The Journal of Organic Chemistry
Note
1.50−1.48(m, 2H), 1.36−1.26 (m, 3H), 1.08−1.00 (m, 12H), 0.83
(t, J = 7.3 Hz, 3H), 0.79−0.69 (m, 4H); 13C NMR (125 MHz, CDCl3) δ
164.6, 137.8, 136.1, 135.1, 133.4, 133.1, 132.2, 130.9, 130.5, 128.9, 128.3,
128.0, 127.8, 127.4, 126.7, 126.2, 126.1, 126.0, 125.9, 125.0, 101.7, 97.1,
96.1 (1JC−H = 176.8 Hz, α-Man), 80.0, 78.9, 77.4, 77.2, 76.9, 75.5, 73.2,
70.6, 68.9, 67.1, 30.9, 22.1, 19.8, 17.5, 13.8, 13.2, 7.2, 4.0, 3.8; MS-ESI
m/z: 721.2 [M + H]+, 743.1 [M + Na]+; HRMS (ESI) m/z: [M + H]+
Calcd for C44H53O7Si: 721.3555, Found: 721.3549, [M + NH4]+ Calcd
for C44H56O7NSi: 738.3821, Found: 738.3820. For 6β: [α]D26 = −27.6
and 7cβ (51 mg, 50%) as a syrup, respectively, were obtained by
purification with silica gel column chromatography (petroleum
ether/ethyl acetate 7:1) according to the general procedure. For 7cα:
[α]D18 = +9.38 (c 0.85, CHCl3); 1H NMR (500 MHz, CDCl3) δ 8.02 (d,
J = 8.0 Hz, 2H), 7.93 (d, J = 8.0 Hz, 2H), 7.88−7.74 (m, 3H), 7.70 (d, J =
7.3 Hz, 1H), 7.63−7.22 (m, 19H), 6.01 (t, J = 9.6 Hz, 1H), 5.60 (s, 1H),
5.20−5.13 (m, 2H), 4.90 (s, 1H), 4.79 (d, J = 12.3 Hz, 1H), 4.72−4.63
(m, 2H), 4.57 (d, J = 11.7 Hz, 1H), 4.22 (t, J = 9.4 Hz, 1H), 4.17−4.11
(m, 2H), 3.99−3.82 (m, 5H), 3.82−3.73(m, 2H), 3.40 (s, 3H), 0.89−
0.63 (m, 13H), 0.40−0.19 (m, 4H); 13C NMR (125 MHz, CDCl3) δ
166.0, 165.7, 138.0, 137.9, 136.3, 133.5, 133.4, 132.97, 130.00, 129.97,
129.4, 129.2, 128.9, 128.6, 128.5, 128.3, 128.1, 128.0, 127.8, 127.7,
126.38, 126.36, 126.1, 125.9, 125.7, 103.6 (1JC−H = 169.2 Hz, α-Man),
101.8, 97.0 (1JC−H = 171.0 Hz, α-Glu), 78.8, 76.1, 75.8, 73.7, 72.73,
72.65, 72.26, 71.31, 70.0, 69.0, 68.5, 65.7, 55.5, 29.9, 17.32, 17.30, 13.0,
7.09, 7.07, 3.6, 3.4; MS-ESI m/z: 1011.51 [M + H]+, 1033.5 [M + Na]+,
1049.5 [M + K]+; HRMS (ESI) m/z: [M + NH4]+ Calcd for
C59H70O13NSi: 1028.4611, Found: 1028.4628, [M + Na]+ Calcd for
C59H66O13NaSi: 1033.4165, Found: 1033.4174. For 7β: [α]D18 = +45.51
(c 1.125, CHCl3); 1H NMR (500 MHz, CDCl3) δ 8.00 (d, J = 7.4 Hz,
4H), 7.88−7.75 (m, 3H), 7.69 (d, J = 6.6 Hz, 1H), 7.61−7.07 (m, 19H),
5.91 (t, J = 9.3, 1H), 5.42 (s, 1H), 5.22−5.12 (m, 2H), 4.90−4.82 (m,
2H), 4.65 (d, J = 12.0 Hz, 1H), 4.38 (d, J = 12.0 Hz, 1H), 4.30 (s, 1H),
