Job/Unit: B11815
/KAP1
Date: 12-04-12 16:11:20
Pages: 13
Disaccharide-Containing Macrocycles
H, major isomer), 4.76–4.63 (m, 5 benzylic H for each major and
minor isomer, 1 H, benzylic H for minor isomer), 4.61–4.53 (m, 2
H, benzylic H for each major and minor isomer), 4.52–04.50 (m, 1
H, for 1b-H major isomer, J = 5.6 Hz and 1b-H for minor isomer
J = 9.2 Hz), 4.48–4.34 (m, 2 benzylic H for each major and minor
isomer, 1 H, benzylic H for major isomer), 4.30 (d, J = 4.8 Hz, 1
H, 1a-H, minor isomer), 4.25 (d, J = 12.8 Hz, 1 H, benzylic H,
minor isomer), 4.19 (d, J = 3.2 Hz, 1 H, 1a-H, major isomer), 4.10
(d, J = 12.0 Hz, 1 H, benzylic H, minor isomer), 4.06 (dd, J = 12.8,
2.4 Hz, 1 H, 6a-H, major isomer), 3.96 (dd, J = 9.2 Hz, 1 H, 3b-
H, minor isomer), 3.88 (m, 1 H, 5b-H, minor isomer), 3.86 (m, 1
H, 5a-H, minor isomer), 3.82 and 3.80 (each dd, each J = 9.2 Hz,
3b-H, 3a-H, major isomer), 3.72 (dd, J = 10.4, 5.6 Hz, 4a-H, minor
isomer), 3.60–3.40 (m, 13 H, 5b-H, major isomer, 4b-H, major iso-
mer, 3a-H, minor isomer, 5a-H, major isomer, 4a-H, major isomer,
2a-H major isomer, 4b-H, minor isomer, 6b-H, minor isomer, 6b-
H, 6aЈ-H, 6bЈ-H, major isomer), 3.32–3.31 (m, 4 H, 2a-H of minor
isomer merged with OCH3 of major isomer), 3.28 (s, 3 H, OCH3,
minor isomer), 3.23 (dd, J = 9.2, 3.6 Hz, 1 H, 2b-H, major iso-
mer) ppm. 13C NMR (100 MHz): δ = 145.31, 145.30, 139.35,
139.31, 139.03, 138.68, 138.38, 138.33, 138.22, 138.13, 138.10,
138.06, 136.72, 133.03, 132.07, 131.81, 131.69, 131.35, 131.23,
129.62, 129.34, 129.19, 128.92, 128.46, 128.41, 128.37, 128.35,
128.32, 128.21, 128.03, 127.99, 127.95, 127.72, 127.60, 127.55,
127.40, 127.38, 127.22, 124.65, 123.47 (Ar-C, major and minor iso-
mer), 101.61 (C-1b, minor isomer), 98.34 (C-1b, major isomer),
97.74, (C-1a, minor isomer), 97.13, (C-1a, major isomer), 85.41,
81.92, 81.91, 80.41, 80.26, 80.25, 78.96, 78.85, 78.19, 77.84, 75.83,
75.33, 75.32, 74.97, 74.90, 74.46, 73.63, 73.38, 73.33, 73.25, 72.08,
71.29, 71.12, 70.44, 69.48, 69.09, 68.83, 66.17 (C-6b, minor isomer),
65.65 (C-6a, major isomer), 55.54 (OCH3, major isomer), 55.06
(OCH3, minor isomer), 52.69 (NCH2Ar, minor isomer), 52.05
(NCH2Ar, major isomer) ppm. HRMS (+ mode): calcd. for
C59H65N3O11 [M + H]+ 990.4541; found 990.4547.
74.64, 73.45, 73.34 and 72.86 (OCH2Ar), 69.20 (C-6a), 68.95 (C-
6b), 68.74 (C-4b), 65.44 (CH2Ar), 55.08 (OCH3), 53.99
(NCH2Ar) ppm. HRMS (+ mode): calcd. for C59H65N3O11 [M +
H]+ 990.4541; found 990.4167.
70β: Rf = 0.41 (30% EtOAc/toluene). [α]2D5 = –9.4 (c = 1, CHCl3).
