The Journal of Organic Chemistry
Note
Methyl 3-O-Allyloxycarbonyl-4,6-O-benzylidene-2-O-(N-phenyl-
carbamoyl)-α-D-glucopyranoside (7). Yield 630 mg (80%) as
colorless needles from methyl 4,6-O-benzylidene-2-O-(N-phenyl-
carbamoyl)-α-D-glucopyranoside (650 mg): [α]2D3 +61.6 (c 0.98,
CHCl3); mp 169−172 °C (hexane−EtOH); IR (KBr disk) ν 3340
82% yield): [α]2D5 +8.9 (c 1.51, CHCl3); mp 131−132 °C (hexane−
EtOH, colorless needles); IR (KBr disk) ν 3369 cm−1 (NH), 1703
1
cm−1 (CO); H NMR (600 MHz, CDCl3) δ 7.55−7.06 (25H, m),
6.55 (1H, br s), 4.94, 4.87 (2H, each d, J = 10.8 Hz), 4.93, 4.75 (2H,
each d, J = 10.2 Hz), 4.85, 4.62 (2H, each d, J = 10.2 Hz), 4.67 (1H, d,
J = 10.2 Hz), 4.44 (1H, d, J = 12.0 Hz), 4.34 (1H, m), 3.74 (1H, dd, J
= 9.0 Hz, J = 9.0 Hz), 3.57−3.53 (2H, m), 3.50 (1H, dd, J = 10.2 Hz, J
= 9.0 Hz); 13C NMR (150 MHz, CDCl3) δ 138.2, 137.8, 137.5, 133.3,
132.4, 129.1, 128.8, 128.5, 128.5, 128.5, 128.4, 128.3, 128.2, 127.8,
123.5, 118.5, 87.6, 86.7, 81.0, 77.2, 77.1, 75.8, 75.5, 75.0; HRMS (ESI-
TOF) calcd for C40H39NO6S m/z [M + Na]+ 684.2396, found
684.2376. Anal. Calcd for C40H39NO6S (661.81): C, 72.59; H, 5.94; N,
2.12. Found: C, 72.21; H, 5.60; N, 1.99.
1
cm−1 (NH), 1716 cm−1 (CO); H NMR (600 MHz, CDCl3) δ
7.47−7.07 (10H, m), 6.83 (1H, s), 5.84 (1H, m), 5.53 (1H, s), 5.41
(1H, dd, J = 9.8 Hz, J = 9.8 Hz), 5.27, 5.13 (2H, each m), 5.07 (1H, d,
J = 3.8 Hz), 4.93 (1H, dd, J = 3.8 Hz, J = 9.8 Hz), 4.60 (2H, m), 4.33
(1H, dd, J = 4.8 Hz, J = 10.3 Hz), 3.95 (1H, ddd, J = 4.8 Hz, J = 9.6
Hz, J = 10.3 Hz), 3.80 (1H, dd, J = 10.3 Hz, J = 10.3 Hz), 3.74 (1H,
dd, J = 9.6 Hz, J = 9.8 Hz), 3.43 (3H, s); 13C NMR (125 MHz,
CDCl3) δ 154.4, 137.3, 136.8, 131.2, 129.1, 129.1, 129.1, 128.2, 128.2,
128.2, 126.2, 126.2, 123.8, 118.9, 118.6, 101.6, 97.9, 79.0, 73.3, 72.1,
68.8, 68.7, 62.3, 55.5, 55.5. Anal. Calcd for C25H27NO9 (485.48): C,
61.85; H, 5.60; N, 2.89. Found: C, 61.82; H, 5.64; N, 2.62.
