9554 J. Am. Chem. Soc., Vol. 123, No. 39, 2001
Plante et al.
3H), 1.31 (s, 3H), 1.21 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 177.1,
138.5, 138.4, 128.7, 128.6, 128.2, 128.1, 128.0, 127.9, 127.8, 127.7,
109.5, 108.8, 101.8, 96.6, 83.6, 78.1, 75.7, 75.2, 73.9, 73.3, 71.5, 70.9,
69.0, 67.4, 39.1, 27.5, 26.4, 26.3, 25.4, 24.7; FAB MS m/z (M)+ calcd
776.3772, found 776.3770.
138.4, 137.9, 128.6, 128.0, 127.9, 127.7, 109.3, 108.7, 101.7, 96.4,
82.8, 74.5, 74.4, 73.9, 72.6, 72.0, 71.3, 70.7, 70.2, 68.9, 67.2, 38.9,
27.3, 26.3, 26.1, 25.2, 24.5; 31P NMR (120 MHz, CDCl3) δ -3.3; ESI
MS m/z (M + Na)+ calcd 709.3194, obsd 709.3161.
4,6-Di-O-benzyl-2-O-pivaloyl-â-D-galactopyranosyl-(1f6)-1,2:3,4-
di-O-isopropylidene-r-D-galactopyranoside 68. General procedure D
with donor 67 (40.8 mg, 64.0 µmol), acceptor 22 (18.3 mg, 70.4 µmol),
and TMSOTf (11.8 µL, 64.0 µmol) at -78 °C for 10 min followed by
30 min at -0 °C afforded 38.3 mg (79%) of 68 as a colorless oil after
n-Pentenyl 2-O-Benzoyl-3,4,6-tri-O-benzyl-â-D-galactopyranosyl-
(1f4)-3-O-acetyl-6-O-benzyl-2-deoxy-2-benzyloxycarbonylamino-
â-D-glucopyranoside 32. General procedure D with donor 7 (63.4 mg,
84.0 µmol), acceptor 27 (24.2 mg, 49.1 µmol), and TBSOTf (20.9 µL,
84.0 µmol) at -50 °C followed by 30 min at -20 °C afforded 50.0
mg (96%) of 32 as a colorless oil after flash silica column chroma-
1
flash silica column chromatography (35% EtOAc/hexanes). H NMR
(500 MHz, CDCl3) δ 7.39-7.27 (m, 10H), 5.48 (d, J ) 5.0 Hz, 1H),
4.97 (dd, J ) 8.0, 9.9 Hz, 1H), 4.72-4.69 (m, 2H), 4.58-4.47 (m,
3H), 4.45 (d, J ) 8.0 Hz, 1H), 4.27 (dd, J ) 2.5, 5.0 Hz, 1H), 4.21
(dd, J ) 1.7, 8.0 Hz, 1H), 4.03 (dd, J ) 4.7, 10.4 Hz, 1H), 3.94-3.89
(m, 2H), 3.70-3.58 (m, 5H), 2.40 (d, J ) 9.6 Hz, 1H), 1.48 (s, 3H),
1.43 (s, 3H), 1.31 (app s, 6H), 1.23 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 179.2, 138.2, 137.8, 128.7, 128.7, 128.3, 128.1, 109.3, 108.7,
101.5, 96.4, 76.6, 75.6, 73.7, 73.5, 73.4, 73.4, 71.3, 70.7, 70.6, 69.0,
68.2, 67.2, 39.1, 27.3, 26.3, 26.1, 25.2, 24.5.