1H NMR (CDCl3, 400 MHz): δ = 7.70 (s, 1 H, triazole H), 7.32
(m, 23 H, Ar-H), 7.12 (dd, J = 8.0, 1.6 Hz, 2 H, Ar-H), 6.98 (d, J
= 8.0 Hz, 1 H, Ar-H), 6.63 (s, 1 H, Ar-H), 5.72 (d, J = 12.0 Hz, 1
H, benzylic H), 5.35 (d, J = 12.8 Hz, 1 H, benzylic H), 5.20 (d, J
= 10.8 Hz, 1 H, benzylic H), 8.77–8.74 (m, 4 H, benzylic H), 4.70
(d, J = 12.0 Hz, 1 H, benzylic H), 4.61 (d, J = 12.0 Hz, 1 H, benz-
ylic H), 4.53 (d, J = 12.0 Hz, 1 H, benzylic H), 4.46 (d, J = 4.0 Hz,
1 H, 1a-H), 4.44 (d, J = 8.0 Hz, 1 H, 1b-H), 4.42 (d, J = 12.0 Hz,
1 H, benzylic H), 4.41 (d, J = 12.0 Hz, 1 H, benzylic H), 4.39 (d,
J = 12.0 Hz, 1 H, benzylic H), 4.38–4.29 (m, 4 H, 6a-H merged
with 3 benzylic H), 3.94–3.88 (m, 2 H, 3b-H, 5a-H), 3.80–3.72 (m,
2 H, 3a-H, 5-H), 3.54 (dd, J = 12.0, 1.6 Hz, 1 H, 6b-H), 3.48–3.36
(m, 4 H, 6aЈ-H, 4a-H, 2a-H, 6bЈ-H), 3.35 (d, J = 9.2 Hz, 1 H, 4a-
H), 3.27 (s, 3 H, OCH3), 3.24 (d, J = 4.0 Hz, 1 H, 2a-H) ppm. 13C
NMR (100 MHz): δ = 146.71, 140.08, 140.01, 138.82, 138.53,
138.13, 138.10, 135.57 (Ar-Cq), 128.41, 128.40, 128.39, 128.38,
128.35, 128.32, 128.31, 128.10, 127.99, 127.97, 127.75, 127.74,
127.69, 127.68, 127.35, 127.34, 125.72, 124.45, 124.03 (Ar-C),
101.28 (C-1b), 98.02 (C-1a), 82.25 (C-3b), 81.28 (C-3a), 80.67 (C-
5b), 79.21 (C-2a), 78.74 (C-4b), 78.25 (C-2b), 75.96, 75.73, 75.06,
73.51, 73.39, 72.60 (OCH2Ar), 71.21 (C-5b), 70.69 (C-4a), 69.72
(C-6a), 69.59 (C-6b), 65.01 (OCH2), 55.33 (OCH3), 53.48
(NCH2Ar) ppm. HRMS: HRMS (+ mode): calcd. for
C59H65N3O11 [M + H]+ 990.4541; found 990.4168.
Compound 77α: Compound 76 (0.4 g, 0.357 mmol) on treatment
with NIS (160 mg, 0.715 mmol) and TMSOTf (45 μL, 0.24 mmol)
in dry CH2Cl2 for 2 h and workup as described in general pro-
cedure D afforded 77α as a colourless oil (0.19 g, 55%). Rf = 0.33
(30% EtOAc/toluene). [α]2D5 = +1.5 (c = 1, CHCl3). 1H NMR
(CDCl3, 400 MHz): δ = 7.96 (d, J = 8.0 Hz, 2 H, Ar-H), 7.50–7.37
(m, 5 H, Ar-H), 7.34–7.11 (m, 22 H, triazole H, Ar-H), 7.01 (dd,
J = 8.4, 2.0 Hz, 1 H, Ar-H), 5.88 and 5.57 (each d, each J =
14.8 Hz, each 1 H, N-benzylic H), 4.85 and 4.83 (each d, each J =
10.8 Hz, each 1 H, benzylic H), 4.79 (d, J = 10.8 Hz, 1 H, benzylic
H), 4.74 (d, J = 11.2 Hz, 1 H, benzylic H), 4.72–4.66 (m, 3 H, 6a-
H merged with benzylic H), 4.66 (d, J = 12.0 Hz, 1 H, benzylic H),
4.62 (d, J = 4.0 Hz, 1 H, 1b-H), 4.57 and 4.53 (each d, each J =
12.0 Hz, each 1 H, benzylic H), 4.51–4.48 (m, 3 H, 1a-H, benzylic
H), 5.45 (d, J = 10.8 Hz, 1 H, benzylic H), 5.43 (d, J = 10.4 Hz, 1
H, benzylic H), 3.76–3.71 (m, 2 H, 5a-H, 3a-H), 3.67 (dd, J = 11.2,
2.0 Hz, 1 H, 6b-H), 3.66–3.57 (m, 3 H, 6bЈ-H, 5b-H, 4b-H), 3.55
(dd, J = 9.6 Hz, 1 H, 3b-H), 3.49–3.38 (m, 3 H, 2b-H, 2a-H, 4a-
H), 3.28 (s, 3 H, OCH3) ppm. 13C NMR (100 MHz): δ = 166.91
(COPh), 145.31, 138.61, 138.36, 138.32, 138.10, 136.02, 134.25,
133.23, 131.93, 130.28, 129.81, 127.51, 129.16, 128.92, 128.86,
128.63, 128.48, 128.45, 128.37, 128.27, 128.00, 127.93, 127.82,
127.72, 127.88, 127.59, 127.48, 123.00 (Ar-C), 97.73 (C-1b), 97.72
(C-1a), 87.12 (C-3a), 86.57 (C-3b), 81.21 (C-2b), 80.95 (C-2a),
80.12 (C-4b), 79.17 (C-4a), 76.77, 75.77, 75.59, 75.06, 73.45, 71.13
(CH2Ar), 70.39 (C-5a), 67.62 (C-5b), 66.72, 63.73 (C-6b, C-6a),
55.13 (OCH3), 50.98 (NCH2Ar) ppm. HRMS (+ mode): calcd. for
C59H63N3O12 [M + H]+ 1004.4334; found 1004.4298.