4.15 (t, J = 9.5 Hz, 1H), 3.95−3.88 (m, 3H), 3.73−3.68 (m, 3H), 3.43 (s,
3H), 3.31 (d, J = 9.5 Hz, 1H), 3.14 (t, J = 10.0 Hz, 1H), 3.08−3.04 (m,
1H), 1.09−0.84 (m, 13H), 0.72−0.57 (m, 4H); 13C NMR (125 MHz,
CDCl3) δ 166.1, 165.3, 137.8, 137.6, 136.3, 133.38, 133.35, 133.0,
132.9, 130.6, 130.1, 129.9, 129.3, 129.0, 128.7, 128.5, 128.3, 128.2, 128.1,
128.0, 127.8, 126.3, 126.2, 126.1, 125.9, 125.7, 101.5 (1JC−H = 156.3 Hz,
β-Man), 101.4, 97.2 (1JC−H = 171.3 Hz, α-Glu), 78.7, 78.2, 76.5, 73.9,
72.5, 72.4, 71.7, 70.3, 69.9, 68.4, 68.3, 67.4, 55.7, 17.6, 17.5, 13.3, 7.4, 7.3,
4.2, 4.1; MS-ESI m/z: 1011.52 [M + H]+, 1033.5 [M + Na]+, 1049.5
[M + K]+; HRMS (ESI) m/z: [M + H]+ Calcd for C59H67O13Si:
1011.4345, Found: 1011.4348, [M + NH4]+ Calcd for C59H70O13NSi:
1028.4611, Found: 1028.4619.
4,6-Di-O-benzylidene-2-O-(diethylisopropylsilyl)-3-O-(2-methyl-
naphthyl)-β-D-mannopyranosyl-(1 → 6)-1,2:3,4-di-O-isopropyli-
dene-α-D-galactopyranoside (7d). Compound 7d was obtained in
87% yield (68 mg, β/α = 20/1) as a syrup by purification with silica gel
column chromatography (petroleum ether/ethyl acetate 7:1) according
to the general procedure. [α]D18 = −69.39 (c 1.12, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.85−7.77 (m, 3H), 7.74−7.69 (m, 1H), 7.54−
7.49 (m, 2H), 7.80−7.44 (m, 3H), 7.40−7.35 (m, 3H), 5.63 (s, 1H),
5.54 (d, J = 5.1 Hz, 1H), 4.90 (d, J = 12.3 Hz, 2H), 4.59 (dd, J = 7.9, 2.1
Hz, 1H), 4.42 (s, 1H), 4.32−4.26 (m, 3H), 4.20 (d, J = 7.9 Hz, 1H), 4.15
(t, J = 9.5 Hz, 1H), 4.05 (dd, J = 11.3, 2.6 Hz, 1H), 3.98 (d, J = 7.9 Hz,
1H), 3.87 (t, J = 10.2 Hz, 1H), 3.67−3.63 (m, 1H), 3.56 (dd, J = 9.7, 2.5
Hz, 1H), 3.33−3.28 (m, 1H), 1.52 (s, 3H), 1.44 (s, 3H), 1.33 (s, 3H),
1.32 (s, 3H), 1.05−1.00 (m, 13H), 0.77−0.69 (m, 4H); 13C NMR (125
MHz, CDCl3) δ 137.8, 136.1, 133.4, 133.0, 129.0, 128.3, 128.0, 127.8,
126.5, 126.3, 126.1, 125.9, 125.8, 109.4, 108.5, 102.5 (1JC−H = 155.7 Hz,
β-Man), 101.7, 96.4 (1JC−H = 176.3 Hz, α-Gal), 78.9, 77.8, 72.2, 71.5,
71.3, 70.8, 70.4, 69.8, 69.0, 67.7, 67.6, 26.1, 25.0, 24.4, 17.71, 17.66, 13.4,
7.43, 7.40, 4.2, 4.0; MS-ESI m/z: 779.5 [M + H]+, 801.4 [M + Na]+,
817.4 [M + K]+; HRMS (ESI) m/z: [M + H]+ Calcd for C43H59O11Si:
779.3821, Found: 779.3830, [M + NH4]+ Calcd for C43H62O11NSi:
796.4087, Found: 796.4095.
