭ 2.4 Hz, 1 H, H-3), 4.03Ϫ4.15, 4.33Ϫ4.42 (2 m, 5 H, H-2Ј, H-
4, H-5, H-6a, H-6b), 4.54 (d, J ϭ 3.7 Hz, 1 H, H-2), 5.81 (d, J ϭ
5-O-(p-Hydroxyphenylsulfonyl)-1,2-O-isopropylidene-3-O-(prop-1Ј-
enyl)-α-D-xylofuranose (33): Compound 33 was obtained from 27
3.7 Hz, 1 H, H-1), 5.97 (dq, J ϭ 6.1 Hz, 1 H and J ϭ 1.6 Hz, H- by the procedure described above (72%). Oil. [α]2D2 ϭ Ϫ8.6 (c ϭ
1Ј), 6.89Ϫ6.93, 7.76Ϫ7.79 (2 m, 4 H, phenyl) ppm. IR (film): ν˜ ϭ 1.17, CH2Cl2). 1H NMR (200 MHz, CDCl3): δ ϭ 1.30, 1.48 (2 s, 6
3411, 1669, 1589, 1357, 1081 cmϪ1. HRMS (EI): calcd. for [M]ϩ
H, 2 ϫ Me), 1.47 (dd, 3 H, J ϭ 1.7 Hz and J ϭ 6.8 Hz, CH3-3Ј),
(C19H26O9S) 430.12975, found 430.12740. C19H26O9S (430.48): 4.16 (d, J ϭ 3.3 Hz, 1 H, H-3), 4.20 (dd, J ϭ 6.6 Hz, 1 H and J ϭ
calcd. C 53.01, H 6.09.found C 52.57, H 6.22.
10.2 Hz, H-5a), 4.31 (dd, J ϭ 5.5 Hz, 1 H and J ϭ 10.2 Hz, H-5b),
2382
Eur. J. Org. Chem. 2002, 2377Ϫ2384