Page 7 of 16
The Journal of Organic Chemistry
1
29.7 (Ar-C), 129.2 (Ar-C), 128.9 (Ar-C), 128.9 (Ar-C),
128.1 (Ar-C), 127.9 (Ar-C), 126.0 (Ar-C), 124.9 (C-2’),
101.4 (C-PhCH), 99.1 (C-1), 93.6 (C-1’), 82.8 (C-4), 78.1
1
2
3
4
1
1
(
28.8 (Ar-C), 128.5 (Ar-C), 128.4 (Ar-C), 128.3 (Ar-C),
28.2 (Ar-C), 125.3 (C-2’), 93.8 (C-1’), 85.9 (C-1), 77.2
C-5), 74.3 (C-3), 70.5 (C-2), 69.5 (C-4) 66.7 (C-5’) 66.5
(C-2), 73.4 (C-PhCH ), 73.1 (C-3), 69.1 (C-6), 66.4 (C-5’),
2
62.7 (C-4’), 62.2 (C-6’), 62.0 (C-5), 55.2 (OCH ), 20.8
3
+
(
C-6), 62.7 (C-6’), 62.6 (C-4’), 20.8 (COCH
COCH ). ESI-HRMS for
13SNa+ (MNa+)
calculated: 819.2087; found: 819.2103.
3
), 20.6
(COCH ), 20.70 (COCH ). ESI-HRMS for C H O Na
(MNa ) calculated: 607.2155; found: 607.2155.
3
3
31 36 11
5
+
(
3
C
43
H
40
O
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
3
-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-
6-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-hex-2-
enopyranosyl)-1,2:4,5- di-O-isopropylidene-α-D-
enopyranosyl)-l,2:5,6-di-O-isopropylidene-α-D-
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
glucofuranose (3h). Following the general glycosylation
procedure, donor 1a (50 mg, 0.18 mmol), B(C F ) (5 mg
6 5 3
0
following purification by silica gel column
chromatography (Hexane:EtOAc, 7:1 to 3:1) 3h as a
colourless oil (44 mg, 67%). H NMR (500 MHz, CDCl
δ 6.16 (ddd, J = 10.0, 5.5, 1.1 Hz, 1H, H-2’), 6.09 – 5.99
galacopyranoside (3e). Following the general
glycosylation procedure, donor 1a (50 mg, 0.18 mmol),
B(C F ) (5 mg 0.01 mmol) and acceptor 2e (36 mg, 0.14
6 5 3
mmol) to afford following purification by silica gel column
chromatography (Hexane:EtOAc, 7:1 to 4:1) 3e as a
.01 mmol) and acceptor 2h (36 mg, 0.14 mmol) to afford
1
3
)
colourless oil (49 mg, 75%). Spectroscopic data in
agreement with literature.15
(
(
m, 1H, H-3’), 5.90 (d, J = 3.6 Hz, 1H, H-1 ), 5.39 – 5.34
m, 1H, H-1’), 5.04 (dt, J = 5.5, 2.8 Hz, 1H, H-4’), 4.63 (d,
2
'-Propyn-1'-yl
4,6-di-O-acetyl-2,3-dideoxy-α/β-D-
J = 3.6 Hz, 1H, H-2), 4.41 – 4.28 (m, 3H, H-5’, H-3, H-
a’), 4.25 – 4.18 (m, 2H, H-4, H-6b’), 4.16 – 4.08 (m, 2H,
H-5, H-6a), 3.99 (dd, J = 8.6, 5.1 Hz, 1H, H-6b), 2.13 (s,
threo-hex-2-enopyranoside (3f). Following the general
glycosylation procedure, donor 1a (50 mg, 0.18 mmol),
B(C F ) (5 mg 0.01 mmol) and acceptor 2f (7.73mg,
6
3
4
H), 2.10 (s, 3H), 1.52 (s, 3H), 1.42 (s, 3H), 1.33 (d, J =
.1 Hz, 6H). 13C NMR (126 MHz, CDCl
) δ 170.8
), 170.3 (COCH ), 130.0 (C-3’), 125.4 (C-2’),
12.0 (4˚C), 109.17(4˚C), 105.4 (C-1), 94.9 (C-1’), 84.3
6
5 3
0
.14 mmol) to afford following purification by silica gel
3
(COCH
3
3
column chromatography (Hexane:EtOAc, 8:1 to 4:1) 3f as
a colourless oil (32 mg, 86%). Spectroscopic data in
agreement with literature.15
1
(C-2), 81.3 (C-4), 80.77 (C-3), 72.7 (C-5), 67.8 (C-6), 67.2
(
C-5’), 63.1 (C-6’), 62.8 (C-4’), 27.0 (CCH
6.5 (CCH ), 25.4 (CCH ), 20.8 (COCH ), 20.7 (COCH
ESI-HRMS for
495.1842; found: 495.1832.
