J. Dinkelaar et al. / Carbohydrate Research 341 (2006) 1723–1729
1727
J = 3 Hz, 11 Hz, H-3), 7.72–7.87 (m, 4H, HaromPhth);
13C NMR (125 MHz): d 17.4 (C-6), 20.3 (CH3Ac),
53.0 (C-2), 63.2 (C-4), 69.3 (C-5), 70.3 (C-3), 92.3 (C-
1), 123.5 (CHPhth), 123.6 (CHPhth), 131.3 (Cq Phth),
131.4 (Cq Phth), 134.3 (CHPhth), 134.4 (CHPhth),
168.0 (C@O Phth), 168.3 (C@O Phth), 170.1 (C@O Ac);
HRMS m/z calcd for C16H16O6Na [M+H]+: 361.11426.
Found 361.15307.
3.88 (dd, 1H, J = 4.5, 12.5 Hz, H-3), 3.92 (dd, 1H,
J = 2.5, 16.5 Hz, H-6), 3.98 (dd, 1H, J = 4.5, 12.5 Hz,
H-2), 4.13 (m, 2H, H-4, H-6), 4.62 (d, 1H,
J = 14.5 Hz, CHHBn), 4.69 (d, 2H, J = 5 Hz, CHHBn),
4.71 (d, 1H, J = 14.5 Hz, CHHBn), 5.29 (d, 1H,
J = 4.5 Hz, H-1), 5.37 (s, 1H, CH–p-OMePhCH), 6.79
(d, 2H, J = 6.0 Hz, Harom–p-OMePhCH), 7.19–7.22
(m, 14H, Harom); 13C NMR (125 MHz): d 55.3 (CH3–
p-OMePhCH), 62.8 (C-5), 69.4 (C-6), 71.7 (CH2Bn),
73.9 (CH2Bn), 74.3 (C-4), 75.7 (C-2,3), 92.3 (C-1),
101.0 (CH–p-OMePhCH), 113.5 (CH–p-OMePhCH),
127.7–128.4 (CHarom), 130.4 (Cq p-OMePhCH), 138.3
(Cq Bn), 138.5 (Cq Bn), 160.0 (Cq p-OMePhCH);
HRMS m/z calcd for C28H30O7NH4 [M+NH4]+:
496.23298. Found 496.23303.
1.2.6. 4,6-O-Benzylidene-2-deoxy-3-O-levulinoyl-2-phthal-
imido-D-glucopyranose (12). The reaction mixture was
quenched after 120 min. Column chromatography
yielded 12 (0.210 g, 85%) as a white solid. IR (neat):
1
1076, 1386, 1716 cmꢀ1; H NMR (500 MHz, CDCl3):
d 1.86 (s, 3H, CH3 Lev), 2.35–2.56 (m, 4H, CH2 Lev),
3.81 (m, 3H, H-6, H-5, H-4), 4.25 (dd, 1H, J = 8.5,
10.0 Hz, H-2), 4.25 (dd, 1H, J = 4.0, 10.0 Hz, H-6),
5.54 (s, 1H, CHPh), 5.63 (d, 1H, J = 8.5 Hz, H-1),
5.93 (t, 1H, J = 10.0 Hz, H-3), 7.35 (m, 3H,
1.2.9. 4-O-Acetyl-2,6-di-O-benzoyl-3-O-tert-butyldimeth-
ylsilyl-D-galactopyranose (18). The reaction mixture
was quenched after 40 min. Column chromatography
yielded 18 (0.231 g, 85%) as a colorless oil. IR (neat):
H
H
aromCHPh), 7.45 (m, 2H, HaromCHPh), 7.67 (m, 2H,
aromPhth), 7.81 (br s, 2H, HaromPhth); 13C NMR
1112, 1270, 1451, 1723 cmꢀ1 1H NMR (500 MHz,
;
(125 MHz): d 27.7 (CH2 Lev), 29.3 (CH3 Lev), 37.6
(CH2 Lev), 56.5 (C-2), 66.3 (C-5), 68.5 (C-6), 69.5 (C-
3), 79.2 (C-4), 93.1 (C-1), 101.4 (CHPh), 123.4–136.8
(CHarom), 168.1 (C@O Phth), 171.9 (C@O Lev), 206.0
(C@O Lev); HRMS m/z calcd for C26H25O9NNa
[M+Na]+: 518.14215. Found 518.14428.
