Crich et al.
Hz, 1H), 2.17 (s, 3H), 1.86 (d, J ) 12.0 Hz, 3H), 1.80 (d, J ) 12.5
Hz, 3H), 1.66 (d, J ) 14.0 Hz, 3H), 1.61 (d, J ) 13.5 Hz, 3H); 13
1JCH ) 168.7 Hz), 98.0, 88.3 (d, J ) 178.8 Hz), 81.1, 78.7, 76.6,
76.0, 74.2 (d, J ) 16.4 Hz), 73.2, 68.7, 64.4, 63.9, 54.9, 28.1, 26.4,
17.4; ESI-HRMS calcd for C30H38FO9 [M + H]+, 561.2494; found,
561.2494. 34â: colorless oil; [R]20D -30.4 (c 0.5, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.52-7.49 (m, 2H), 7.41-7.27 (m, 8H), 5.62
(s, 1H), 5.02 (d, J ) 19.0 Hz, 1H), 4.87-4.77 (dd, J ) 2.5, 50.0
Hz, 1H), 4.86 (s, 1H), 4.85 (d, J ) 12.5 Hz, 1H), 4.79 (d, J ) 12.5
Hz, 1H), 4.32-4.29 (dd, J ) 5.0, 10.5 Hz, 1H), 4.19 (t, J ) 6.5
Hz, 1H), 4.12-4.08 (m, 2H), 3.92 (t, J ) 10.5 Hz, 1H), 3.73-
3.66 (ddd, J ) 2.5, 10.0, 27.5 Hz, 1H), 3.68-3.63 (m, 2H), 3.38-
3.33 (m, 1H), 3.37 (s, 3H), 1.50 (s, 3H), 1.33 (s, 3H), 1.30 (d, J )
6.0 Hz, 3H); 13C NMR (125.9 MHz, CDCl3) δ 137.4, 137.3, 129.0,
128.5, 128.3, 127.9, 127.8, 126.0, 109.4, 101.6, 97.8, 97.7 (d, J )
C
NMR (125.9 MHz, CDCl3) δ 138.5, 137.3, 129.0, 128.32, 128.25,
127.8, 127.6, 126.0, 101.3, 90.12 (d, J ) 20.0 Hz), 90.06 (d, J )
193.1 Hz), 81.5 (d, J ) 9.7 Hz), 78.1, 75.3, 74.7, 69.1, 62.1, 42.4,
36.2, 30.6; ESI-HRMS calcd for C30H36FO5 [M + H]+, 495.2541;
found, 495.2541. 32â: white crystalline solid; mp 146 °C; [R]17
D
1
-11.3 (c 0.6, CHCl3); H NMR (500 MHz, CDCl3) δ 7.51-7.48
(m, 2H), 7.42-7.26 (m, 8H), 5.55 (s, 1H), 4.88-4.83 (m, 3H),
4.38-4.25 (dt, J ) 8.0, 49.5 Hz, 1H), 4.32-4.29 (dd, J ) 5.0,
10.5 Hz, 1H), 3.87-3.80 (dt, J ) 9.0, 15.0 Hz, 1H), 3.79 (t, J )
10.0 Hz, 1H), 3.67 (d, J ) 9.5 Hz, 1H), 3.45-3.41 (dt, J ) 5.0,
10.0 Hz, 1H), 2.18 (s, 3H), 1.87 (d, J ) 11.0 Hz, 3H), 1.78 (d, J
) 11.5 Hz, 3H), 1.66 (d, J ) 12.5 Hz, 3H), 1.62 (d, J ) 12.0 Hz,
1
15.1 Hz, JCH ) 157.4 Hz), 88.4 (d, J ) 190.1 Hz), 78.4 (d, J )
3H); 13C NMR (125.9 MHz, CDCl3) δ 138.1, 137.2, 129.0, 128.33,
25.2 Hz), 78.3, 76.2, 75.8 (d, J ) 16.4 Hz), 72.4, 68.5, 67.2, 63.9,
54.8, 27.8, 26.4, 17.4; ESI-HRMS calcd for C30H38FO9 [M + H]+,
561.2494; found, 561.2494.