Dibutyl 3,4,6-Tri-O-benzyl-2-O-pivaloyl-â-D-glucopyranosyl-
(1f6)-3,4-O-carbonyl-2-O-pivaloyl-r-D-galactopyranoside Phos-
phate 81. General procedure D with donor 1 (76.3 mg, 105 µmol),
acceptor 80 (48.3 mg, 0.100 mmol), and TMSOTf (19.4 µL, 105 µmol)
afforded 89.0 mg (89%) of 81 as a colorless oil after flash silica column
chromatography (40% EtOAc/hexanes). [R]24D +6.7° (c 2.56, CH2Cl2);
IR (thin film) 2962, 1817, 1740, 1138, 1068 cm-1; 1H NMR (500 MHz,
CDCl3) δ 7.37-7.25 (m, 13H), 7.17-7.16 (m, 2H), 5.67-5.64 (m,
1H), 5.12 (d, J ) 8.5 Hz, 1H), 5.06-5.02 (m, 2H), 4.77 (d, J ) 10.7
Hz, 1H), 4.75 (d, J ) 11.0 Hz, 1H), 4.69 (d, J ) 11.0 Hz, 1H), 4.58
(d, J ) 11.9 Hz, 1H), 4.55-4.46 (m, 3H), 4.44 (d, J ) 7.9 Hz, 1H),
4.09-3.99 (m, 5H), 3.86-3.84 (m, 1H), 3.74-3.66 (m, 4H), 3.56-
3.52 (m, 1H), 1.67-1.61 (m, 4H), 1.44-1.40 (m, 4H), 1.22 (s, 9H),
1.19 (s, 9H), 0.95-0.91 (m, 6H); 13C NMR (125 MHz, CDCl3) δ 177.1,
176.1, 153.3, 138.1, 138.0, 128.7, 128.6, 128.1, 128.0, 127.9, 127.6,
102.3, 94.1, 83.2, 77.8, 75.3, 75.2, 73.7, 73.2, 71.9, 71.5, 69.4, 68.9,
68.4, 66.9, 39.0, 32.3, 27.3, 27.2, 18.8, 13.8, 13.7; 31P NMR (120 MHz,
CDCl3) δ -3.3; ESI MS m/z (M + Na)+ calcd 1021.4321, obsd
1021.4356.
tography (30%f50% EtOAc/hexanes). [R]24 +29.3° (c 1.10,
D
1
CH2Cl2); IR (thin film) 3029, 2872, 1726, 1540, 1453, 1367, 736; H
NMR (500 MHz, CDCl3) δ 8.05 (d, J ) 7.0 Hz, 1H), 7.70 (t, J ) 7.5
Hz, 1H), 7.57-7.27 (m, 28H), 5.87-5.85 (m, 1H), 5.62 (dd, J ) 8.0,
10.0 Hz, 1H), 5.22 (s, 2H), 5.11 (d, J ) 11.5 Hz, 1H), 5.10-5.04 (m,
2H), 4.92-4.90 (m, 1H), 4.74 (d, J ) 12.5 Hz, 1H), 4.70 (d, J ) 12.0
Hz, 1H), 4.63 (d, J ) 12.5 Hz, 1H), 4.57 (s, 2H), 4.56 (d, J ) 11.5
Hz, 1H), 4.38 (d, J ) 12.0 Hz, 1H), 4.33 (d, J ) 7.5 Hz, 1H), 4.13 (d,
J ) 2.5 Hz, 1H), 4.00 (app t, J ) 9.0 Hz, 1H), 3.91 (dt, J ) 3.0, 6.5
Hz, 1H), 3.84-3.77 (m, 3H), 3.71-3.59 (m, 6H), 3.46-3.44 (m, 2H),
2.22-2.12 (m, 2H), 1.98 (s, 3H), 1.77-1.66 (m, 2H); 13C NMR (125
MHz, CDCl3) δ 170.9, 165.0, 156.1, 138.7, 138.4, 138.2, 137.8, 136.7,
133.2, 130.1, 130.0, 128.6, 128.5, 128.4, 128.1, 127.8, 127.7, 127.6,
115.0, 102.0, 100.8, 79.8, 74.7, 74.6, 73.7, 73.4, 73.1, 72.4, 72.3, 71.5,
69.1, 68.1, 66.8, 55.9, 30.1, 28.7, 20.9; FAB MS m/z (M)+ calcd
1049.4561, obsd 1049.4528.
2-(2′,3′,4′,6′-Tetra-O-benzyl-r-D-mannopyranosyl)-3,4,5-trimeth-
oxyphen-1-ol 56. Diphenyl 2,3,4,6-tetra-O-benzyl-R-D-mannopyranosyl
phosphate 36 (35 mg, 45 µmol) was coevaporated with toluene and
dissolved in CH2Cl2 (2.0 mL), and the solution was cooled to 0 °C.
3,4,5-Trimethoxyphenol 51 (25.0 mg, 136 µmol) was added, followed
by the addition of TMSOTf (10.0 µL, 55.0 µmol). The reaction mixture
was allowed to warm to ambient temperature over 1 h. Triethylamine
(Et3N, 15 µL) was added and the solvent was removed in vacuo.