1
(c 0.97, CHCl3); H NMR (500 MHz, CDCl3) δ 7.96 (d, J = 7.8 Hz,
1H), 7.89−7.66 (m, 4H), 7.60−7.32 (m, 10H), 7.28 (t, J = 7.6 Hz, 1H),
5.88 (s, 1H), 5.66 (s, 1H), 5.00 (d, J = 12.3 Hz, 1H), 4.93 (d, J = 12.3 Hz,
1H), 4.4−4.33 (m, 2H), 4.24 (t, J = 9.5 Hz, 1H), 3.91 (t, J = 10.2 Hz,
1H), 3.75 (dd, J = 9.6, 2.5 Hz, 1H), 3.56−3.52 (m, 1H), 2.46 (t, J = 7.1
Hz, 2H), 1.65−1.58 (m, 2H), 1.52−1.49 (m, 2H), 1.00−0.90 (m, 16H),
0.72−0.58 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 164.2, 137.7, 135.8,
134.4, 133.4, 133.1, 132.2, 130.8, 130.5, 129.1, 128.4, 128.10, 128.05,
127.8, 127.0, 126.8, 126.3, 126.14, 126.09, 126.81, 125.5, 101.8, 97.0,
94.4 (1JC−H = 160.7 Hz, β-Man), 78.91, 78.86, 77.8, 77.4, 77.2, 76.9, 73.2,
71.3, 68.8, 68.4, 30.8, 22.2, 19.7, 17.60, 17.57, 13.8, 13.4, 7.3, 4.21, 4.15;
MS-ESI m/z: 721.2 [M + H]+, 743.1 [M + Na]+; HRMS (ESI) m/z:
[M + NH4]+ Calcd for C44H56O7NSi: 738.3821, Found: 738.3830,
[M + Na]+ Calcd for C44H52O7NaSi: 743.3375, Found: 743.3374.
Diosgenyl 4,6-Di-O-benzylidene-2-O-(diethylisopropylsilyl)-3-O-
(2-methylnaphthyl)-β-D-mannopyranoside (7a). Compound 7a
was obtained in 93% yield (86 mg, β only) as a foam by purification
with silica gel column chromatography (petroleum ether/ethyl acetate/
21
CH2Cl2 20:1:1) according to the general procedure. [α]D = −66.4
(c 1.03, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.86−7.78 (m, 3H),
7.74−7.68 (m, 1H), 7.63−7.30 (m, 8H), 5.62 (s, 1H), 5.32 (d, J =
4.0 Hz, 1H), 4.96−4.88 (m, 2H), 4.46 (s, 1H), 4.43−4.37 (m, 1H), 4.27
(dd, J = 10.4, 4.7 Hz, 1H), 4.16−4.09 (m, 2H), 3.88 (t, J = 10.2 Hz, 1H),
3.58−3.45 (m, 3H), 3.37 (t, J = 10.9 Hz, 1H), 3.32−3.26 (m, 1H), 2.33−
2.28 (m, 1H), 2.23−2.16 (m, 1H), 1.05 (s, 3H), 1.02 (s, 3H), 1.01 (s,
3H), 0.97 (d, J = 6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 140.8,
137.9, 136.2, 133.4, 133.0, 128.9, 128.3, 128.0, 127.8, 126.5, 126.3, 126.1,
126.0, 125.9, 121.7, 109.4, 101.7, 99.6 (1JC−H = 153.0 Hz, β-Man), 81.0,
79.0, 78.4, 78.0, 72.3, 69.1, 67.6, 67.0, 62.2, 56.7, 50.3, 41.8, 40.4, 39.9,
38.9, 37.4, 37.0, 32.2, 32.0, 31.6, 31.5, 30.5, 29.6, 29.0, 21.0, 19.5,
17.7, 17.3, 16.4, 14.7, 13.5, 7.4, 4.3, 4.0; MS-ESI m/z: 933.8 [M + H]+,
955.8 [M + Na]+; HRMS (ESI) m/z: [M + H]+ Calcd for C58H81O8Si:
933.5695, Found: 933.5683, [M + NH4]+ Calcd for C58H84O8NSi:
950.5961, Found: 950.5953.
Phenyl 4,6-Di-O-benzylidene-2-O-(diethylisopropylsilyl)-3-O-(2-
methylnaphthyl)-β-D-manno-pyranosyl-(1 → 4)-2,6-di-O-benzyl-3-
O-(2-methylnaphthyl)-1-thio-α-D-mannopyranoside (7b). Com-
pound 7b was obtained in 64% yield (71 mg, β/α = 8.6/1) as a syrup
by purification with silica gel column chromatography (petroleum
ether/ethyl acetate 13:1 to 8:1) according to the general procedure.
