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DOI: 10.1055/s-0030-1260966
Odorless Eco-Friendly Synthesis of Thio- and Selenoglycosides in Ionic Liquid
Publication History
Publication Date:
25 July 2011 (online)
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Abstract
An environmentally benign odorless methodology for the preparation of 1,2-trans-thio- and selenoglycosides is reported. In a one-pot condition, the reductive cleavage of disulfides and diselenides using triethylsilane and borontrifluoride diethyletherate combination followed by the reaction of the in situ generated thiolate and selenoetes with glycosyl acetate derivatives in recyclable room-temperature ionic liquid, [BMIM]˙BF4 resulted in excellent yields of thio- and selenoglycosides avoiding the use of obnoxious thiols/selenols and metallic catalysts.
Key words
thioglycoside - selenoglycoside - disulfide - diselenide - triethylsilane - ionic liquid
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
Spectral data of products, which have
not been reported earlier, are presented below.
p
-Nitrophenyl
2,3,4,6-Tetra-
O
-acetyl-1-thio-β-
d
-glucopyranoside
(16)
Yellow solid; mp 180-182 ˚C; [α]D -32.7
(c 1.2, CHCl3). IR (KBr):
2923, 2368, 1753, 1344, 1220, 1042, 770 cm-¹. ¹H NMR
(200 MHz, CDCl3): δ = 8.16 (d, J = 8.9 Hz,
2 H), 7.59 (d, J = 8.8
Hz, 2 H), 5.28 (t, J = 9.2
Hz each, 1 H, H-3), 5.08 (t, J = 9.7
Hz each, 1 H, H-2), 5.04 (t, J = 9.6
Hz each, 1 H, H-4), 4.89 (d, J = 10.0
Hz, 1 H, H-1), 4.25-4.21 (m, 2 H, H-6a,b), 3.85-3.80
(m, 1 H, H-5), 2.10, 2.08, 2.04, 2.0 (4 s, 12 H, 4 COCH3). ¹³C
NMR (50 MHz, CDCl3): δ = 170.2, 169.9, 169.2,
169.0, 147.6, 141.6, 131.7 (2 C), 124.1 (2 C), 84.6, 76.6, 74.0,
70.0, 68.3, 62.2, 21.0, 20.9, 20.8 (2 C). ESI-MS: m/z = 508.1 [M + Na]+.
Anal. Calcd for C20H23NO11S (485.10):
C, 49.48; H, 4.78. Found: C, 49.25; H, 5.0.
Benzyl
2,3,4,6-Tetra-
O
-acetyl-1-seleno-β-
d
-gluco-pyranoside
(31)
Yellow oil; [α]D
²5 -30
(c 1.5, CHCl3). IR (neat):
2934, 1769, 1357, 1242, 1074, 764 cm-¹. ¹H
NMR (300 MHz, CDCl3):
δ = 7.40-7.21
(m, 5 H, ArH), 5.88 (d, J = 8.5
Hz, 1 H), 5.27 (t, J = 9.5
Hz each, 1 H), 5.06-4.89 (m, 2 H), 4.34-4.19 (m, 2
H), 3.90 (d, J = 11.1
Hz, 1 H), 3.83-3.67 (ABq, J = 12.0 Hz,
2 H), 2.08, 2.02, 1.99 (3 s, 12 H, 4 COCH
3). ¹³C
NMR (50 MHz, CDCl3): δ = 171.0, 170.8,
169.9 (2 C), 135.0-127.0 (ArC), 78.8, 76.3, 71.7, 71.2,
69.9, 68.6, 62.0, 26.6, 21.0, 20.9 (2 C). ESI-MS: m/z = 525.0 [M + Na]+.
Anal. Calcd for C21H26O9Se (502.07):
C, 50.31; H, 5.23. Found: C, 50.08; H, 5.50.
Benzyl 2,3,4,6-Tetra-
O
-acetyl-1-seleno-α-
d
-manno-pyranoside
(33)
Yellow oil; [α]D
²5 +126.8
(c 1.0, CHCl3). IR (neat):
2972, 2362, 1742, 1598, 1373, 1246, 1107, 1050, 977, 756 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.28-7.09
(m, 5 H, ArH), 5.35 (br s, 1 H, H-2), 5.24 (br s, 1 H, H-1), 5.20-5.16
(m, 2 H, H-3 and H-4), 4.24-4.20 (m, 2 H, H-6ab),
3.91-3.85 (m, 1 H, H-5), 3.77-3.73 (ABq, J = 12.0 Hz,
2 H, CH2Ph), 2.07, 2.03, 1.98, 1.90 (4 s, 12 H, 4 COCH3). ¹³C
NMR (50 MHz, CDCl3): δ = 170.2, 169.4
(2 C), 169.3, 137.6, 128.6 (2 C), 128.3 (2 C), 126.8, 77.6, 71.4,
70.6, 69.7, 65.8, 61.8, 27.4, 20.5, 20.4, 20.3, 20.2. ESI-MS: m/z = 525 [M + Na]+.
