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0 0
C-1), 53.41 (C-1 ), 23.15 (C-2 ). HRMS (ESP): calcd for 2 equiv.) and acetic acid (0.007 mL, 0.120 mmol, 2 equiv.) were
(
+
C H ClNO [M + H] : 402.1467; found: 402.1467.
added. The reaction mixture was reuxed overnight. Aer that,
2
2
25
4
9
-Chloro-10-(3-methoxyallyl)anthracene (13). To a mixture of the solvent was evaporated, and the residue was puried by
+
ꢁ
Ph P CH OCH Cl (158 mg, 0.447 mmol, 1.5 equiv.) in dry THF ash chromatography (CHCl , then CHCl /MeOH 8/1) to give 15
3
2
3
3
3
ꢀ
(
1
10 mL) under nitrogen at 0 C, n-BuLi (0.28 mL, 0.447 mmol, (23 mg, 82%) as a yellow solid.
.5 equiv., 1.6 M in hexane) was added dropwise. The reaction
1
R
f
¼ 0.50 (DCM/MeOH: 7/1). H NMR (DMSO-d
6
, 500 MHz):
ꢀ
3
3
0
mixture was stirred at 0 C for 20 min, then a solution of 2-(10- d 8.47 (t, 4H, JHa,Hb ¼ JHa
0
,Hc ¼ 8.8 Hz, 2 ꢂ H-a, 2 ꢂ H-a ), 7.74
chloroanthracen-9-yl)acetaldehyde (11) (76 mg, 0.298 mmol, (m, 2H, 2 ꢂ H-b), 7.65 (m, 2H, 2 ꢂ H-c), 4.70 (m, 2H, C3–OH,
3
1
equiv.) was added. The reaction mixture was stirred at room C4–OH), 4.67 (d, 1H,
J
H2,OH ¼ 4.5 Hz, C2–OH), 4.36 (t, 1H,
3
temperature overnight. Aer that, the reaction mixture was
ltered to remove triphenylphosphine oxide. Water and diethyl H-6, 2 ꢂ H-3 ), 3.33–3.30 (m, 1H, H-2), 3.14–3.05 (m, 2H, H-1 ,
JH6,OH ¼ 5.1 Hz, C6–OH), 3.85 (m, 1H, H-6), 3.67–3.49 (m, 3H,
0
0
0
ether were added and the aqueous phase was extracted with H-4), 2.98–2.85 (m, 2H, H-3, H-1), 2.71 (m, 1H, H-1 ), 2.01–1.72
0
13
diethyl ether. The combined organic layers were dried over (m, 4H, H-5, H-1, 2 ꢂ H-2 ). C NMR (DMSO-d
6
, 125 MHz):
), 127.20(2C) (2 ꢂ C-b),
quat
MgSO
4
, ltered and concentrated under vacuum. The residue d 129.51(3C), 127.94(3C) (6 ꢂ C
was puried by ash chromatography (PE/DCM: 3/1) to give the Z 126.14(2C) (2 ꢂ C-c), 125.17(2C) (2 ꢂ C-a), 124.66(2C) (2 ꢂ C-
0
isomer (15 mg, 18%) and E isomer (30 mg, 35%) as yellow solids. a ), 79.17 (C-3), 71.02 (C-4), 69.50 (C-2), 66.87 (C-5), 59.58 (C-6),
1
0 0 0
Z isomer: R
d 8.58 (d, 2H, J
f
¼ 0.67 (PE/DCM: 3/2) H NMR (CDCl
3
, 500 MHz): 57.17 (C-1), 52.06 (C-1 ), 26.90 (C-2 ), 25.44 (C-3 ). HRMS (ESP):
3
3
+
¼ 8.8 Hz, 2 ꢂ H-a), 8.40 (d, 2H, J
0
¼
calcd for C H ClNO [M + H] : 416.1629; found: 416.1632.
23 27 4
Ha,Hb
Ha ,Hc
0
9
.0 Hz, 2 ꢂ H-a ), 7.62–7.55 (m, 4H, 2 ꢂ H-b, 2 ꢂ H-c), 5.98 (d, 1H,
2,3,4,6-Tetra-O-tert-butyldimethylsilyl-D-glucono-d-lactam (17).