[α]D18 = +17.11 (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.85−
7.76 (m, 6H), 7.72−7.67 (m, 1H), 7.52−7.22 (m, 27H), 5.59 (d, J = 2.6
Hz, 1H), 5.50 (s, 1H), 5.05 (d, J = 12.0 Hz, 1H), 4.89 (d, J = 12.5 Hz,
1H), 4.82 (d, J = 12.5 Hz, 1H), 4.72−4.62 (m, 4H), 4.39−4.32 (m, 2H),
4.32−4.27 (m, 1H), 4.24 (s, 1H), 4.10 (dd, J = 10.1, 4.7 Hz, 1H), 4.04 (t,
J = 9.5 Hz, 1H), 3.98 (brs, 2H), 3.91 (d, J = 5.4 Hz, 1H), 3.74 (dd, J =
10.8, 4.4 Hz, 1H), 3.67 (d, J = 9.5 Hz, 1H), 3.56 (t, J = 10.3 Hz, 1H), 3.31
(dd, J = 9.6, 2.3 Hz, 1H), 3.10−3.04 (m, 1H), 1.03−0.95 (m, 13H),
0.74−0.64 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 138.2, 138.1, 137.9,
136.7, 136.3, 134.7, 133.42, 133.37, 133.03, 132.99, 131.4, 129.1, 129.0,
128.5, 128.4, 128.3, 128.02, 127.97, 127.91, 127.86, 127.8, 127.7, 127.4,
126.4, 126.3, 126.2, 126.13, 126.07, 125.96, 125.90, 125.87, 125.8, 101.8
(1JC−H = 155.9 Hz, β-Man), 101.6, 86.1 (1JC−H = 166.6 Hz, α-Man), 79.0,
78.2, 77.7, 77.6, 77.0, 73.5, 73.2, 72.8, 72.5, 72.4, 72.2, 69.4, 68.9, 67.4,
29.8, 17.7, 13.5, 7.5, 7.4, 4.4, 4.2; MS-ESI m/z: 1111.7 [M + H]+, 1133.7
[M + Na]+, 1149.7 [M + K]+; HRMS (ESI) m/z: [M + H]+ Calcd for
C68H75O10SSi: 1111.4845, Found: 1111.4844, [M + NH4]+ Calcd for
C68H78O10NSSi: 1128.5110, Found: 1128.5123.
Phenyl 4,6-Di-O-benzylidene-2-O-(diethylisopropylsilyl)-3-O-(2-
methylnaphthyl)-β-D-manno-pyranosyl-(1 → 6)-2,3,4-tri-O-benzyl-
1-thio-α-D-mannopyranoside (7e). Compound 7e was obtained in
77% yield (82 mg, β only) as a syrup by purification with silica gel
column chromatography (petroleum ether/ethyl acetate 15:1 to 12:1)
according to the general procedure. [α]D18 = +2.24 (c 1.03, CHCl3); 1H
NMR (500 MHz, CDCl3) δ 7.87−7.80 (m, 3H), 7.76−7.69 (m, 1H),
7.55−7.43 (m, 5H), 7.42−7.07 (m, 23H), 5.61 (s, 1H), 5.55 (s, 1H),
4.96−4.86 (m, 3H), 4.72 (d, J = 12.4 Hz, 1H), 4.65−4.52 (m, 4H),
4.32−4.25 (m, 2H), 4.25−4.19 (t, J = 8.4, 1H), 4.15−4.08 (m, 2H), 4.01
(d, J = 2.3 Hz, 1H), 3.98 (brs, 1H), 3.86−3.82 (m, 2H), 3.81−3.73
(m, 2H), 3.44 (dd, J = 9.6, 2.4 Hz, 1H), 3.25−3.21 (m, 1H), 1.04−0.86
(m, 13H), 0.67−0.60 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 138.3,
Methyl 4,6-Di-O-benzylidene-2-O-(diethylisopropylsilyl)-3-O-(2-
methylnaphthyl)-D-manno-pyranosyl-(1 → 4)-2,3-di-O-benzoyl-6-
O-benzyl-α-D-glucopyranoside (7c). Compounds 7cα (32 mg, 32%)
H
J. Org. Chem. XXXX, XXX, XXX−XXX