CDCl3): d 0.02 (s, 3H, CH3–Me–TBDMS), 0.13 (s,
3H, CH3–Me–TBDMS), 0.76 (s, 9H, CH3–tBu–
TBDMS), 2.19 (s, 3H, CH3Ac), 3.40 (s, 1H, OH), 4.33
(m, 1H, H-6), 4.46 (m, 2H, H-3, H-6), 4.60 (t, 1H,
J = 6 Hz, H-5), 5.39 (d, 1H, J = 7.5 Hz, H-2), 5.51 (s,
1H, H-4), 5.89 (s, 1H, H-1), 7.46 (m, 4H, Harom), 7.58
(m, 2H, Harom), 8.08 (m, 4H, Harom); 13C NMR
(125 MHz): d ꢀ5.0 (CH3–Me–TBDMS), ꢀ4.8 (CH3–
Me–TBDMS), 17.7 (CH3Ac), 25.3 (CH3–tBu–TBDMS),
62.9 (C-6), 66.6 (C-3), 67.0 (C-5), 71.0 (C-4), 71.7 (C-2),
91.1 (C-1), 128.3–133.4 (CHBz), 166.0 (C@O Bz), 166.2
(C@O Bz), 170.3 (C@O Ac); HRMS m/z calcd for
C28H36O9SiNa [M+Na]+: 567.20208. Found 567.20453.
1.2.7. 2-O-Benzyl-4,6-O-benzylidene-3-O-p-methoxybenz-
yl-D-mannopyranose (14). The reaction mixture was
quenched after 30 min. Column chromatography
yielded 14 (0.191 g, 80%) as a colorless oil. IR (neat):
1026, 1090, 1512, 1612 cmꢀ1 1H NMR (500 MHz,
;
CDCl3): d 3.45 (d, 1H, J = 3.5 Hz, OH), 3.75 (s, 3H,
CH3OMe), 3.77 (m, 1H, H-2), 3.82 (t, 1H,
J = 10.5 Hz, H-6), 3.97 (dd, 2H, J = 3.0 Hz, 10.5 Hz,
H-5, H-3), 4.19 (m, 2H, H-4, H-6), 4.56 (d, 1H,
J = 12 Hz, CHHBn), 4.65 (d, 1H, J = 12 Hz, CHHBn),
4.71 (d, 1H, J = 12 Hz, CHHBn), 4.74 (d, 1H,
J = 12 Hz, CHHBn), 5.07 (s, 1H, H-1), 5.61 (s, 1H,
CHPh), 6.82 (d, 2H, J = 8.5 Hz, HaromPMB), 7.29 (m,
12H, Harom); 13C NMR (125 MHz): d 55.1 (CH3
PMB), 64.1 (C-5), 68.8 (C-6), 72.6 (CH2Bn), 73.4
(CH2Bn), 75.4 (C-3), 76.5 (C-2), 79.0 (C-4), 93.9
(C-1), 101.4 (CHPh), 113.6 (CHaromPMB), 126.0–129.5
(CHarom), 130.6 (Cq arom), 137.6 (Cq arom), 138.0
(Cq arom), 159.0 (Cq PMB); HRMS m/z calcd for
C28H30O7Na [M+Na]+: 501.18837. Found 501.18893.
1.2.10. 4-O-Acetyl-2,3-O-isopropylidene-L-rhamnopyr-
anose (20).23 The reaction mixture was quenched after
30 min. Column chromatography yielded 20 (0.102 g,
83%) as a white solid. IR (neat): 1045, 1130, 1221,
1
1375, 1740 cmꢀ1; H NMR (500 MHz, CDCl3): d 1.16
(d, 3H, J = 6.3 Hz, H-6), 1.36 (s, 3H, CH3 isoprop),
1.57 (s, 3H, CH3 isoprop), 2.11 (s, 3H, CH3Ac), 3.21
(d, 1H, J = 2.9 Hz, OH), 3.97 (dq, 1H, H-5,
J = 6.3 Hz, 10.0 Hz, H-5), 4.18 (d, 1H, J = 5.4 Hz, H-
2), 4.22 (dd, 1H, J = 5.4 Hz, 7.7 Hz, H-3), 4.87 (dd,
1H, J = 7.7 Hz, 10.0 Hz H-4), 5.42 (d, 1H, J = 2.2 Hz,
H-2); 13C NMR (125 MHz): d 17.0 (C-6), 21.0 (CH3Ac),
26.4 (CH3 isoprop), 27.6 (CH3 isoprop), 64.2 (C-5), 74.4
(C-4), 75.5 (C-3), 76.1 (C-2), 91.8 (C-1), 109.8 (Cq iso-
prop), 170.2 (C@O Ac).
1.2.8. 2,3-Di-O-benzyl-4,6-O-p-methoxybenzylidene-D-
galactopyranose (16). The reaction mixture was
quenched after 20 min. Column chromatography
yielded 16 (0.168 g, 70%) as a colorless oil. IR (neat):
1.2.11. 3,4-Di-O-Acetyl-2-O-chloroacetyl-L-rhamnopyr-
anose (22). The reaction mixture was quenched after
30 min. Column chromatography yielded 22 (0.139 g,
86%) as a colorless oil. IR (neat): 1049, 1219, 1371,
1028, 1051, 1093, 1248, 1517, 1614 cmꢀ1 1H NMR
;
(500 MHz, CDCl3): d 2.90 (br s, 1H, OH), 3.73 (s, 3H,
CH3–p-OMePhCH), 3.76 (d, 1H, J = 1.0 Hz, H-5),
1740 cmꢀ1 1H NMR (500 MHz, CDCl3): d 1.22 (d,
;