3
J ¼ 6.0 Hz, CHOCH ), 4.57 (m, 1H, CHCHOCH ), 4.39 (m, 2H, Lactam 16 (70 mg, 0.393 mmol, 1 equiv.) and DMAP (9.6 mg,
3
3
1
3
2
ꢂ CHCHCHOCH
3
), 3.79 (s, 3H, OCH
3
). C NMR (CDCl
3
, 125 0.079 mmol, 0.2 equiv.) were dissolved in pyridine (10 mL). The
), 133.88(2C), 130.29(2C), 128.90(2C) solution was cooled to 0 C, and tert-butyldimethylsilyl triate
ꢀ
MHz): d 146.09 (CHOCH
3
quat
(
(
(
6 ꢂ C ), 126.45(2C) (2 ꢂ C-b), 125.82(2C) (2 ꢂ C-c), 125.64(2C) (0.828 mL, 3.54 mmol, 9 equiv.) was added. The reaction mixture
0
ꢀ
3
), 55.99 was heated to 60 C and stirred overnight. Then methanol was
2 ꢂ C-a), 125.25(2C) (2 ꢂ C-a ), 105.25 (CHCHOCH
CHCHCHOCH ), 23.29 (OCH ). HRMS (ESP): calcd for C18
3
3
H
15
-
added, and the solution was diluted with ethyl acetate. The
+
ClONa [M + Na] : 305.0709; found: 305.1090.
organic phase was washed with water (3 ꢂ 20 mL). The combined
1
E isomer: R ¼ 0.57 (PE/DCM: 3/2). H NMR (CDCl , 500 MHz): organic layers were dried over MgSO , ltered and concentrated
f
3
3
4
3
d 8.58 (d, 2H, J
¼ 8.9 Hz, 2 ꢂ H-a), 8.30 (d, 2H, J
0
¼
under vacuum. The residue was puried by ash chromatography
Ha,Hb
Ha ,Hc
0
8
.8 Hz, 2 ꢂ H-a ), 7.62–7.54 (m, 4H, 2 ꢂ H-b, 2 ꢂ H-c), 6.33 (d, 1H, (PE/EtOAc: 30/1, then 20/1) and afforded lactam 17 (150 mg, 60%)
3
1
J ¼ 13.1 Hz, CHOCH
ꢂ CHCHCHOCH ), 3.42 (s, 3H, OCH
MHz): d 148.68 (CHOCH ), 139.59(2C), 130.17(2C), 128.77(2C) (m, 1H, H-6), 3.65 (m, 1H, H-5), 3.56 (m, 1H, H-4), 3.49 (dd, 1H,
3
), 5.07 (m, 1H, CHCHOCH
3
), 4.25 (m, 2H, as a white solid. R
f
¼ 0.50 (PE/EtOAc: 10/1). H NMR (CDCl
3
, 500
1
3
3
2
3
3
). C NMR (CDCl
3
, 125 MHz): d 3.96 (m, 1H, H-3), 3.86 (d, 1H, JH2,H3 ¼ 3.3 Hz, H-2), 3.79
3
quat
3
2
(
(
5
6 ꢂ C ), 126.35(2C) (2 ꢂ C-b), 125.93(2C) (2 ꢂ C-c), 125.61(2C)
J
H5,H6 ¼ 8.4 Hz, JH6,H6
0
¼ 10.3 Hz, H-6), 0.88 (s, 9H, C(CH
3 3
) ), 0.87
0
2 ꢂ C-a), 124.85(2C) (2
ꢂ C-a ), 101.19 (CHCHOCH ), (br, 18H, 2 ꢂ C(CH ) ), 0.85 (s, 9H, C(CH ) ), 0.13, 0.12, 0.10, 0.08,
3
3 3
3 3
13
5.90 (CHCHCHOCH ), 26.35 (OCH ). HRMS (ESP): calcd for 0.07, 0.06 (6s, 18H, 6 ꢂ SiCH ), 0.05 (s, 6H, 2 ꢂ SiCH ). C NMR
3
+
3
3
3
C H ClONa [M + Na] : 305.0709; found: 305.2644.
