2
098
T. Opatz et al. / Carbohydrate Research 337 (2002) 2089–2110
solution of 1,2,4,6-tetra-O-acetyl-3-O-allyl-b-
D
-gluco-
N-[2-(2-O-Acetyl-3-O-allyl-6-O-tert-butyldiphenylsil-
yl-i- -glucopyranosylsulfanyl)ethyl]succinimide (7).—
To a solution of 6 (1.0 g, 2.48 mmol) in dry CH Cl (20
pyranoside (6.0 g, 15.5 mmol) and 5 (3.32 g, 18.5 mmol)
in dry CH Cl (120 mL), a solution of BF ·OEt (17.5
D
2
2
3
2
2
2
mL, 139 mmol) in 20 mL dry CH Cl was added
mL) were added imidazole (583 mg, 10.7 mmol) and
tert-butylchlorodiphenylsilane (0.74 mL, 3.57 mmol).
After addition of catalytic amounts of DMAP, the
solution was stirred for 2 h at room temperature. The
reaction mixture was diluted with CH Cl (100 mL) and
2
2
dropwise at 0 °C under an Ar atmosphere. After com-
plete addition, the ice bath was removed, and stirring
was continued for 6 h while the solution was allowed to
warm up to room temperature. The mixture was
2
2
washed with satd aq NaHCO (2×), and the organic
washed with 1N HCl and brine. The organic layer was
3
layer was dried over MgSO . After removal of the
dried over MgSO , concentrated in vacuo, and the
4
4
solvent under reduced pressure, the crude product was
purified by column chromatography on silica gel (elu-
ent: 60:30:1 hexanes–EtOAc–HOAc) to yield 6.80 g
crude product was purified by column chromatography
on silica gel (3:1 hexanes–EtOAc) to yield 7 (1.43 g,
90%) as a colorless solid: R 0.47 (1:1 hexanes–EtOAc);
f
1
(
85%) 5 as a colorless amorphous solid: Rf 0.44
mp 39–40 °C. [h]D −2.0° (c 1, CHCl ). H NMR (400
3
1
(
EtOAc); mp 75–77 °C. [h]D −5.3° (c 1, CHCl ). H
MHz, CDCl ): l 7.67–7.65 (m, 4H, PhSi), 7.42–7.33
3
3
NMR (200 MHz, CDCl ): l 6.33 (t, br, 1H, J 5.1 Hz,
(m, 6H, PhSi), 5.89–5.82 (m, 1H, CH CH-), 5.24 (dd,
3
2
NH), 5.80–5.61 (m, 1H, CH CH-), 5.18–4.87 (m, 4H,
1H Jtrans 17.2 Hz, Jgem 1.6 Hz, CH CH-), 5.14 (dd, 1H,
2
2
CH CH-, H-2%, H-4%), 4.38 (d, 1H, J 9.8 Hz, H-1%),
Jcis 10.4 Hz, Jgem 1.6 Hz, CH CH-), 4.91 (Ct, 1H,
2
2
4
.11–4.00 (m, 4H, H-6%a+b, allyl-OCH ), 3.62 (s, 3H,
J:9.6 Hz, H-2%), 4.42 (d, 1H, J 10.0 Hz, H-1%), 4.25–
2
OMe), 3.59–3.41 (m, 3H, H-3%, H-4%, H-5%), 3.38–3.24
m, 2H, CH N), 2.89–2.51 (m, 4H, SCH2,
4.14 (m, 2H, allyl-OCH ), 3.90 (d, 2H, J 4.5 Hz,
2
(
H-6%a+b), 3.76 (Ct, 1H, J:9.2 Hz, H-4%), 3.70–3.63
2
CH CO Me), 2.43 (t, 2H, J 6.4 Hz, CH CONH), 2.05,
(m, 2H, H-3%, H-5%), 3.47–3.41 (m, 2H, NCH ), 2.89 (s,
2
2
2
2
13
2
.02, 2.01 (3s, 9H, OAc). C NMR (50.3 MHz,
1H, OH), 2.87–2.81 (m, 1H, SCH ), 2.75–2.62 (m, 1H,
2
CDCl ): l 173.3, 171.6 (COCH ), 170.7, 169.4, 169.3
SCH ), 2.61 (s, 4H, 2×CH CO), 2.07 (s, 3H, OAc),
3
2
2
2
13
(
COCH ), 134.1 (CH CH-), 117.0 (CH CH-), 83.9,
1.01 (s, 9H, tBu). C NMR (100.6 MHz, CDCl ): l
3
2
2
3
8
1.0, 76.2, 73.3, 71.1, 69.4 (C-1%–C-5%, allyl-OCH ), 62.3
176.6 (COCH ), 169.5 (COCH ), 135.6, 135.5 (PhSi),
2
2
3
(
C-6%), 51.8 (OMe), 39.3 (NCH ), 30.7, 30.4 (CH CO),
134.8 (CH CH-), 133.1, 133.0 (PhSi), 129.8, 127.7
2
2
2
2
9.2 (SCH ), 21.0, 20.8, 20.7 (Ac). Anal. Calcd for
(PhSi), 117.0 (CH CH-), 83.7, 83.1, 79.3, 73.4, 71.4
2
2
C H NO S: C, 50.82; H, 6.40; N, 2.70; S, 6.17.
