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6 ꢂ CH2 Bn), 4.92 (dd, 1H, H-2’, J2’,3’ = 9.9 Hz), 4.54 (d, 1H, H-1, J1,2 = 3.0 Hz), 4.43
(dd, 1H, H-5, J5,4 = 9.8 Hz), 3.98 (ddd, 1H, H-5’, J5’,4’ = 9.9 Hz, J5’,6a’ = 3.2 Hz,
J5’,6b’ = 1.2 Hz), 3.90 (t, 1H, H-3’, J3’,4’ = J3’,2’ = 9.4 Hz), 3.89 (t, 1H, H-3,
J3,4 = J3,2 = 9.3 Hz), 3.76–3.61 (m, 3H, 2 ꢂ H-6’, H-4’), 3.55–3.48 (m, 2H, H-2, H-4),
3.42 (s, 3H, OMe), 1.91 (s, 3H, CH3 Ac).
Methyl 7-deoxy-2,3,4-tri-O-benzyl-7-(3,4-di-O-benzyl-6-O-trityl- -D-glucopyra-
nosyl)- -D-gluco-hept-6-ynopyranoside (11). 13C NMR (CDCl3): d 143.5 (Cq Ph),
138.3, 138.2, 137.8, 137.6, 137.5 (5 ꢂ Cq Bn), 128.5–126.6 (CHarom), 98.0 (C-1), 86.6,
85.9 (Cq Tr, C ), 83.5, 81.9, 80.5 (3 ꢂ OCH), 80.3 ( C), 78.9, 77.3 (2 ꢂ OCH),
75.5, 75.0, 74.5 (4 ꢂ CH2 Bn), 73.9 (OCH), 73.1 (CH2 Bn), 70.9, 68.3 (2 ꢂ OCH),
61.8 (C-6’), 61.5 (OCH), 55.4 (OMe). MS/ESI: m/z 1043.5 [M + H]+. Data of the 2’-
1
OAc derivative: H NMR (CDCl3): d 7.48–7.12 (m, 40H, CHarom), 5.17 (dd, 1H, H-1’,
J1’,2’ = 6.0 Hz, J1’,5 = 1.7 Hz), 5.04 (dd, 1H, H-2’, J2’,3’ = 9.4 Hz), 4.98–4.46 (m, 9H,
4 ꢂ CH2 Bn, CHH Bn), 4.52 (d, 1H, H-1, 3.5 Hz), 4.39 (dd, 1H, H-5, J5,4 = 9.9 Hz),
4.31 (d, 1H, CHH Bn), 3.95–3.84 (m, 4H, H-3, H-3’, H-4’, H-5’), 3.59–3.47 (m, 3H,
H-2, H-4, H-6a’), 3.40 (s, 3H, OMe), 3.21 (dd, 1H, H-6b’, J6b’,6a’ = 10.2 Hz, J6b’,5’ = 2.4
Hz), 1.95 (s, 3H, CH3 Ac).
Methyl 7-deoxy-2,3,4-tri-O-benzyl-7-(3,4-di-O-benzyl-6-O-tert-butyldiphenylsi-
lyl- -D-galacto-pyranosyl)- -D-gluco-hept-6-ynopyranoside (13). 13C NMR
(CDCl3): d 138.8–138.1 (Cq Bn), 135.6–127.5 (CHarom), 133.2 (Cq Ph), 98.5 (C-1),
86.0 (C ), 82.3, 81.2, 81.0 (3 ꢂ OCH), 80.7 ( C), 79.2 (OCH), 75.9, 75.4, 74.8
(3 ꢂ CH2 Bn), 74.3 (OCH), 73.6 (CH2 Bn), 73.5 (OCH), 72.1 (CH2 Bn), 68.7, 67.5
(2 ꢂ OCH), 62.2 (C-6’), 61.8 (OCH), 55.9 (OMe), 27.0 (CH3t-Bu), 19.3 (Cqt-Bu). MS/
1
ESI: m/z 1039.5 [M + H]+. Data for the 2’-OAc derivative: H NMR (CDCl3): d 7.65–
7.18 (m, 30H, CHarom), 5.31 (dd, 1H, H-2’, J2’,1’ = 6.0 Hz, J2’,3’ = 10.2 Hz), 5.07 (dd,
1H, H-1’, J1’,5 = 1.5 Hz), 4.95–4.65 (m, 7H, 3 ꢂ CH2, CHH Bn), 4.57 (d, 1H, H-1,
J1,2 = 3.5 Hz), 4.54 (d, 1H, CHH Bn), 4.45 (dd, 1H, H-5, J5,4 = 9.9 Hz), 4.38 (AB, 2H,
CH2 Bn), 4.02–3.96 (m, 2H, H-4’, H-5’), 3.92 (t, 1H, H-3, J3,2 = J3,4 = 9.3 Hz), 3.85–
3.72 (m, 3H, H-3’, 2 ꢂ H-6’), 3.56–3.47 (m, 2H, H-2, H-4), 3.48 (OMe), 1.06 (s, 9H, t-
Bu). MS: m/z 1099 [M + NH4]+, 1104 [M + Na]+, 1120 [M + K]+.
(3,4,6-Tri-O-benzyl- -D-glucopyranosyl)phenylethyne (17). Colourless syrup.
13C NMR (CDCl3): d 138.4, 137.9, 137.7 (3 ꢂ Cq Bn), 131.9 (CH Ph), 128.7–127.6
(CH Bn), 121.8 (Cq Ph), 89.9 (C ), 83.5 (OCH), 83.3 ( C), 77.6 (OCH), 75.2, 75.0
1
(2 ꢂ CH2 Bn), 73.9 (OCH), 73.4 (CH2 Bn), 71.4, 68.9 (2 ꢂ OCH), 68.4 (C-6). H
NMR (CDCl3): d 7.46–7.14 (m, 20H, Harom), 5.04 (d, 1H, H-1, J1,2 = 5.1 Hz), 4.97–
4.49 (m, 6H, 3 ꢂ CH2 Bn), 4.07 (m, 1H, H-5), 3.85–3.65 (m, 5H, H-2, H-3, H-4, H-6).
ESI-MS: m/z 557 [M + Na]+, 573 [M + K]+.
(3,4,6-Tri-O-benzyl- -D-glucopyranosyl)ethyne (18). A cooled (0°C) suspension
of sodium acetylide (16.6 mmol, 5.2 mL 18 wt% slurry in xylenes/mineral oil) in THF
(15 mL) was treated with a solution of anhydrous ZnCl2 (16.6 mL, 1 M in THF).
Almost immediately, the inhomogeneous mixture became more transparent and stirring
was continued for 15 min. Epoxide 1 (8.3 mmol, 3.6 g) was added in THF (15 mL) and