1
128.27, 128.0, 127.7, 126.1, 101.3, 94.1 (d, J ) 23.9 Hz, JCH
)
158.6 Hz), 93.0 (d, J ) 187.6 Hz), 80.4 (d, J ) 10.1 Hz), 79.2 (d,
J ) 18.9 Hz), 75.9, 74.3, 68.8, 66.1, 42.4, 36.2, 30.7; ESI-HRMS
calcd for C30H35FO5Na [M + Na]+, 517.2361; found, 517.2355.
Methyl 2,3,6-Tri-O-benzyl-4-O-(3-O-benzyl-4,6-O-benzylidene-
2-deoxy-2-fluoro-R-D-glucopyranosyl)-R-D-glucopyranoside (33R)
and Methyl 2,3,6-Tri-O-benzyl-4-O-(3-O-benzyl-4,6-O-benzylidene-
2-deoxy-2-fluoro-â-D-glucopyranosyl)-R-D-glucopyranoside (33â).
Prepared by the general procedure with a combined yield of 67.5
(1-Adamantanyl) 3-O-Benzyl-4,6-O-benzylidene-2-deoxy-2-
fluoro-R-D-mannopyranoside (35R) and (1-Adamantanyl) 3-O-
Benzyl-4,6-O-benzylidene-2-deoxy-2-fluoro-â-D-mannopyrano-
side (35â). Prepared by the general procedure with a combined
yield of 67.8 mg (82%, 1:1.3 R/â). Donor 11 (5.3 mg, 7%) was
recovered from this reaction. 35R: colorless oil; [R]20 +55.0 (c
D
1
0.2, CHCl3); H NMR (500 MHz, CDCl3) δ 7.52-7.49 (m, 2H),
mg (68%, 1:4.6 R/â). Donor 10 (4.5 mg, 8%) was recovered from
7.40-7.26 (m, 8H), 5.64 (s, 1H), 5.36-5.34 (dd, J ) 2.0, 8.0 Hz,
1H), 4.89 (d, J ) 12.0 Hz, 1H), 4.76 (d, J ) 12.0 Hz, 1H), 4.67-
4.56 (dt, J ) 2.0, 49.5 Hz, 1H), 4.26-4.23 (dd, J ) 4.5, 10.0 Hz,
1H), 4.12-3.97 (m, 3H), 3.81 (t, J ) 10.0 Hz, 1H), 2.15 (s, 3H),
1.81 (d, J ) 11.0 Hz, 3H), 1.76 (d, J ) 10.5 Hz, 3H), 1.65 (d, J )
12.5 Hz, 3H), 1.59 (d, J ) 12.0 Hz, 3H); 13C NMR (125.9 MHz,
CDCl3) δ 138.3, 137.5, 128.9, 128.4, 128.2, 127.8, 127.7, 126.1,
101.5, 91.8 (d, J ) 30.2 Hz, 1JCH ) 169.6 Hz), 89.9 (d, J ) 178.8
Hz), 79.1, 75.5, 74.5 (d, J ) 16.4 Hz), 73.1, 68.8, 63.6, 42.3, 36.1,
30.6; ESI-HRMS calcd for C30H35FO5Na [M + Na]+, 517.2361;
1
this reaction. 33R: colorless oil; [R]21 +40.0 (c 0.3, CHCl3); H
D
NMR (500 MHz, CDCl3) δ 7.49-7.47 (m, 2H), 7.41-7.21 (m,
23H), 5.74 (d, J ) 4.5 Hz, 1H), 5.52 (s, 1H), 5.01 (d, J ) 10.5 Hz,
1H), 4.88 (d, J ) 11.5 Hz, 1H), 4.82 (d, J ) 12.0 Hz, 1H), 4.78
(d, J ) 6.0 Hz, 1H), 4.76 (d, J ) 3.5 Hz, 1H), 4.65-4.54 (m, 4H),
4.51-4.39 (ddd, J ) 4.0, 9.0, 48.5 Hz, 1H), 4.08-4.02 (m, 3H),
3.93 (t, J ) 9.0 Hz, 1H), 3.83-3.77 (m, 3H), 3.69 (d, J ) 9.0 Hz,
1H), 3.62-3.55 (m, 3H), 3.40 (s, 3H); 13C NMR (125.9 MHz,
CDCl3) δ 138.6, 138.3, 138.03, 138.00, 137.2, 129.0, 128.5, 128.43,
