Crich and Sharma
JOCArticle
5.59 (s, 1H), 5.12 (dd, J=11.0, 4.0 Hz, 1H), 4.82 (d, J=12.0 Hz,
1H), 4.76 (t, J=7.0 Hz, 1H), 4.55 (d, J=12.0 Hz, 1H),4.25-4.21
(m, 2H), 3.84 (t, J=10.0 Hz, 1H), 3.80 (dd, J=1.0, 3.5 Hz, 1H),
3.69-3.65 (m, 1H), 2.96 (s, 1H), 2.95 (s, 1H), 1.98 (s, 3H), 1.18
(s, 9H); 13C NMR (125.6 MHz, CDCl3) δ 212.6, 170.7, 138.0,
137.5, 129.3, 128.6, 128.5, 128.1, 126.4, 101.9, 76.4, 72.9, 72.4,
70.4, 69.3, 67.4, 44.8, 36.1, 26.3, 21.2; ESI-HRMS calcd for C28-
H34O7Na [M þ Na]þ 505.2202, found 505.2210.
4,6-O-Benzylidene-2-O-benzyl-3-O-tert-butoxycarbonyl-1-de-
oxy-1-allyl-r-D-mannopyranose (16r) and 4,6-O-Benzylidene-2-
O-benzyl-3-O-tert-butoxycarbonyl-1-deoxy-1-allyl-β-D-manno-
pyranose (16β). Prepared by the general procedure 1 with a com-
bined yield of 44 mg (44%, 7.8:1 R/β). Both anomers were sepa-
rated by flash column chromatography on silica gel (10% methyl
tert-butyl ether/hexane). 16r: [R]23 -0.174 (c = 0.5, CHCl3);
D
1H NMR (500 MHz, CDCl3) δ 7.51-7.49 (m, 2H), 7.40-7.29
(m, 8H), 5.74-5.66 (m, 1H), 5.59 (s, 1H), 5.16-5.10 (m, 2H),
5.04 (dd, J = 3.0, 10.0 Hz, 1H), 4.66 (q, J = 12.0 Hz, 2H),
4.28-4.22 (m, 2H), 4.08 (t, J=7.5 Hz, 1H), 3.97 (dd, J=1.5,
3.0 Hz, 1H), 3.83 (t, J = 10.0 Hz, 1H), 3.74-3.69 (m, 1H),
2.61-2.55 (m, 1H), 2.37-2.31 (m, 1H), 1.49 (s, 9H); 13C NMR
(125.6 MHz, CDCl3) δ 153.2, 138.0, 137.6, 133.3, 129.2, 18.6,
128.4, 128.3, 128.1, 126.4, 118.4, 101.9, 82.9, 77.1, 76.9, 76.3,
73.6, 73.4, 69.3, 65.9, 33.8, 28.0; ESI-HRMS calcd for C28H34-
O7Na [M þ Na]þ 505.2202, found 505.2206. 16β: [R]23D -35.50
3-O-Acetyl-2-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(2-oxo-
2-phenylethyl)-r-D-mannopyranose (12r). Prepared by general pro-
cedure 1 (eluent 15% ethyl acetate/hexane) with a yield of 40 mg
(79%): [R]22 -17.9 (c = 1.0, CHCl3); 1H NMR (500 MHz,
D
CDCl3) δ 7.98-7.96 (m, 2H), 7.64-7.61 (m, 1H), 7.53-7.44
(m, 6H), 7.38-7.31 (m, 6H), 5.60 (s, 1H), 5.23 (dd, J= 11.0, 4.0
Hz, 1H), 4.94-4.90 (m, 1H), 4.86 (d, J=12.0 Hz, 1H), 4.65 (d, J=
12.0 Hz, 1H), 4.28-4.23 (m, 2H), 3.97 (dd, J=1.5, 3.0 Hz, 1H), 3.85
(t, J=10.0 Hz, 1H), 3.79-3.76 (m, 1H), 3.52 (dd, J=5.0, 17.50 Hz,
1H), 3.37 (dd, J=8.5, 17.5 Hz, 1H), 1.99 (s, 3H); 13C NMR (125.6
MHz, CDCl3) δ196.7, 170.8, 138.0, 137.5, 136.7, 134.6, 134.0, 129.3,
129.2, 129.1, 128.7, 128.6, 128.5, 128.3, 128.1, 128.0, 126.4, 102.0,
76.9, 76.6, 73.0, 72.6, 70.4, 69.3, 67.3, 38.1, 21.2; ESI-HRMS calcd
for C30H30O7Na [M þ Na]þ 525.1889, found 525.1866.
