M. Benazza et al. / Tetrahedron 65 (2009) 8885–8890
8889
4
.2.5.2. Method B. Allyl bromide (0.28 ml, 3.3 mmol) and 1
169.6 (C]O), 113.1 (C(i-Pr)), 105.1 (C-1), 83.4 (C-2), 79.6 (C-5), 74.5
ꢀ
0
(
3
100 mg, 0.33 mmol) were reacted at 120 C in a closed reactor for
h to give 6 with an 82% yield. [
cyclohexane/EtOAc); C NMR (CDCl
C]O), 132.6 (C-2 ), 118.5 (C-3 ), 112.9 (C(i-Pr)), 105.2 (C-1), 83.3
C-2), 77.9 (C-5), 74.9 (C-4), 70.9 (C-3), 34.0 (C-1 ), 32.9 (C-6), 26.9,
6.4 (CH
(C-4), 71.6 (C-3), 34.1 (C-1 ), 27.0, 26.4 (CH
3
(i-Pr)), 20.9 (CH
3
CO), 5.7
), 5.90
2
0
1
a
]
D
¼ꢁ30 (c 0.1, CHCl
3
); R
f
¼0.3 (5:1,
(C-6). H NMR (CDCl
3
, 300 MHz):
d
¼6.70–6.30 (br d, 2H; NH
2
13
3
, 75 MHz):
d
¼169.9, 169.4
(d, J¼3.5 Hz, 1H; H-1), 5.35 (d, J¼3.5 Hz, 1H; H-4), 5.00–4.90 (m, 1H;
0
0
(
(
2
(
3
H-3), 4.50 (d, J¼3.5 Hz, 1H; H-2), 4.60 (dd, J¼2.8 and 2.8 Hz, 1H;
0
0
H-5), 4.00–3.60 (m, 4H; H-6 and H-1 ), 2.08 (s, 3H; C(O)CH
3
), 1.50 (s,
20INa-
1
3
(i-Pr)), 20.8 (CH
3
CO); H NMR (CDCl
3
, 300 MHz):
d¼5.88
3H; CH
3
(i-Pr)), 1.30 (s, 3H; CH
3
(i-Pr)). HRMS calcd for C14
H
0
þ
þ
d, J¼3.7 Hz,1H; H-1), 5.88–5.75 (m, 2H; H-2 ), 5.35–5.10 (m, 4H; H-
NO S [(M Na) ] 511.9852; found 511.9837.
8
0
, H-4 and H-3 ), 4.48 (d, J¼3.5 Hz, 1H; H-2), 4.42 (dd, J¼3.0 Hz, 1H;
H-5), 3.75 (dd, J¼2.7 and 11.6 Hz, 1H; H-6a), 3.58 (dd, J¼5.6 and
4.2.9. 6-S-Allylthioether-5-O-allylthiolcarbonate-1,2-O-isopropylidene-
-glucofuranose (16). To cooled solution of (280 mg,
0.79 mmol) in 1:1 DMSO/THF (4 ml) were added allylthiol (132 l,
0.95 mmol) and CsCO (310 mg, 0.95 mmol). The mixture was
0
1
1
C
1.6 Hz, 1H; H-6b), 3.50–3.47 (m, 2H; H-1 ), 2.04 (s, 3H; CH
3
CO),
a-D
a
6
.50 (s, 3H; CH
H
3
(i-Pr)), 1.26 (s, 3H; CH
S [(M Na) ] calcd 447.0089; found 447.0074.
3
(i-Pr)). HRMS calcd for
m
þ
þ
15
21BrNaO
7
3
ꢀ
stirred for 15 min at 0 C. After extraction with ether/H
ganic layer was dried on MgSO and concentrated. The chroma-
tography on silica gel with 95:5 cyclohexane/EtOAc as eluent, gave
2
O, the or-
4
.2.6. 3-O-Acetyl-5-O-allylthiocarbonyl-6-iodo-6-deoxy-1,2-O-iso-
-glucofuranose (7).