128.38, 128.3, 128.24, 128.18, 128.0, 127.9, 127.7, 127.6, 127.5,-
127.4, 126.1, 101.3, 97.9, 97.4 (d, J ) 20.0 Hz, 1JCH ) 175.4 Hz),
90.0 (d, J ) 191.3 Hz), 81.7, 81.0 (d, J ) 8.6 Hz), 80.3, 76.6,
76.5, 75.3, 75.1, 74.7, 73.5 (d, J ) 23.7 Hz), 69.4, 69.1, 68.7, 63.1,
54.7; ESI-HRMS calcd for C48H52FO10 [M + H]+, 807.3539; found,
807.3531. 33â: colorless oil; [R]21D +8.1 (c 1.0, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.49-7.47 (m, 2H), 7.44-7.21 (m, 23H),
5.47 (s, 1H), 4.87-4.78 (m, 5H), 4.68 (d, J ) 12.0 Hz, 1H), 4.63
(d, J ) 12.5 Hz, 1H), 4.61 (d, J ) 4.0 Hz, 1H), 4.50-4.48 (dd, J
) 3.5, 7.5 Hz, 1H), 4.40 (d, J ) 12.0 Hz, 1H), 4.28-4.15 (dt, J )
8.0, 49.5 Hz, 1H), 4.03-4.00 (dd, J ) 5.0, 10.5 Hz, 1H), 3.94-
3.86 (m, 3H), 3.76 (d, J ) 9.5 Hz, 1H), 3.66 (d, J ) 10.5 Hz, 1H),
3.61-3.51 (m, 3H), 3.44 (t, J ) 10.5 Hz, 1H), 3.39 (s, 3H), 3.07-
3.02 (dt, J ) 5.0, 9.5 Hz, 1H); 13C NMR (125.9 MHz, CDCl3) δ
139.2, 138.2, 138.1, 137.9, 137.2, 129.1, 128.6, 128.44, 128.38,
128.3, 128.20, 128.16, 128.0, 127.9, 127.8, 127.4, 126.1, 101.3,
101.2 (d, J ) 22.7 Hz, 1JCH ) 159.2 Hz), 98.3, 93.5 (d, J ) 187.6
Hz), 80.5 (d, J ) 10.1 Hz), 80.2, 79.2, 78.6 (d, J ) 18.9 Hz), 77.9,
75.4, 74.2, 73.6 (d, J ) 10.1 Hz), 69.6, 68.5, 67.7, 65.6, 55.3; ESI-
HRMS calcd for C48H52FO10 [M + H]+, 807.3539; found, 807.3546.
Methyl 4-O-(3-O-Benzyl-4,6-O-benzylidene-2-deoxy-2-fluoro-
R-D-mannopyranosyl)-2,3-O-isopropylidene-R-L-rhamnopyrano-
side (34R) and Methyl 4-O-(3-O-Benzyl-4,6-O-benzylidene-2-
deoxy-2-fluoro-â-D-mannopyranosyl)-2,3-O-isopropylidene-R-L-
rhamnopyranoside (34â). Prepared by the general procedure with
a combined yield of 45.8 mg (73%, 1:3.7 R/â). 34R: colorless oil;
[R]20D +59.5 (c 0.2, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.53-
7.51 (m, 2H), 7.40-7.26 (m, 8H), 5.64 (s, 1H), 5.04 (d, J ) 8.0
Hz, 1H), 4.89 (d, J ) 12.0 Hz, 1H), 4.85 (s, 1H), 4.76 (d, J ) 12.0
Hz, 1H), 4.73 (d, J ) 49.0 Hz, 1H), 4.30-4.27 (dd, J ) 4.5, 10.0
Hz, 1H), 4.14-4.05 (m, 4H), 3.96-3.89 (dd, J ) 9.5, 28.0 Hz,
1H), 3.83 (t, J ) 10.0 Hz, 1H), 3.66-3.60 (m, 1H), 3.39-3.35
(m, 1H), 3.37 (s, 3H), 1.52 (s, 3H), 1.33 (s, 3H), 1.24 (d, J ) 6.5
Hz, 3H); 13C NMR (125.9 MHz, CDCl3) δ 138.1, 137.5, 129.0,
128.4, 128.3, 127.8, 126.1, 109.3, 101.6, 98.9 (d, J ) 15.1 Hz,