3
), 26.9 (CCH
3
),
).
2
3
3
3
3
Methyl
3-O-(4,6-di-O-acetyl-2,3-dideoxy-α-D-threo-
22 32
C H O
11Na+ (MNa+) calculated:
hex-2-enopyranosyl)-4,6-O benzylidene 2-O-benzyl-α-
D-glucopyranoside (3g). Following the general
glycosylation procedure, donor 1a (50 mg, 0.18 mmol),
B(C F ) (5 mg 0.01 mmol) and acceptor 2g (51 mg, 0.14
6 5 3
mmol) to afford following purification by silica gel column
chromatography (Hexane:EtOAc, 5:1 to 3:1) 3g as a
4
-Methoxyphenyl,
4,6-di-O-acetyl-2,3-dideoxy-α-D-
threo-hex-2-enopyranoside (3i). Following the general
glycosylation procedure, donor 1a (50 mg, 0.18 mmol),
B(C F ) (5 mg 0.01 mmol) and acceptor 2i (17 mg, 0.14
mmol) to afford following purification by silica gel column
chromatography (Hexane:EtOAc, 9:1 to 3:1) 3i as a
1
colourless oil (55 mg, 68%) H NMR (500 MHz, CDCl
.42 (dd, J = 6.7, 2.8 Hz, 2H, Ar-H), 7.37 – 7.32 (m, 7H,
Ar-H), 7.32 – 7.29 (m, 1H, Ar-H), 6.07 (dd, J = 3.2, 1.8 Hz,
H, H-2’, H-3’), 5.54 (d, J = 2.0 Hz, 1H, H-1), 5.51 (s, 1H,
H-PhCH), 5.00 (dd, J = 4.3, 2.7 Hz, 1H, H-4’), 4.81 – 4.69
3
) δ
6
5 3
7
1
2
colourless oil (36 mg, 82%) H NMR (500 MHz, CDCl ) δ
3
7.10 – 7.05 (m, 4H, Ar-H), 6.88 – 6.83 (m, 2H, Ar-H), 6.27
(ddd, J = 9.9, 5.4, 1.0 Hz, 1H, H-2), 6.21 (dd, J = 10.0, 3.0
Hz, 1H, H-3), 5.64 (dt, J = 3.0, 0.6 Hz, 1H, H-1), 5.13 (dd,
J = 5.4, 2.5 Hz, 1H, H-4), 4.54 (ddd, J = 7.7, 5.3, 2.5 Hz,
1H, H-5), 4.29 – 4.23 (m, 2H, H-6a, H-6b), 3.80 (s, 3H,
OCH ), 2.12 (s, COCH ), 1.98 (s, 3H, COCH ). C NMR
3 3 3
(126 MHz, CDCl ) δ 170.6 (COCH ), 170.4 (COCH ),
155.2 (Ar-C), 151.0 (Ar-C), 129.9 (C-3), 125.9 (C-2),
118.8 (Ar-C), 114.5 (Ar-C), 93.7 (C-1), 67.5 (C-5), 62.6
(C-4), 62.5 (C-6), 55.7 (OCH ), 20.8 (COCH ), 20.7
(
(
m, 1H, PhCHH), 4.57 (d, J = 12.2 Hz, 1H, PhCHH), 4.54
d, J = 3.7 Hz, 1H, H-1), 4.51 – 4.46 (m, 1H, H-5’), 4.41 (t,
J = 9.4 Hz, 1H, H-3), 4.25 (ddt, J = 13.2, 7.3, 3.3 Hz, 2H,
H-6a’, H-6a), 4.05 (dd, J = 11.2, 7.2 Hz, 1H, H-6b’), 3.82
(td, J = 9.9, 4.8 Hz, 1H, H-5), 3.69 (t, J = 10.3 Hz, 1H, H-
1
3
3
3
3
6
3
6
b), 3.56 (t, J = 9.5 Hz, 1H, H-4), 3.46 (ddd, J = 13.1, 9.4,
.6 Hz, 1H, H-2), 3.35 (s, 3H, OCH ), 2.06 (d, J = 6.1 Hz,
H, 2 COCH ) δ 170.8
). 13C NMR (126 MHz, CDCl
), 170.4 (COCH ), 138.2 (Ar-C), 137.2 (Ar-C),
30.8 (C-3’), 129.0 (Ar-C), 128.4 (Ar-C), 128.3 (Ar-C),
3
3
3
(COCH
3
3
3
3
1
7
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