Phenyl 3-O-Benzoyl-4,6-O-benzylidene-2-O-(N-phenylcarbamo-
yl)-1-thio-β-D-glucopyranoside (1210c). To a solution of 12a21 (50
mg, 0.11 mmol) in pyridine (2 mL) were added phenyl isocyanate (13
μL, 0.12 mmol) and 4-dimethylaminopyridine (5 mg, 41 μmol) at 0
°C and the mixture stirred at room temperature for 30 min. After
disappearance of the starting compound on TLC with toluene−
acetone (16:1 v/v), the mixture was evaporated in vacuo. The resulting
crude crystal was purified by recrystallization with hexane−EtOAc to
give 12 (57.5 mg, 92% yield): [α]2D5 +14.2 (c 1.0, CHCl3); mp 192−
193 °C (hexane−EtOH, colorless prisms); IR (KBr, disk) ν 3295 cm−1
Methyl 4,6-O-Benzylidene-3-O-methanesulfonyl-2-O-(N-phenyl-
carbamoyl)-α-D-glucopyranoside (8). Yield 940 mg (78%) as
colorless needles from methyl 4,6-O-benzylidene-2-O-(N-phenyl-
carbamoyl)-α-D-glucopyranoside (1.00 g): [α]D23 +75.5° (c 1.02,
CHCl3); mp 192−194 °C (hexane−EtOH); IR (KBr disk) ν 3356
cm−1 (NH), 1711 cm−1 (CO), 1539 cm−1 (CC), 1361, 1168
1
cm−1 (SO2); H NMR (600 MHz, CDCl3) δ 7.46−7.26 (10H, m),
1
(NH), ν 1722 cm−1 (CO); H NMR (600 MHz, CDCl3) δ 8.05−
7.01 (1H, s), 5.58 (1H, s), 5.12 (1H, d, J = 3.8 Hz), 5.11 (1H, dd, J =
9.6 Hz, J = 9.6 Hz), 4.91 (1H, dd, J = 9.6 Hz, J = 3.8 Hz), 4.35 (1H,
dd, J = 4.8 Hz, J = 10.3 Hz), 3.94 (1H, ddd, J = 9.6 Hz, J = 10.5 Hz, J =
4.8 Hz), 3.82 (1H, dd, J = 10.3 Hz, J = 10.5 Hz), 3.78 (1H, dd, J = 9.6
Hz, J = 9.6 Hz), 3.45 (3H, s), 2.96 (3H, s); 13C NMR (125 MHz,
CDCl3) δ 136.5, 129.4, 129.1, 128.4, 126.0, 126.0, 101.9, 98.3, 79.0,
77.6, 77.2, 68.8, 62.4, 55.6, 38.8. Anal. Calcd for C22H25NO9S
(479.50): C, 55.11; H, 5.26; N, 2.92. Found: C, 55.42; H, 5.30; N,
2.61.
7.23 (15H, m), 6.70 (1H, br s), 5.67 (1H, dd, J = 9.6 Hz, J = 9.6 Hz),
5.51 (1H, s), 5.19 (1H, dd, J = 10.2 Hz, J = 9.6 Hz), 4.91 (1H, d, J =
10.2 Hz), 4.42 (1H, dd, J = 4.9 Hz, J = 10.6 Hz), 3.86 (1H, dd, J = 9.6
Hz, J = 9.6 Hz), 3.85 (1H, dd, J = 10.6 Hz, J = 9.6 Hz), 3.68 (1H, ddd,
J = 9.6 Hz, J = 4.9 Hz, J = 9.6 Hz); 13C NMR (150 MHz, CDCl3) δ
165.9, 136.7, 133.3, 132.9, 132.0, 129.9, 129.1, 129.1, 129.0, 128.4,
128.3, 128.2, 126.1, 120.6, 101.5, 86.9, 78.4, 73.4, 70.9, 68.5. Anal.
Calcd for C33H29NO7S (583.65): C, 67.91; H, 5.01; N, 2.40. Found:
C, 68.18; H, 5.11; N, 2.05.