.2.6.1. Method A. Allyl iodide (0.30 ml, 3.3 mmol) and 1 (100 mg,
4
propylidene-a-D
2
0
4
compound 16 as syrup in 60% yield (165 mg). [
a
]
D
¼ꢁ22 (c 0.1,
1
3
0
1
(
.33 mmol) were reacted under 250 W microwave irradiation, at
CHCl
75 MHz):
3
); R
f
¼0.32 EtOAc/cyclohexane (5/95; v/v); C NMR (CDCl3,
ꢀ
0
20 C during 10 min. After concentration and flash chromatography
d
0
¼169.9, 169.7 (C]O), 134.0 (C-2 ), 132.9 (C-8), 118.5 (C-9),
5:1, cyclohexane/EtOAc), 7wasisolatedasayellowsyrup(96 mg,70%).
117.9 (C-3 ), 112.7 (C(i-Pr)), 105.2 (C-1), 83.5 (C-2), 78.5 (C-4), 75.2
0
(
C-3), 71.9 (C-5), 35.4 (C-6), 34.7 (C-1 ), 32.6 (C-7), 26.9, 26.4 (CH
3
(i-
1
4.2.6.2. Method B. Allyl iodide (0.75 ml, 8.3 mmol) and
1
Pr)), 20.9 (CH
3
(OAc))ppm. H NMR (CDCl
3
, 300 MHz):
d
¼5.88 (d,
ꢀ
0
(
1
250 mg, 0.83 mmol) were reacted in a closed reactor at 120 C for
h to give 7 with a 62% yield. [
cyclohexane/EtOAc); C NMR (CDCl
C]O), 132.6 (C-2 ), 118.5 (C-3 ), 112.8 (C(i-Pr)), 105.1 (C-1), 83.3 (C-
), 79.5 (C-5), 74.7 (C-4), 70.6 (C-3), 34.0 (C-1 ), 26.9, 26.4 (CH
i-Pr)), 20.8 (CH
J¼3.0 Hz, 1H; H-1), 5.85–5.65 (m, 2H; H-2 and H-8), 5.35–5.10 (m,
2
0
0
a]
D
¼ꢁ19 (c 0.1, CHCl
3
); R
f
¼0.3 (6:1,
6H; H-3, H-4, H-3 and H-9), 4.50 (d, J¼3.1 Hz, 1H; H-2), 4.45 (dd,
13
0
3
, 75 MHz):
d
¼169.7, 169.4
J¼2.1 and 6.2 Hz, 1H; H-5), 3.51–3.45 (m, 2H; H-1 ), 3.15
0
0
(
2
(
(
4
(
3
3
C
(d, J¼7.2 Hz, 2H; H-7), 3.10 (dd, J¼3.0 and 14.9 Hz, 1H; H-6b), 2.70
0
3
(dd, J¼7.0 and 14.9 Hz,1H; H-6a), 2.05 (s, 3H, CH
3
(OAc)),1.57 (s, 3H;
1
3
CO), 6.4 (C-6). H NMR (CDCl
3
, 300 MHz):
d
¼5.84
CH
3
(i-Pr)), 1.3 (s, 3H; CH
3
(i-Pr)) ppm. HRMS calcd for C18
H
26
O
7
S
2
0
þ
þ
d, J¼3.7 Hz,1H; H-1), 5.83–5.75 (m, 2H; H-2 ), 5.30–5.10 (m, 2H; H-
[(M Na) ] calcd 441.1018; found 441.1016.