1
(c = 0.40, CHCl3); H NMR (500 MHz, CDCl3) δ 7.51-7.49
(m, 2H), 7.42-7.31 (m, 8H), 5.74-5.65 (m, 1H), 5.58 (s, 1H),
5.07-5.04 (m, 2H), 4.92-4.88 (m, 2H), 4.56 (d, J=11.0 Hz, 1H),
4.30 (dd, J=4.5, 10.5 Hz, 1H), 4.21 (t, J=10.0 Hz, 1H), 4.03 (d,
J = 3.0 Hz, 1H), 3.84 (t, J = 10.0 Hz, 1H), 3.58 (t, J =
7.0 Hz, 1H), 3.51-3.46 (m, 1H), 2.50-2.44 (m, 1H), 2.28-2.23
(m, 1H), 1.51 (s, 9H); 13C NMR (125.6 MHz, CDCl3) δ 153.3,
138.0, 137.7, 134.2, 129.2, 128.7, 128.6, 128.4, 128.2, 126.5, 117.9,
101.8, 83.0, 79.5, 77.8, 76.6, 76.1, 75.6, 72.1, 68.8, 35.6, 28.0; ESI-
HRMS calcd for C28H34O7Na [M þ Na]þ 505.2202, found
505.2208.
4,6-O-Benzylidene-2-O-benzyl-3-O-(N,N-dibenzylcarbonyl)-
1-deoxy-1-allyl-r-D-mannopyranose (13). Prepared by the gen-
eral procedure 1 (eluent 10% ethyl acetate/hexane) with a yield of
33 mg (73%): [R]22D -16.3 (c=0.4, CHCl3); 1H NMR (500 MHz,
CDCl3) δ 7.49-7.15 (m, 18H), 7.04 (t, J=7.5 Hz, 2H), 5.77-
5.70 (m, 1H), 5.59 (s, 1H), 5.36 (dd, J=3.5, 10.5 Hz, 1H), 5.20-
5.12 (m, 2H), 4.70-4.59 (m, 4H), 4.29-4.18 (m, 4H), 4.11 (t, J=
8.0 Hz, 1H), 4.08 (dd, J=2.0, 3.5 Hz, 1H), 3.86-3.76 (m, 2H),
2.68-2.62 (m, 1H), 2.44-2.39 (m, 1H); 13C NMR (125.6 MHz,
CDCl3) δ 156.3, 138.1, 137.7, 137.4, 137.3, 133.5, 129.2, 128.8,
128.6, 128.5, 128.2, 128.0, 127.9, 127.7, 126.5, 118.4, 102.0, 73.4,
72.5, 69.4, 65.9, 49.5, 49.3, 33.9; ESI-HRMS calcd for C38H39-
NO6Na [M þ Na]þ 628.2675, found 628.2616.