Methyl 4,6-O-Benzylidene-2-O-(N-phenylcarbamoyl)-3-O-tolyl-
sulfonyl-α-D-glucopyranoside (9). Yield 610 mg (68%) as colorless
needles from methyl 4,6-O-benzylidene-2-O-(N-phenylcarbamoyl)-α-
D-glucopyranoside (650 mg): [α]2D5 +57.3 (c 1.05, CHCl3); mp 179−
182 °C (hexane−EtOH); IR (KBr disk) ν 3365 cm−1 (NH), 1712
cm−1 (CO), 1365, 1173 cm−1 (SO2); 1H NMR (600 MHz, CDCl3)
δ 7.70−6.96 (14H, m), 6.73 (1H, s), 5.42 (1H, s), 5.20 (1H, dd, J =
9.6 Hz, J = 9.6 Hz), 5.06 (1H, d, J = 3.8 Hz), 4.89 (1H, dd, J = 3.8 Hz,
J = 9.6 Hz), 4.31 (1H, dd, J = 4.8 Hz, J = 10.3 Hz), 3.90 (1H, ddd, J =
4.8 Hz, J = 9.6 Hz, J = 10.4 Hz), 3.76 (1H, dd, J = 10.4 Hz, J = 10.3
Hz), 3.68 (1H, dd, J = 9.6 Hz, J = 9.6 Hz), 3.43 (3H, s), 2.20 (3H, s);
13C NMR (150 MHz, CDCl3) δ 152.0, 144.3, 137.3, 136.7, 134.4,
3,4-Di-O-benzyl-6-O-(N-phenylcarbamoyl)-D-glucal (13). To a
solution of 13a22 (622 mg, 1.91 mmol) in dry pyridine (10 mL)
was added phenyl isocyanate (227 μL, 2.1 mmol) at 0 °C and the
mixture stirred at rt for 8 h. After the reaction was complete, the
mixture was evaporated in vacuo. The remaining residue was purified
by recrystallization with hexane−acetone to give 13 (680 mg, yield
80%): [α]2D5 +41 (c 0.3, CHCl3); mp 133−134 °C (hexane−acetone,
colorless needles); IR (KBr disk) ν 3337 cm−1 (NH), 1701 cm−1 (C
1
O), 1646, 1598, 1531 cm−1 (CC); H NMR (600 MHz, CDCl3) δ
7.37−7.06 (15H, m), 6.57 (1H, br s), 6.41 (1H, d, J = 6.0 Hz), 4.93
(1H, dd, J = 3.0 Hz, J = 6.0 Hz), 4.85, 4.71 (2H, each d, J = 11.4 Hz),
4.67, 4.57 (2H, each d, J = 12.0 Hz), 4.50 (1H, dd, J = 2.4 Hz, J = 12.0
Hz), 4.45 (1H, dd, J = 4.8 Hz, J = 11.4 Hz), 4.24 (1H, ddd, J = 6.0 Hz,
J = 3.0 Hz, J = 2.4 Hz), 3.98 (1H, ddd, J = 8.4 Hz, J = 2.4 Hz, J = 2.4
Hz), 3.79 (1H, dd, J = 8.4 Hz, J = 6.0 Hz); 13C NMR (150 MHz,
CDCl3) δ 144.3, 138.1, 137.7, 129.1, 128.5, 128.5, 128.3, 127.9, 127.8,
123.5, 100.1, 75.4, 75.2, 73.5, 70.5, 63.3; HRMS (ESI-TOF) calcd for
C27H27NO5Na m/z [M + Na]+ 468.1787, found 468.1795. Anal. Calcd
for C27H27NO5 (445.19): C, 72.79; H, 6.11; N, 3.14. Found: C, 72.41;
H, 5.88; N, 3.18.
129.3, 129.1, 128.1, 127.9, 126.3, 123.8, 118.8, 101.7, 98.3, 78.8, 77.3,
71.8, 68.7, 62.5, 55.5, 21.5. Anal. Calcd for C28H29NO9S (555.60): C,
60.53; H, 5.26; N, 2.52. Found: C, 60.69; H, 5.58; N, 2.19.
