L. Encinas, J. L. Chiara
FULL PAPER
2.8 Hz, 2 H, 6s-H), 3.86–3.91 (m, 8 H, OCH2 ϫ3, 5Ј-H, SCH2), Supporting Information (see also the footnote on the first page of
4.02 (t, J = 9.3 Hz, 1 H, 3Ј-H), 4.32 (d, J = 9.9 Hz, 1 H, 1-H), 4.44
this article): 1H NMR of the anomerization reaction of 22b pro-
(d, J = 11.0 Hz, 1 H, PhCH2), 4.45 (d, J = 12.3 Hz, 1 H, PhCH2), moted by TMSOTf.
4.51 (d, J = 10.3 Hz, 1 H, PhCH2), 4.62 (d, J = 12.0 Hz, 1 H,
PhCH2), 4.66 (d, J = 10.3 Hz, 1 H, PhCH2), 4.67 (d, J = 11.1 Hz,
1 H, PhCH2), 4.71 (d, J = 10.8 Hz, 1 H, PhCH2), 4.74 (d, J =
Acknowledgments
We thank the Ministry of Education and Science of Spain for fin-
12.0 Hz, 1 H, PhCH2), 4.78 (d, J = 11.0 Hz, 1 H, PhCH2), 4.85 (d,
J = 11.7 Hz, 1 H, PhCH2), 4.82 (d, J = 10.6 Hz, 1 H, PhCH2), 4.84
(d, J = 10.7 Hz, 1 H, PhCH2), 4.87 (d, J = 10.7 Hz, 1 H, PhCH2),
4.93 (d, J = 10.8 Hz, 1 H, PhCH2), 5.14 (d, J = 3.3 Hz, 1 H, 1Ј-
H), 6.50 (s, 2 H, Ar-H), 7.09–7.41 (m, 35 H, Ar-H) ppm. 13C NMR
(125 MHz, CDCl3): δ = 14.2 (CH3), 22.7, 26.2, 29.4, 29.5, 29.5,
29.7, 29.7, 31.9, 34.7 (SCH2), 65.4 (C6), 68.4 (C6Ј), 69.0
(OCH2 ϫ2), 70.0 (C5Ј), 72.2 (PhCH2), 73.3 (PhCH2), 73.4 (OCH2),
74.8 (PhCH2), 75.0 (PhCH2), 75.3 (PhCH2), 75.5 (PhCH2), 75.6
(PhCH2), 77.4 (C4Ј), 77.6 (C4), 78.9 (C5), 80.0 (C2Ј), 81.6 (C2),
81.7 (C3Ј), 83.2 (C1), 86.4 (C3), 97.0 (C1Ј), 107.2 (ArCH), 127.4,
127.6, 127.9, 128.0, 128.1, 128.2, 128.3, 128.3, 128.3, 128.4, 128.4,
132.3, 137.1, 137.9, 137.9, 138.1, 138.4, 138.5, 138.5, 138.7, 153.0
ppm. C110H154O13S (1716.46): calcd. C 76.97, H 9.04, S 1.87; found
C 76.86, H 8.95, S 1.73.
ancial support (project CTQ-2006-15515-C02-02/BQU) and for a
FPU predoctoral fellowship to L. E.