3-O-Acetyl-2-O-benzyl-4,6-O-benzylidene-1-deoxy-1-allyl-r-
D-glucopyranose (17). Prepared by the general procedure 1 (eluent
10% ethyl acetate/hexane) with a yield of 30.0 mg (63%): [R]23
D
þ13.8(c=1.0, CHCl3); 1H NMR(500 MHz, CDCl3) δ7.46-7.45
(m, 2H), 7.38-7.30 (m, 8H), 5.80-5.71 (m, 1H), 5.48 (s, 1H), 5.43
(t, J=9.0 Hz, 1H), 5.16-5.09 (m, 2H), 4.64 (s, 2H), 4.26 (dd, J=
10.0, 4.5 Hz, 1H), 4.13-4.11 (m, 1H), 3.75-3.71 (m, 2H), 3.66 (t,
J=10.0 Hz, 1H), 3.60 (t, J=9.5 Hz, 1H), 2.65-2.58 (m, 1H),
2.55-2.52 (m, 1H), 2.08 (s, 3H); 13C NMR (125.6 MHz, CDCl3)
δ 170.4, 138.0, 137.3, 134.2, 129.2, 128.7, 128.5, 128.2, 128.0,
126.4, 117.7, 101.7, 80.2, 77.9, 74.9, 73.1, 71.5, 69.7, 63.7, 31.0,
21.3; ESI-HRMS calcd for C25H28O6Na [M þ Na]þ 447.1784,
found 447.1791.
4,6-O-Benzylidene-2-O-benzyl-3-O-(N,N-dibenzylcarbonyl)-
1-deoxy-1-(3,3-dimethyl-2-oxo-butyl)-r-D-mannopyranose (14).
Prepared by the general procedure 1 (eluent 15% ethyl acetate/
hexane) with a yield of 37 mg (76%): [R]22 -17.9 (c = 1.0,
D
1
CHCl3); H NMR (500 MHz, CDCl3) δ 7.49-7.47 (m, 2H),
7.40-7.39 (m, 3H), 7.33-7.31 (m, 2H), 7.27-7.267 (m, 5H),
7.20-7.15 (m, 6H), 7.05-7.02 (m, 2H), 5.59 (s, 1H), 5.31 (dd, J=
3.0, 10.0 Hz, 1H), 4.81-4.78 (m, 2H), 4.67 (d, J=16.5 Hz, 1H),
4.60-4.57 (m, 2H), 4.30-4.15 (m, 4H), 4.02 (d, J=2.0 Hz, 1H),
3.84 (t, J=10.0 Hz, 1H), 3.76-3.71 (m, 1H), 3.10 (dd, J=6.0,
3-O-Acetyl-2-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(3,3-di-
methyl-2-oxo-butyl)-r-D-glucopyranose (18r). Prepared by the
general procedure 1 (eluent 15% ethyl acetate/hexane) with a
1
yield of 33 mg (41%): [R]22 þ21.2 (c = 1, CHCl3); H NMR
D
17.5 Hz, 1H), 2.88 (dd, J=8.0, 17.5 Hz, 1H), 1.20 (s, 9H); 13
C
(500 MHz, CDCl3) δ 7.46-7.44 (m, 2H), 7.38-7.27 (m, 8H),
5.48 (s, 1H), 5.33 (t, J=9.0 Hz, 1H), 4.94-4.91 (m, 1H), 4.58 (d,
J=11.5 Hz, 1H), 4.52 (d, J=12.0 Hz, 1H), 4.25-4.23 (m, 1H),
3.76-3.73 (m, 1H), 3.70-3.67 (m, 2H), 3.61 (t, J=9.0 Hz, 1H),
2.98 (dd, J=5.5, 17.5 Hz, 1H), 2.88 (dd, J=7.0, 17.5 Hz, 1H),
2.07 (s, 3H), 1.12 (s, 9H); 13C NMR (125.9 MHz, CDCl3) δ
212.5, 170.5, 137.7, 129.3, 128.6, 128.5, 128.2, 126.3, 101.7, 79.9,
73.0, 71.6, 71.5, 69.6, 65.1, 44.7, 34.4, 26.3, 21.3; ESI-HRMS
calcd for C28H34O7Na [M þ Na]þ 505.2202, found 505.2213.