found, 517.2362. 35â: white crystalline solid; mp 86-87 °C; [R]17
D
1
+4.8 (c 1.0, CHCl3); H NMR (500 MHz, CDCl3) δ 7.51-7.49
(m, 2H), 7.41-7.26 (m, 8H), 5.61 (s, 1H), 4.86-4.78 (m, 3H),
4.72-4.62 (dd, J ) 2.0, 50.0 Hz, 1H), 4.31-4.28 (dd, J ) 5.0,
10.5 Hz, 1H), 4.10 (t, J ) 10.0 Hz, 1H), 3.90 (d, J ) 10.5 Hz,
1H), 3.72-3.63 (ddd, J ) 2.5, 10.0, 26.5 Hz, 1H), 3.40-3.35 (dt,
J ) 5.0, 10.0 Hz, 1H), 2.18 (s, 3H), 1.88 (d, J ) 11.5 Hz, 3H),
1.78 (d, J ) 11.5 Hz, 3H), 1.66 (d, J ) 12.5 Hz, 3H), 1.62 (d, J )
12.5 Hz, 3H); 13C NMR (125.9 MHz, CDCl3) δ 137.9, 137.4, 129.0,
1
128.5, 128.3, 127.8, 126.1, 101.6, 92.7 (d, J ) 16.4 Hz, JCH
)
153.6 Hz), 90.3 (d, J ) 188.8 Hz), 78.3, 76.2 (d, J ) 16.4 Hz),
76.0, 72.4, 68.7, 66.9, 42.3, 36.1, 30.7. Anal. Calcd for C30H35-
FO5: C, 72.85; H, 7.13. Found: C, 73.11; H, 7.27.
Methyl 2,3,6-Tri-O-benzyl-4-O-(3-O-benzyl-4,6-O-benzylidene-
2-deoxy-2-fluoro-R-D-mannopyranosyl)-R-D-glucopyranoside (36R)
and Methyl 2,3,6-Tri-O-benzyl-4-O-(3-O-benzyl-4,6-O-benzylidene-
2-deoxy-2-fluoro-â-D-mannopyranosyl)-R-D-glucopyranoside (36â).
Prepared by the general procedure with a combined yield of 67.5
mg (64%, 1:3.1 R/â). Donor 11 (6.0 mg, 12%) was recovered from
1
this reaction. 36R: colorless oil; [R]16 +33.3 (c 0.3, CHCl3); H
D
NMR (500 MHz, CDCl3) δ 7.49-7.47 (m, 2H), 7.38-7.24 (m,
23H), 5.59 (s, 1H), 5.44-5.42 (dd, J ) 1.5, 8.0 Hz, 1H), 5.00 (d,
J ) 11.0 Hz, 1H), 4.78 (d, J ) 12.0 Hz, 1H), 4.73 (d, J ) 12.0
Hz, 1H), 4.66-4.50 (m, 7H), 4.10-4.05 (m, 2H), 3.88-3.67 (m,
8H), 3.55-3.52 (dt, J ) 3.5, 10.0 Hz, 1H), 3.39 (s, 3H); 13C NMR
(125.9 MHz, CDCl3) δ 138.0, 137.9, 137.8, 137.4, 128.9, 128.6,
128.5, 128.39, 128.36, 128.20, 128.16, 128.1, 127.8, 127.7, 127.6,
1
127.0, 126.1, 101.6, 100.0 (d, J ) 31.6 Hz, JCH ) 173.3 Hz),
97.8, 88.4 (d, J ) 180.3 Hz), 81.2, 80.2, 78.5, 77.6, 75.5, 74.0 (d,
J ) 16.0 Hz), 73.7, 73.2, 73.0, 69.4, 68.9, 68.5, 64.8, 55.4; ESI-
HRMS calcd for C48H51FO10Na [M + Na]+, 829.3364; found,
829.3387. 36â: colorless oil; [R]21D +2.1 (c 0.15, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.49-7.47 (m, 2H), 7.42-7.21 (m, 23H),
5.53 (s, 1H), 4.91 (d, J ) 10.5 Hz, 1H), 4.88 (d, J ) 11.5 Hz, 1H),
4.80 (d, J ) 12.5 Hz, 1H), 4.72-4.54 (m, 7H), 4.41 (d, J ) 12.0
1688 J. Org. Chem., Vol. 72, No. 5, 2007