0
and H-3 ), 4.93–4.86 (m, 1H; H-3), 4.46 (d, J¼3.6 Hz,1H; H-2), 4.30
0
dd, J¼3.0, 1H; H-5), 3.58 (dd, J¼3.1 and 11.4 Hz, 1H; H-6a), 3.45–
4.2.10. Synthesis of 10-membered thiolcarbonate 17a: (Z)-10(S)-[3 -
0
0
0
0
.40 (m, 2H; H-1 ), 3.38 (dd, J¼5.6 and 11.4 Hz, 1H; H-6b), 2.00 (s,
O-acetyl-1 ,2 -O-isopropylidene-4 -deoxy-
trihydro-10H-8-thia-1,3-oxathiecin-2-one. To
(50 mg, 0.12 mmol) in distilled and degazed CH
D
-erythrofuranose]-4,7,9-
solution of 16
Cl (25 ml), was
H; CH
H
3
CO), 1.50 (s, 3H; CH
3
(i-Pr)), 1.26 (s, 3H; CH
3
(i-Pr)). HRMS for
a
þ
þ
15
21INaO
7
S [(M Na) ] calcd 494.9951; found 494.9955.
2
2
added Grubbs second generation (15 mg, 0.018 mmol, in 1 ml of
ꢀ
4
.2.7. 3-O-Acetyl-6-bromo-6-deoxy-5-O-propargylthio-carbonyl-1,2-
O-isopropylidene- -glucofuranose (8).
.2.7.1. Method A. Propargyl bromide (0.71 ml, 6.6 mmol) and 1
CH
2
Cl
2
). The mixture was stirred at 50 C for 2 h. The compound 17a
a-D
was isolated in 75% yield (35 mg) after chromatography on silica gel
with 95:5 cyclohexane/EtOAc as eluent. [
2
0
4
a
]
D
¼ꢁ27 (c 0.1, CHCl
3
);
13
(
200 mg, 0.67 mmol) were reacted under 250 W microwave irradi-
R
f
¼0.3, 95:5 cylohexane/EtOAc. C NMR (CDCl
3
, 75 MHz):
d
¼169.9,
ꢀ
0
ation, at 120 C during 30 min. After concentration and flash chro-
matography (5:1, cyclohexane/EtOAc), 8 was isolated as a yellow
syrup (195 mg, 70%).
168.2 (C]O), 128.3 (C-6), 127.9 (C-5), 113.1 (C(i-Pr)), 105.2 (C-1 ),
0
0
0
83.5 (C-2 ), 76.1 (C-4 ), 74.6 (C-3 ), 72.9 (C-10), 30.7 (C-9), 29.0 (C-4),
1
28.0 (C-7), 27.2, 26.7 (CH
CDCl3, 300 MHz):
3
(i-Pr)), 20.9 (CH
3
(OAc)) ppm; H NMR
0
(
d
¼5.90 (d, J¼3.36 Hz, 1H; H-1 ), 5.75 (tq, J¼4.6
4
.2.7.2. Method B. Propargyl bromide (0.71 ml, 6.6 mmol) and 1
and 11.2 Hz, 1H; H-5), 5.67 (dt, J¼2.7 and 9.6 Hz, 1H; H-10), 5.51 (dt,
ꢀ
0
(
200 mg, 0.67 mmol) were reacted at 120 C in a closed for 3 h to
J¼3.2 and 11.3 Hz, 1H; H-6), 5.40 (d, J¼2.5 Hz, 1H; H-3 ), 4.95
2
0
0
0
give the desired product 8 with a 72% yield. [
CHCl
a
]
D
¼ꢁ23 (c 0.1,
(dd, J¼2.7 and 9.6 Hz, 1H; H-4 ), 4.50 (d, J¼3.4 Hz, 1H; H-2 ), 4.10 (t,
J¼13.9 Hz, 1H; H-4b), 3.85 (t, J¼13.5 Hz, 1H; H-7b), 2.96 (dd, J¼1.8
and 15.5 Hz,1H; H-9b), 2.87 (d, J¼14.0 Hz,1H; H-7a), 2.81 (dd, J¼4.5
and 13.7 Hz, 1H; H-4a), 2.68 (dd, J¼3.2 and 15.5 Hz, 1H; H-9a), 2.05
13
3
); R
f
¼0.3 (5:1, cyclohexane/EtOAc); C NMR (CDCl
3
, 75 MHz):
d
¼170.0, 169.5 (C]O), 112.9 (C(i-Pr)), 105.2 (C-1), 83.3 (C-2), 78.2
0
0
0
(
C-2 ), 77.8 (C-5), 74.9 (C-4), 71.9 (C-3 ), 71.6 (C-3), 32.7 (C-1 ), 26.9,
1
2
3
5
6.4 (CH
3
(i-Pr)), 20.8 (CH
3
CO), 19.8 (C-6).