(CDCl , 125 MHz): d 171.28 (NCOCH), 77.92 (C-2), 74.87 (C-3),
3
1
8
15
3
-(10-Chloroanthracen-9-yl)propanal (14). A solution of the E 73.83 (C-4), 58.32 (C-5), 63.86 (C-6), 25.93(3C), 25.85(6C),
isomer of the enol ether 13 (30 mg, 0.106 mmol, 1 equiv.) in 25.80(3C) (12 ꢂ C(CH )), 18.32, 18.22, 18.01, 17.96 (4 ꢂ C(CH ),
diethyl ether (2 mL) was added dropwise to a pre-cooled mixture ꢁ3.72, ꢁ4.12, ꢁ4.53, ꢁ4.74, ꢁ4.86, ꢁ5.06, ꢁ5.25, ꢁ5.29 (8 ꢂ
3
3 3
)
+
4 2 3 5 4
of 70% HClO (0.053 mL, 0.424 mmol, 4 equiv.), H O (0.053 mL) SiCH ). HRMS (ESP): calcd for C30H68NO Si [M + H] : 635.2160;
and diethyl ether (1 mL). The reaction mixture was then reuxed found: 635.3584.
ꢀ
at 40 C. Aer being stirred for 2 h, the reaction mixture was
N-(10-Chloro-9-anthracenemethyl)-2,3,4,6-tetra-O-tert-butyl-
cooled to room temperature, then sat. NaHCO was added to dimethylsilyl-D-glucono-d-lactam (18). To a solution of 17
3
neutralize the acid. The aqueous phase was extracted with (75 mg, 0.118 mmol, 1 equiv.) in THF (5 mL), sodium hydride
dichloromethane. The combined organic layers were dried over (9.5 mg, 0.236 mmol, 2 equiv., 60% in mineral oil) was added
MgSO
was puried by ash chromatography (PE/DCM: 3/1, then 2/1) Tetrabutylammonium iodide (8.7 mg, 0.024 mmol, 0.2 equiv.)
to give aldehyde 14 (21 mg, 78%) as a yellow solid. R
¼ 0.25 was added, followed by dropwise addition of 10-chloro-9-
, 500 MHz): d 9.89 (br, 1H, anthracenemethyl chloride (9, 62 mg, 0.236 mmol, 2 equiv.).
¼ 9.2 Hz, 2 ꢂ H-a), 8.16 (d, 2H, The reaction mixture was stirred at room temperature overnight.
4
, ltered and concentrated under vacuum. The residue portionwise under nitrogen. The mixture was stirred for 15 min.
f
1
(
PE/DCM: 3/2). H NMR (CDCl
3
3
CH CH CHO), 8.53 (d, 2H, J
2
2
Ha,Hb
3
0
J
0
¼ 9.2 Hz, 2 ꢂ H-a ), 7.57–7.50 (m, 4H, 2 ꢂ H-b, 2 ꢂ H-c), Water was added slowly and the mixture was extracted with
Ha ,Hc
3
.88 (m, 2H, 2 ꢂ CHCH CHO), 2.89 (m, 2H, 2 ꢂ CH CHCHO).
diethyl ether (3 ꢂ 30 mL). The combined organic layers were
dried over MgSO , ltered and concentrated under vacuum. The
15). A mixture of 1-DNJ (1, 10 mg, 0.060 mmol, 1 equiv.) and residue was puried by ash chromatography (PE/DCM: 5/1, then
aldehyde 14 (16 mg, 0.060 mmol, 1 equiv.) in methanol (10 mL) 4/1) and afforded lactam 18 (50 mg, 49%) as a yellow solid. R
2
2
1
-(3-(10-Chloroanthracen-9-yl)propyl)-1-deoxynojirimycin
4
(
f
¼
1
3
and chloroform (1 mL) was heated to reux until a homogenous 0.32 (PE/DCM: 2/1). H NMR (CDCl , 500 MHz): d 8.58 (d, 2H,
3
3
solution was formed. Then NaBH
3
CN (7.5 mg, 0.120 mmol,
J
Ha,Hb ¼ 8.9 Hz, 2 ꢂ H-a), 8.47 (d, 2H, JHa
0
,Hc ¼ 8.7 Hz, 2H, 2 ꢂ
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Chem. Sci.