Compounds 70α and 70β: Compound 69 (250 mg, 0.227 mmol) on
treatment with NIS (101 mg, 0.455 mmol) and TMSOTf (25 μL,
0.13 mmol) in dry CH2Cl2 (15 mL) for 2 h and workup as described
in general procedure D afforded 70α and 70β as a colourless oil
(185 mg, 82%, α/β = 1:2). The two compounds were successfully
separated in pure form and characterized by their comparative
spectroscopic data.
70α: Rf = 0.32 (30% EtOAc/toluene). [α]2D5 = +27.2 (c = 1, CHCl3).
1H NMR (CDCl3, 400 MHz): δ = 7.73 (s, 1 H, triazole H), 7.30–
7.15 (m, 29 H, Ar-H), 7.12 (s, 1 H, Ar-H), 7.10 and 7.08 (each d,
each J = 8.0 Hz, each 1 H, Ar-H), 7.02 (d, J = 8.0 Hz, 1 H, Ar-
H), 5.59 and 5.22 (each d, each J = 15.2 Hz, each 1 H, N-benzylic
H), 4.98, 4.91, 4.86, 4.82, 4.79 and 4.77 (each d, each J = 12.0 Hz,
each 1 H, benzylic H), 4.71–4.65 (m, 1 H, benzylic H), 4.55 (d, J
= 12.0 Hz, 1 H, benzylic H), 4.52 (d, J = 4.0 Hz, 1 H, 1a-H), 4.49
(d, J = 4.0 Hz, 1 H, 1b-H), 4.42 (d, J = 12.0 Hz, 1 H, benzylic H),
4.35 and 4.31 (each d, each J = 12.8 Hz, each 1 H, benzylic H),
4.23 (d, J = 12.0 Hz, 1 H, benzylic H), 4.07 and 4.05 (each dd,
each J = 9.6 Hz, each 1 H, 3b-H, 3a-H), 3.93 (d, J = 9.6 Hz, 1 H,
4b-H), 3.66 (dd, J = 12.0, 4.0 Hz, 1 H, 6a-H), 3.59–3.50 (m, 2 H,
5b-H, 5a-H), 3.49 (dd, J = 8.8 Hz, 1 H, 6aЈ-H), 3.45 (d, J =
12.0 Hz, 1 H, 6b-H), 3.37–3.30 (m, 3 H, 6bЈ-H, 2a-H, 4a-H), 3.17–
3.12 (m, 4 H, 2b-H, 4a-H), 3.17–3.12 (m, 5 H, OCH3, 3b-H, 4a-
H) ppm. 13C NMR (100 MHz): δ = 139.96, 138.66, 138.18, 138.13,
138.06, 137.99, 137.93, 135.65 (Ar-Cq), 128.72, 128.49, 128.45,
128.40, 128.36, 128.26, 128.17, 127.99, 127.96, 127.84, 127.80,
127.66, 127.62, 127.59, 127.36, 127.21, 127.22, 124.04 (Ar-C), 97.72
(C-1b), 97.63 (C-1a), 86.32 (C-5b), 80.99 (C-5a), 78.43 (C-2b),
77.98 (C-2a), 75.89 (C-4a), 75.46 (C-3b), 75.38 (C-3a), 74.88, 74.79,
Supporting Information (see footnote on the first page of this arti-
cle): Synthetic methods for all donors, acceptors and intermediates
required to investigate the intramolecular glycosylation reactions
and the 1H and 13C NMR spectra of all the synthesized com-
pounds.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
11