5
296
T. Uchiyama et al. / Tetrahedron Letters 57 (2016) 5294–5296
J = 11.0 Hz); 13C NMR (125 MHz,
To remove the TMS groups, the crude product was treated with acidic resin
(
D
2
O, d) 78.0, 70.3, 70.2; HRESIMS m/z
+
+
Dowex 50 W, H form) in MeOH (15 mL), the reaction could be monitored by
TLC, and the reaction was normally finished within 1 h. After filtration of the
resin and concentration, the residue was purified by silica gel column
chromatography (CHCl
powder.
3
/MeOH = 20:1–4:1) to afford final product as white
Compound 1 (1,5-anhydro-
.0, H
O); 1H NMR (600 MHz, D
d, J = 11.5 Hz), 3.48 (1H, br dd, J = 4.5, 11.5 Hz), 3.39 (1H, m), 3.24 (1H, m), 3.15
D
-glucitol, 1,5-AG): mp 139–140 °C; [
D
a] +38.9 (c
1
2
2
O, d) 3.78 (1H, dd, J = 5.5, 11.0 Hz), 3.68 (1H, br
1
3
(
7
1
2H, m), 3.08 (1H, t, J = 11.0 Hz); C NMR (125 MHz, D
2
O, d), 81.1, 78.3, 70.5,
0.2, 69.6, 61.7; HRESIMS m/z 187.0581 [M+Na] (calcd for Na,
87.0582).
+
6 12 5
C H O
Compound 2 (1,5-anhydro-
O); 1H NMR (600 MHz, D
J = 3.5 Hz), 3.64 (1H, ddd, J = 5.5, 10.0, 10.0 Hz), 3.55–3.48 (2H, m), 3.38 (2H,
D
-galactitol): mp 125–126 °C; [
a
]
D
+78.7 (c 1.0,
19. Multi-gram preparation of 1 from D-glucose: To a stirred solution of D-glucose
H
2
2
O, d) 3.80 (1H, dd, J = 5.5, 11.0 Hz), 3.76 (1H, d,
1
3
m), 3.00 (1H, t, J = 11.0 Hz); C NMR (125 MHz, D
2
O, d) 80.2, 74.9, 70.0, 69.9,
7.5, 62.2; HRESIMS m/z 187.0580 [M+Na]+ (calcd for C
Na, 187.0582).
À48.2 (c 1.0,
O, d) 3.79 (1H, br t, J = ꢀ0.5 Hz), 3.74 (1H, dd,
J = 2.0, 12.5 Hz), 3.70 (1H, dd, J = 2.5, 12.5 Hz), 3.50 (1H, dd, J = 7.0, 12.5 Hz),
.45 (2H, m), 3.40 (1H, t, J = 9.5 Hz), 3.11 (1H, ddd, J = 2.5, 7.0, 9.5 Hz); 13C NMR
125 MHz, D O, d) 81.3, 74.3, 70.6, 69.9, 68.1, 62.0; HRESIMS m/z 187.0582 [M
Na]+ (calcd for C
Na, 187.0582).
-rhamnitol): mp 120–122 °C; [
NMR (600 MHz, CD OD, d) 3.84–3.82 (2H, m), 3.52 (1H, br d,
J = 13.0 Hz), 3.41 (1H, dd, J = 3.5, 9.5 Hz), 3.34–3.30 (1H, overlapped with
solvent), 3.14 (1H, dq, J = 6.0, 9.5 Hz), 1.26 (3H, d, J = 6.0 Hz); 13
NMR
OD, d) 78.9, 76.4, 75.1, 72.1, 71.8, 19.1; HRESIMS m/z 171.0632
M+Na] (calcd for C Na, 171.0633).
(1,5-anhydro- -fucitol): mp 118–120 °C;
MeOH); 1H NMR (600 MHz, CD
OD, d) 3.84 (1H, dd, J = 5.5, 11.0 Hz), 3.74
1H, m), 3.62 (1H, br d, J = 3.5 Hz), 3.50 (1H, br q, J = 6.5 Hz), 3.37 (1H, dd,
6
6
H
12
O
5
Compound 3 (1,5-anhydro-D-mannitol): mp 153–155 °C; [a]
D
H
2
O); 1H NMR (600 MHz, D
2
(20.5 g, 0.114 mol) in dry pyridine (100 ml), trimethylsilyl chloride (79 mL,
0.627 moL) was slowly added at rt under Ar atmosphere and the reaction
mixture was stirred for 4 h at rt. n-Hexane (400 ml) and crushed ice (100 mL)
were added to the reaction mixture successively, and the organic layer was
3
(
2
+
6 12 5
H O
Compound 4 (1,5-anhydro-
L
a
]
D
+82.8 (c 1.0,
extracted with iced water (100 mL Â 4), dried over Na
vacuo to afford per-O-TMS-glycoside as an oil in quantitative yield. To a
solution of the per-O-TMS-glycoside (0.114 mmol) in dry CH Cl (100 mL),
trimethylsilyl iodide (16 mL, 0.114 mmol) was added at rt under Ar
atmosphere and the reaction mixture was stirred for 0.5 h. Then, 3 mol LiBH
2 4
SO , and evaporated in
H
2
O); 1
H
3
2
2
C
(
[
125 MHz, CD
3
4
+
6
H
12
O
4
solution (76 mL, 0.228 mmol) in THF was added to the reaction mixture, and
stirred for another 4 h at rt. n-Hexane (300 ml) and crushed ice (100 mL) were
slowly added to the reaction mixture successively, and the organic layer was
Compound
5
L
[
a
]
D
À62.4 (c 1.0,
3
(
extracted with iced water (100 mL Â 5) to neutralize, dried over Na
2 4
SO , and
1
3
J = 3.5, 9.5 Hz), 3.07 (1H, t, J = 11.0 Hz), 1.21 (3H, d, J = 6.5 Hz); C NMR
evaporated in vacuo to afford crude product as an oil. To remove the TMS
groups, the crude product was treated with acidic resin (Dowex 50 W, H+ form)
in MeOH (100 mL), the reaction monitored by TLC was finished within 1 h.
After filtration of the resin and concentration, recrystallization from MeOH of
the residue gave 1 (14.4 g, 77%) as colorless crystalline material.
(
125 MHz, CD
3
OD, d) 77.5, 77.3, 74.3, 72.0, 69.0, 17.9; HRESIMS m/z 171.0631
+
[
M+Na] (calcd for C Na, 171.0633).
6 12 4
H O
Compound 6 (1,5-anhydroxylitol): mp 86–89 °C; 1H NMR (600 MHz, D
O, d)
.75 (2H, dd, J = 5.0, 11.0 Hz), 3.38 (2H, m), 3.20 (1H, t, J = 9.5 Hz), 3.03 (2H, t,
2
3