ESI-MS: m/z = 525.0 [M + Na]+.
Anal. Calcd for C21H26O9Se (502.07):
C, 50.31; H, 5.23. Found: C, 50.09; H, 5.52.
Benzyl 2,3,4-Tri-
O
-acetyl-1-seleno-α-
l
-rhamno-pyranoside (36)
Yellow
oil; [α]D
²5 -114
(c 1.2, CHCl3). IR (neat):
2367, 1756, 1600, 1366, 1230, 955 cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 7.28-7.14
(m, 5 H, ArH), 5.34 (br s, 1 H, H-1), 5.32-5.30 (m, 1 H,
H-2), 5.18 (dd, J = 9.7,
3.0 Hz, 1 H, H-3), 5.04 (t, J = 9.7
Hz each, 1 H, H-4), 4.12-4.02 (m, 1 H, H-5), 3.83 (ABq, J = 12.2 Hz,
2 H, PhCH2), 2.08, 2.01, 1.93 (3 s, 9 H, 3 COCH3),
1.18 (d, J = 6.2
Hz, 1 H, CCH3). ESI-MS: m/z = 467.0 [M + Na]+.
Anal. Calcd for C19H24O7Se (444.07):
C, 51.47; H, 5.46. Found: C, 51.25; H, 5.70.
Benzyl 2,3,4,6-Tetra-
O
-acetyl-α-
d
-glucopyranosyl-(1→4)-2,3,6-tri-
O
-acetyl-1-seleno-β-
d
-glucopyranoside (39)
Yellow
oil; [α]D
²5 +51
(c 1.0, CHCl3). IR (neat):
3023, 1764, 1418, 1257, 1086, 769 cm-¹. ¹H
NMR (400 MHz, CDCl3):
δ = 7.32-7.20
(m, 5 H, ArH), 5.40-5.23 (m, 2 H), 5.18-5.09 (m,
1 H), 5.06-4.88 (m, 2 H), 4.86-4.76 (m, 1 H),
4.54-4.49 (m, 1 H), 4.46-4.38 (m, 1 H), 4.26-4.16
(m, 2 H), 4.06-3.82 (m, 5 H), 3.58-3.49 (m, 1
H), 2.13, 2.07, 1.99, 1.96, 1.95, 1.94 (6 s, 21 H, 7 COCH3).
ESI-MS: m/z = 813.1 [M + Na]+. Anal.
Calcd for C33H42O17Se (790.16):
C, 50.19; H, 5.36. Found: C, 50.0; H, 5.60.
Phenyl
2,3,4,6-Tetra-
O
-acetyl-β-
d
-galactopyranosyl-(1→4)-2,3,6-tri-
O
-acetyl-1-seleno-β-
d
-glucopyranoside (40)
Yellow
oil; [α]D
²5 +9
(c 1.0, CHCl3). IR (neat):
3036, 1790, 1432, 1276, 1094, 766 cm-¹. ¹H
NMR (400 MHz, CDCl3):
δ = 7.56-7.26
(m, 5 H, ArH), 5.30-5.28 (m, 1 H), 5.16 (t, J = 9.1 Hz
each, 1 H), 5.05 (dd, J = 7.3
Hz each, 1 H), 4.94-4.82 (m, 3 H), 4.51-4.46 (m,
1 H), 4.42 (d, J = 7.9
Hz, 1 H), 4.12-4.02 (m, 3 H), 3.85-3.81 (m, 1
H), 3.70 (t, J = 9.1
Hz each, 1 H), 3.62-3.56 (m, 1 H), 2.13, 2.07, 2.05, 2.01,
2.0, 1.94 (6 s, 21 H, 7 COCH3). ESI-MS: m/z = 799.1 [M + Na]+. Anal.
Calcd for C32H40O17Se (776.14):
C, 49.55; H, 5.20. Found: C, 49.32; H, 5.50.
Benzyl 2,3,4,6-Tetra-
O
-acetyl-β-
d
-galactopyranosyl-(1→4)-2,3,6-tri-
O
-acetyl-1-seleno-β-
d
-glucopyranoside (41)
Yellow
oil; [α]D
²5 +21
(c 1.0, CHCl3). IR (neat):
3023, 1767, 1424, 1281, 1089, 769 cm-¹. ¹H
NMR (400 MHz, CDCl3):
δ = 7.30-7.27
(m, 5 H, ArH), 5.40-5.28 (m, 2 H), 5.20-4.88 (m,
4 H), 4.54-4.44 (m, 2 H), 4.22-4.06 (m, 4 H),
4.02-3.86 (m, 2 H), 3.82-3.70 (m, 1 H), 3.56-3.48
(m, 1 H), 2.17, 2.15, 2.14, 2.06, 2.03, 2.0, 1.97 (7 s, 21 H, 7
COCH3). ESI-MS:
m/z = 813.1 [M + Na]+.
Anal. Calcd for C33H42O17Se (790.16):
C, 50.19; H, 5.36. Found: C, 50.0; H, 5.58.