Purification by flash silica column chromatography (5:1 hexanes:
EtOAc) afforded 27.0 mg (85%) of 56 as a colorless oil. [R]24D +12.7°
(c 1.82, CH2Cl2); IR (thin film) 3364, 2933, 1621, 1495, 1362, 1100
cm-1; 1H NMR (500 MHz, CDCl3) δ 8.40 (s, 1H), 7.38-7.26 (m, 13H),
7.21-7.10 (m, 6H), 6.27 (s, 1H), 4.92 (d, J ) 11.0 Hz, 1H), 4.82 (d,
J ) 0.9 Hz, 1H), 4.70 (app s, 2H), 4.64 (d, J ) 12.2 Hz, 1H), 4.62 (d,
J ) 12.0 Hz, 1H), 4.57 (d, J ) 11.0 Hz, 1H), 4.54-4.50 (m, 2H), 4.17
(app t, J ) 9.8 Hz, 1H), 3.90 (app d, J ) 1.9 Hz, 1H), 3.82 (s, 3H),
3.79-3.71 (m, 6H), 3.70 (s, 3H), 3.57-3.54 (m, 1H); 13C NMR (125
MHz, CDCl3) δ 153.9, 153.7, 150.2, 138.6, 138.5, 138.4, 138.2, 134.6,
128.8, 128.6, 128.6, 128.5, 128.5, 128.2, 128.2, 127.9, 127.9, 127.8,
127.8, 127.7, 127.6, 107.6, 97.0, 84.2, 79.7, 77.0, 76.8, 75.5, 74.4, 73.6,
72.4, 68.8, 61.1, 60.9, 56.0. FAB MS m/z (M + Na)+ calcd 729.3010
obsd 729.3034.
Acknowledgment. Financial support from the donors of the
Petroleum Research Fund, administered by the American
Chemical Society (ACS-PRF 34649-G1), for partial support of
this research; the Mizutani Foundation for Glycoscience; the
Kenneth M. Gordon Scholarship Fund (Fellowship for O.J.P.);
the NIH (Biotechnology Training Grant for O.J.P.); Pfizer (ACS
Division of Organic Chemistry-Pfizer Fellowship for O.J.P.);
NSF (Predoctoral Fellowship for R.B.A.); Merck (Predoctoral
Fellowship for E.R.P.); and Boehringer-Ingelheim (Predoctoral
Fellowship for E.R.P.) is gratefully acknowledged. Funding for
the MIT-DCIF Inova 501 was provided by NSF (Award No.
CHE-9808061). Funding for the MIT-DCIF Avance (DPX) 400
was provided by NIH (Award No. 1S10RR13886-01). Funding
for the MIT-DCIF Mercury 300 was provided by NSF (Award
No. CHE-9808061) and NSF (Award No. DBI-9729592).
3,6-Di-O-benzyl-2-O-pivaloyl-â-D-glucopyranosyl-(1â6)-1,2:3,4-
di-O-isopropylidene-f-D-galactopyranoside 65. General procedure
D with donor 64 (63.7 mg, 100. µmol), acceptor 22 (31.2 mg, 0.120
mmol), and TMSOTf (12.0 µL, 0.100 mmol) afforded 64.6 mg (94%)
of 65 as a colorless oil after flash silica column chromatography (30%
EtOAc/hexanes). [R]24D -37.2° (c 5.11, CH2Cl2); IR (thin film) 3507,
1
2978, 1740, 1318, 1071 cm-1; H NMR (500 MHz, CDCl3) δ 7.38-
Supporting Information Available: Detailed experimental
7.27 (m, 10H), 5.49 (d, J ) 4.9 Hz, 1H), 5.06 (dd, J ) 8.2, 9.8 Hz,
1H), 4.74 (d, J ) 11.3 Hz, 1H), 4.70 (d, J ) 11.3 Hz, 1H), 4.62 (d, J
) 11.9 Hz, 1H), 4.59-4.56 (m, 2H), 4.48 (d, J ) 7.9 Hz, 1H), 4.29
(dd, J ) 2.4, 4.9 Hz, 1H), 4.24 (dd, J ) 1.8, 8.2 Hz, 1H), 4.06 (dd, J
) 5.2, 10.4 Hz, 1H), 3.95-3.92 (m, 1H), 3.77-3.73 (m, 4H), 3.62-
3.55 (m, 2H), 3.51-3.49 (m, 1H), 1.51 (s, 3H), 1.44 (s, 3H), 1.33 (s,
3H), 1.32 (s, 3H), 1.23 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 177.0,
1
procedures and compound characterization data, including H
NMR and 13C NMR spectral data for all described compounds
and five additional schemes (PDF). This material is available
JA016227R