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6-O-(2,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl)-3,4,5-tris(tretrade-
cyloxy)benzyl 2,3,4-Tri-O-benzyl-1-thio-α-
D-glucopyranoside (24ba):
1
Colorless solid; m.p. 57–58 °C. H NMR (500 MHz, CDCl3): δ =
0.88 (t, J = 7.0 Hz, 9 H, CH3), 1.26 [br. s, 60 H, (CH2)10], 1.38–
1.49 (m, 6 H, OCH2CH2CH2), 1.69–1.77 (m, 6 H, OCH2CH2), 3.43
(ddd, J = 9.4, J = 4.8, J = 1.8 Hz, 1 H, 5Ј-H), 3.50 (dd, J = 9.0, J
= 7.8 Hz, 1 H, 2Ј-H), 3.56–3.65 (m, 5 H, 4-H, 4Ј-H, 3Ј-H, SCH2),
3.68 (dd, J = 10.9, J = 4.8 Hz, 1 H, 6Ј-H), 3.73 (dd, J = 9.6, J =
5.5 Hz, 1 H, 2-H), 3.74 (dd, J = 10.8, J = 1.6 Hz, 1 H, 6Ј-H), 3.78
(dd, J = 11.2, J = 4.6 Hz, 1 H, 6-H), 3.84 (t, J = 9.4 Hz, 1 H, 3-
H), 3.83–3.93 (m, 6 H, OCH2 ϫ3), 4.21 (dd, J = 11.1, J = 1.7 Hz,
1 H, 6-H), 4.34 (ddd, J = 10.1, J = 4.4, J = 1.7 Hz, 1 H, 5-H), 4.39
(d, J = 7.8 Hz, 1 H, 1Ј-H), 4.39 (d, J = 11.7 Hz, 1 H, PhCH2), 4.48
(d, J = 11.7 Hz, 1 H, PhCH2), 4.50 (d, J = 11.1 Hz, 1 H, PhCH2),
4.53 (d, J = 10.9 Hz, 1 H, PhCH2), 4.54 (d, J = 12.2 Hz, 1 H,
PhCH2), 4.61 (d, J = 12.2 Hz, 1 H, PhCH2), 4.69 (d, J = 11.0 Hz,
1 H, PhCH2), 4.72 (d, J = 11.1 Hz, 1 H, PhCH2), 4.77 (d, J =
11.0 Hz, 1 H, PhCH2), 4.78 (d, J = 11.0 Hz, 1 H, PhCH2), 4.81 (d,
J = 11.3 Hz, 1 H, PhCH2), 4.90 (d, J = 10.9 Hz, 1 H, PhCH2), 4.93
(d, J = 10.9 Hz, 1 H, PhCH2), 4.97 (d, J = 11.0 Hz, 1 H, PhCH2),
5.26 (d, J = 5.5 Hz, 1 H, 1-H), 6.51 (s, 2 H, Ar-H), 7.15–7.34 (m,
35 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 14.1 (CH3),
22.7, 26.1, 29.4, 29.4, 29.4, 29.5, 29.6, 29.7, 29.7, 29.8, 29.8, 30.3,
31.9, 33.6 (SCH2), 68.5 (C6), 68.9 (C6Ј), 69.0 (OCH2 ϫ2), 70.9
(C5), 71.6 (PhCH2), 73.4 (PhCH2), 73.4 (OCH2), 74.9 (PhCH2),
75.0 (C5Ј), 75.6 (PhCH2), 75.7 (PhCH2), 77.6 (C4), 77.8 (C4Ј), 78.8
(C2), 82.0 (C2Ј), 82.1 (C1), 82.5 (C3), 84.8 (C3Ј), 103.8 (C1Ј), 107.2
(ArCH), 127.5, 127.6, 127.6, 127.6, 127.7, 127.7, 127.7, 127.7,
127.8, 127.9, 127.9, 128.0, 128.3, 128.3, 128.3, 128.4, 128.4, 133.0,
137.0, 137.5, 138.0, 138.1, 138.2, 138.3, 138.4, 138.7, 153.0 ppm.
C110H154O13S (1716.46): calcd. C 76.97, H 9.04, S 1.87; found C
76.86, H 8.95, S 1.73.
6-O-(2,3,4,6-Tetra-O-benzyl-β-D-glucopyranosyl)-3,4,5-tris(tretrade-
cyloxy)benzyl 2,3,4-Tri-O-benzyl-1-thio-β-D-glucopyranoside (24bb):
1H NMR (500 MHz, CDCl3): δ = 0.88 (t, J = 7.0 Hz, 9 H, CH3),
1.25 [br. s, 60 H, (CH2)10], 1.38–1.45 (m, 6 H, OCH2CH2CH2),
1.69–1.75 (m, 6 H, OCH2CH2), 3.41–3.96 (m, 20 H), 4.20 (d, J =
9.5 Hz, 1 H), 4.38 (d, J = 9.8 Hz, 1 H, 1-H), 4.41 (d, J = 7.8 Hz,
1 H, 1Ј-H), 4.50–5.03 (m, 14 H, PhCH2), 6.43 (s, 2 H, Ar-H), 7.13–
7.47 (m, 35 H, Ar-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 83.9
(C1), 104.2 (C1Ј), 107.2 ppm.
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2172
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