Methyl 4-O-Acetyl-3-O-methoxymethyl-2-O-(N-phenylcarbamo-
yl)-6-O-triphenylmethyl-α-D-glucopyranoside (10). Yield 411 mg (3
steps, 74%) as colorless amorphous from 6 by hydrolysis, tritylation
and acetylation (510 mg): [α]2D5 +63.8 (c 0.99, CHCl3); IR (KBr neat)
1
ν 3323 cm−1 (CONH), 1740 cm−1 (CO); H NMR (600 MHz,
CDCl3) δ 7.47−7.27 (20H, m), 6.87 (1H, s), 5.04 (1H, d, J = 3.4 Hz),
5.00 (1H, dd, J = 10.3 Hz, J = 10.3 Hz), 4.92 (1H, dd, J = 3.4 Hz, J =
10.3 Hz), 4.68, 4.61 (2H, each d, J = 6.9 Hz), 4.01 (1H, dd, J = 10.3
Hz, J = 10.3 Hz), 3.88 (1H, ddd, J = 6.2 Hz, J = 1.4 Hz, J = 10.3 Hz),
3.50 (3H, s), 3.25 (3H, s), 3.18 (1H, dd, J = 10.3 Hz, J = 6.2 Hz), 3.10
(1H, dd, J = 1.4 Hz, J = 10.3 Hz), 1.78 (3H, s); 13C NMR (150 MHz,
CDCl3) δ 169.2, 143.7, 143.7, 143.7, 137.9, 137.4, 129.1, 129.1, 129.0,
129.0, 129.0, 128.7, 128.7, 128.7, 128.2, 128.2, 127.8, 127.8, 127.7,
127.7, 127.7, 126.9, 125.2, 123.7, 97.7, 97.0, 86.6, 76.5, 73.2, 70.3, 69.0,
62.7, 55.8, 55.0, 21.4, 20.6, 20.6. Anal. Calcd for C37H39NO9 (664.7):
C, 69.25; H, 6.13; N, 2.18. Found: C, 68.89; H, 6.15; N, 1.82.
Phenyl 2,3,4-Tri-O-benzyl-6-O-(N-phenylcarbamoyl)-1-thio-β-D-
glucopyranoside (11). To a solution of 11a20 (501 mg, 0.924
mmol) in pyridine (20 mL) was added phenyl isocyanate (121 μL, 1.1
mmol) at 0 °C and the mixture stirred for 1 h. After the disappearance
of the starting compound on TLC with hexane−EtOAc (2:1 v/v), the
mixture was evaporated in vacuo. The resulting crude crystal was
purified by recrystallization with hexane-EtOH to give 11 (501 mg,
Methyl 3-O-Acetyl-4,6-O-benzylidene-2-O-(N-phenylcarbamoyl)-
α-D-mannopyranoside (14). Yield 106 mg (88%) as colorless
amorphous from 14a: [α]2D5 −29.9 (c 0.95, CHCl3); IR (KBr disk) ν
1
3332 cm−1 (NH), 1743 cm−1 (CO); H NMR (600 MHz, CDCl3)
δ 7.47−7.09 (10H, m), 6.86 (1H, br s), 5.59 (1H, s), 5.43 (1H, dd, J =
3.5 Hz, J = 10.3 Hz), 5.36 (1H, dd, J = 1.4 Hz, J = 3.5 Hz), 4.80 (1H,
d, J = 1.4 Hz), 4.33 (1H, dd, J = 4.8 Hz, J = 10.3 Hz), 4.10 (1H, dd, J =
10.3 Hz, J = 10.3 Hz), 4.00 (1H, ddd, J = 10.3 Hz, J = 10.3 Hz, J = 4.8
Hz), 3.87 (1H, dd, J = 10.3 Hz, J = 10.3 Hz), 3.44 (3H, s), 2.03 (3H,
s); 13C NMR (150 MHz, CDCl3) δ 169.9, 137.4, 137.0, 129.2, 128.3,
126.2, 102.1, 99.9, 76.2, 68.8, 68.5, 63.7, 55.3, 20.9; HRMS (ESI-TOF)
calcd for C23H25NO8Na m/z [M + Na]+ 466.1480, found 466.1495.
Methyl 3-O-Benzoyl-4,6-O-benzylidene-2-O-(N-phenylcarbamo-
yl)-α-D-mannopyranoside (15). Yield 211 mg (86%) as colorless
amorphous from 15a: [α]2D8 −68.6 (c 0.23, CHCl3); IR (KBr disk) ν
1
3386 cm−1 (NH), 1729, 1710 cm−1 (CO); H NMR (600 MHz,
CDCl3) δ 7.99−7.07 (10H, m), 6.84 (1H, br s), 5.73 (1H, dd, J = 3.6
8806
dx.doi.org/10.1021/jo4007128 | J. Org. Chem. 2013, 78, 8802−8808