(3,3-Dimethyl-2-buten-2-yl) 3-O-acetyl-2-O--benzyl-4,6-O-
benzylidene-r-D-glucopyranoside (18β). Prepared by the gen-
eral procedure 1 (eluent 10% ethyl acetate/hexane) with a
yield of 17 mg (21%); [R]22D þ42.2 (c=0.5, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.47-7.45 (m, 2H), 7.37-7.30 (m, 8H),
5.61 (t, J=10.0 Hz, 1H), 5.48 (s, 1H), 5.36 (d, J=3.5 Hz, 1H),
4.64 (d, J=12.0 Hz, 1H), 4.57 (d, J=12.0 Hz, 1H), 4.28-4.24
(m, 1H), 4.22 (d, J = 2.0 Hz, 1H), 4.13 (d, J = 2.5 Hz, 1H),
3.89-3.84 (m, 1H), 3.71-3.64 (m, 2H), 3.58 (t, J = 10.0 Hz,
1H), 2.09 (s, 3H), 1.17 (s, 9H); 13C NMR (125.6 MHz, CDCl3)
δ 170.0, 169.3, 138.0, 137.3, 129.2, 128.7, 128.4, 128.1, 127.8,
126.4, 101.7, 94.8, 82.6, 79.8, 77.7, 72.5, 71.0, 69.3, 63.2, 36.5,
28.5, 21.3; ESI-HRMS calcd for C28H34O7Na [M þ Na]þ
505.2202, found 505.2158.
NMR (125.6 MHz, CDCl3) δ 212.5, 156.3, 138.3, 137.7, 137.4,
137.3, 129.2, 128.9, 128.7, 128.5, 128.2, 127.9, 127.7, 127.6,
126.5, 101.9, 78.3, 73.3, 72.9, 72.1, 69.3, 67.3, 49.5, 49.3, 44.8,
36.1, 26.4; ESI-HRMS calcd for C41H45NO7Na [M þ Na]þ
686.3094, found 686.3115.
4,6-O-Benzylidene-2-O-benzyl-3-O-(N,N-dibenzylcarbonyl)-
1-deoxy-1-(2-oxo-2-phenylethyl)-r-D-mannopyranose (15). Pre-
pared by the general procedure 1 (eluent 20% ethyl acetate/
hexane) with a yield of 44 mg (86%): [R]20 -9.5 (c = 1.0,
D
CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.98 (d, J=7.0 Hz, 2H),
7.62 (t, J=7.0 Hz, 1H), 7.53-7.50 (m, 5H), 7.41-7.25 (m, 10H),
7.20-7.15 (m, 5H), 7.03 (t, J=7.5 Hz, 2H), 5.60 (s, 1H), 5.41
(dd, J=3.0, 10.0 Hz, 1H), 4.97 (t, J=6.5 Hz, 1H), 4.83 (d, J=
12.0 Hz, 1H), 4.70-4.65 (m, 2H), 4.57 (d, J=15.5 Hz, 1H), 4.31
(dd, J = 9.0, 10.5 Hz, 1H), 4.25-4.19 (m, 3H), 4.16-4.15
(m, 2H), 3.85-3.83 (m, 2H), 3.58 (dd, J = 6.0, 17.5 Hz, 1H),
3.40 (dd, J=8.0, 17.0 Hz, 1H); 13C NMR (125.6 MHz, CDCl3) δ
196.6, 156.3, 138.2, 137.7, 137.4, 137.3, 136.7, 133.9, 129.3,
129.1, 128.8, 128.7, 128.6, 128.5, 128.4, 128.2, 128.1, 128.0,
127.9, 127.7, 127.6, 126.5, 102.0, 78.3, 73.3, 73.0, 72.1, 69.3,
67.3, 49.6, 49.3, 38.2; ESI-HRMS calcd for C43H41NO7Na
[M þ Na]þ 706.2781, found 706.2772.
J. Org. Chem. Vol. 75, No. 24, 2010 8389