H
NMR (CDCl
3
,
(s, 3H, CH
HRMS pour C16
3
(OAc)),1.60 (s, 3H; CH
3
(i-Pr)),1.50 (s, 3H; CH
[(M Na) ] calcd 413.0705; found 413.0700.
3
(i-Pr)) ppm.
þ
þ
00 MHz):
d
¼5.90 (d, J¼3.5 Hz, 1H; H-1), 5.40–5.30 (m, 1H; H-3),
H
22
O
7
S
2
.25 (d, J¼2.7 Hz, 1H; H-4), 4.50 (d, J¼3.6 Hz, 1H; H-2), 4.60
(
(
(
dd, J¼3 Hz, 1H; H-5), 3.68 (dd, J¼2.7 and 11.7 Hz, 1H; H-6a), 3.53
Acknowledgements
0
dd, J¼5.5 and 10.1 Hz, 1H; H-6b), 3.60 (d, J¼5.5 Hz, H-1 ), 2.25
0
t, J¼2.7 Hz, 1H; H-3 ), 2.10 (s, 3H; C(O)CH
3
), 1.50 (s, 3H; CH
3
(i-Pr)),
We thank the Conseil R e´ gional de Picardie and le Fonds Social
Europ e´ en for their financial support.
þ þ
7
H19BrNaO S [(M Na) ]
1
.26 (s, 3H; CH
3
(i-Pr)). HRMS calcd for C15
4
46.9913; found 446.9913.
References and notes
4
.2.8. 5-O-Acetamidothiocarbonyl-3-O-acetyl-6-iodo-6-deoxy-1,2-
-glucofuranose (9).
.2.8.1. Method B. The mixture of iodoacetamide (310 mg,
O-isopropylidene-
a-
D
1. (a) Derwent Drug File; Thomson Scientific: 14 Great Queen Street, London
WC2B 5DF, 2004; (b) Harusawa, S.; Takemura, S.; Yoneda, R.; Kurihara, T.
Tetrahedron 1993, 49, 10577–10586; (c) Harusawa, S.; Takemura, S.; Osaki, H.;
Yoneda, R.; Kurihara, T. Tetrahedron 1993, 49, 7657–7666; (d) Harusawa, S.;
Ohishi, H.; Osaki, H.; Tomii, S.; Yoneda, R.; Kurihara, T. Chem. Pharm. Bull.
4
1.65 mmol) and 1 (100 mg, 0.33 mmol) in dried toluene (0.5 ml)
ꢀ
was reacted at 120 C in a closed reactor for 1 h. After concentration
and flash chromatography (1:1, cyclohexane/EtOAc), 9 was isolated
as a yellow syrup (142 mg, 88%). [
1992, 40, 2185–2187; (e) Harusawa, S.; Osaki, H.; Fujii, H.; Yoneda, R.;
Kurihara, T. Tetrahedron 1992, 48, 9433–9450; (f) Harusawa, S.; Osaki, H.;
Kurukawa, T.; Fujii, H.; Yoneda, R.; Kurihara, T. Chem. Pharm. Bull. 1991, 39,
1659–1667.
2
0
a
]
D
¼ꢁ19 (c 0.1, CHCl
3
); R
¼170.6, 170.1,
f
¼0.3
13
(
1:1, cyclohexane/EtOAc); C NMR (CDCl , 75 MHz):
3
d