(C-1%–C-5%, allyl-OCH ), 64.4 (C-6%), 38.2 (NCH ), 28.1
2
2
33
11
2
2
Found: C, 50.74; H, 6.44; N, 2.76; S, 6.23.
N-[2-(2 - O - Acetyl - 3 - O - allyl - i - - glucopyranosyl-
(CH CO), 27.1 (SCH ), 26.8 (tBu), 21.0 (Ac), 19.2 (C ,
tBu). Anal. Calcd for C H NO SSi: C, 61.75; H, 6.75;
33 43 9
2 2 q
D
sulfanyl)ethyl]succinimide (6).—To a solution of 5 (2.6
g, 5 mmol) in MeOH (50 mL), NaOMe (54 mg, 1
mmol) was added, and the resulting solution was stirred
under Ar at 0 °C until TLC monitoring showed com-
plete conversion of the starting material (ca. 6 h). The
reaction mixture was neutralized by addition of the
acidic cation-exchange resin, Amberlyst™ 15. After
filtration, the solution was concentrated in vacuo, and
the resulting crude product was subjected to column
chromatography on silica gel (toluene–EtOH) to yield
N, 2.18; S, 5.00. Found: C, 61.58; H, 7.12; N, 2.17; S,
4.81.
N-[2-(2%-O-Acetyl-6%-O-tert-butyldiphenylsilyl-3-O-
propyl - i -
D - glucopyranosylsulfanyl)ethyl]succinimide
(8).—In an ice cold solution of 7 (10.0 g, 15.5 mmol) in
dry CH CN (200 mL), potassium azodicarboxylate (3.7
3
g, 21.8 mmol) was suspended. HOAc (2.8 mL, 44.0
mmol) was added, and the mixture stirred at 0 °C for 2
h. The solution was poured into a mixture of 2:1
Et O–water (600 mL). The organic layer was washed
2
6
(1.8 g, 90%) as a colorless amorphous solid: R 0.44
twice with 1 N HCl and with satd aq NaHCO , and
f
3
(
4:1 toluene–EtOH); mp 90–91 °C. [h] −18.7° (c 1,
dried over MgSO . The solvent was removed in vacuo.
Since the H NMR spectrum still showed small
D
4
1
1
CHCl ). H NMR (200 MHz, CDCl ): l 5.92–5.73 (m,
3
3
1
1
4
3
H, CH CH-), 5.24–5.08 (m, 2H, CH CH-), 4.86 (Ct,
amounts of the nonhydrogenated compound, the hy-
drogenation procedure was repeated three times. Fi-
nally, the crude product was purified by column
chromatography on silica gel (3:1 hexanes–EtOAc) to
2
2
H, J:9.5 Hz, H-2%), 4.37 (d, 1H, J 9.8 Hz, H-1%),
.25–4.08 (m, 2H, allyl-OCH ), 3.91–3.55 (m, 4H, H-
2
%, H-4%, H-6%a+b), 3.49–3.34 (m, 4H, H-5%, NCH2,
OH), 2.99–2.71 (m, 2H, SCH ), 2.68 (s, 4H, 2×
yield 8 (10.0 g, 98%) as a colorless oil: R 0.47 (hex-
2
3
f
1
1
CH CO), 2.04 (s, 3H, OAc). C NMR (50.3 MHz,
anes–EtOAc 1:1). [h]D −30.8° (c 1, CHCl ). H NMR
2
3
CDCl ): l 177.2 (COCH ), 169.5 (COCH ), 134.7
(200 MHz, CDCl ): l 7.69–7.64 (m, 4H, PhSi), 7.39–
3
2
3
3
(
6
2
CH CH-), 116.9 (CH CH-), 83.5, 83.2, 80.4, 73.5, 71.2,
7.30 (m, 6H, PhSi), 4.89 (Ct, 1H, J:9.8 Hz, H-2%),
4.42 (d, 1H, J 10.0 Hz, H-1%), 3.91–3.89 (m, 2H,
H-6%a+b), 3.77–3.33 (m, 7H, H-3%, H-4%, H-5%, NCH2,
2
2
9.6 (C-1%–C-5%, allyl-OCH ), 62.0 (C-6%), 39.2 (NCH ),
2
2
8.1 (CH CO), 26.6 (SCH ), 20.9 (Ac). Anal. Calcd for
2
2
C H NO S: C, 50.61; H, 6.25; N, 3.47; S, 7.95.
propyl-OCH ), 3.00 (s, br, 1H, OH), 2.89–2.67 (m, 2H,
1
7
25
8
2
Found: C, 49.85; H, 6.59; N, 3.87; S, 7.95.
SCH , 2.60 (s, 4H, 2×CH CO), 2.06 (s, 3H, OAc),
2
2