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A. Arcelli et al. / Tetrahedron 57 12001) 3439±3444
for 4 h at room temperature. The crude reaction mixture,
diluted with CH2Cl2 <15 mL), was treated with a saturated
solution of Na2S2O5 to destroy the excess of m-CPBA, then
washed with a saturated solution of NaHCO3. By evapo-
ration of the organic layer, 0.55 g <1.4 mmol, 93%) of 5
was obtained. The title compound, recovered as a white
crystalline product, mp 214±2168C, was used for the next
reaction, without any further puri®cation. In fact, the puri-
®cation of this compound by ¯ash chromatography on SiO2
4.1.3. +1)-+1S,2R,3R,4R)-2,3-Diazido-1,4-dimethoxycyclo-
hex-5-ene +8). To 0.20 g <0.70 mmol) of 6, CCl4 <2.9 mL),
t-BuOH <1.9 mL) and H2O <0.3 mL) were added under N2.
After complete dissolution of 6, 1.94 g of ®nely powdered
KOH were added and a vigorous stirring was continued for
2 h. Finally, H2O was added and the reaction mixture was
extracted with CH2Cl2 giving 0.14 g <0.60 mmol, 90%) of 8
as yellow oil, which was used without any further puri®-
cation. Nevertheless the title compound can be puri®ed by
¯ash chromatography <SiO2; CH2Cl2/light petroleum 3:1).
1H NMR: d 6.05±5.93 <ddd, 1H, CHv, J10.15, 4.64,
1.61 Hz), 5.92±5.84 <dd, 1H, CHv, J10.12, 1.90 Hz),
3.97±3.80 <m, 2H, 2CH), 3.73 <m, 1H, CH), 3.45 <s, 6H,
2CH3O), 3.15 <dd, 1H, CHN3, J11.35, 3.70 Hz). 13C NMR
d: 130.4 <CHv), 126.1 <CHv), 80.9 <CHO), 74.6 <CHO),
61.9 <CHN3), 61.8 <CHN3), 58.2 <CH3O), 57.0 <CH3O).
1
carried to decomposition of the product. H NMR: d 4.99
<m, 2H, 2CHOMs), 4.18 <m, 1H, CHOCH3), 3.90 <m, 1H,
CHOCH3), 3.73 <m, 2H, CH2SO2), 3.50 <s, 3H, OCH3), 3.45
<s, 3H, OCH3), 3.45 <m, 2H, CH2SO2), 3.22 <s, 3H,
CH3SO2), 3.20 <s, 3H, CH3SO2). 13C NMR: d 81.0
<CHO), 79.6 <CHO), 76.3 <CHO), 74.8 <CHO), 57.9
<CH3O), 57.2 <CH3O), 54.6 <CH2S), 52.5 <CH2S), 38.7
27
25
<CH3SO2), 38.2 <CH3SO2). [a]D 20.2 <c1.60,
[a]D 133.2 <c1.30, CHCl3). m/z: 224 <,1), 154 <70),
CH3CN). m/z: 317 <8), 285 <18), 221 <19), 178 <100), 165
<49), 121 <76), 99 <32), 79 <78). IR <KBr) nmax <cm21): 2920,
1470, 1310, 1110. Anal. Calcd for C10H20O10S3: C, 30.30;
H, 5.08. Found: C, 30.32; H, 5.11.
114 <100), 99 <48), 71 <52). IR <neat) nmax <cm21): 2950,
2120, 1470, 1280, 1100. Anal. Calcd for C8H12N6O2: C,
42.85; H, 5.39; N, 37.48. Found: C, 42.82; H, 5.41; N, 37.52.
4.1.4.
+1)-+1S,2R,3R,4R)-2,3-Diamino-1,4-dimethoxy-
4.1.2. +2)-+3R,4R,5R,6S)-4,5-Diazido-3,6-dimethoxythie-
pane-S,S-oxide +6) and cis-+2)-+1R,4S,5R,6R,7R)-5-azido-
cyclohex-5-ene +9). To 60 mg <0.27 mmol) of the diazido
derivative 8, dissolved in MeOH <2.4 mL), were added
0.27 mL <2.73 mmol) of 1,3-propanedithiol and 0.38 mL
<2.73 mmol) of Et3N. After 48 h the solid formed was
removed by ®ltration and the reaction mixture was evapo-
rated. The residue, treated with 5 mL of methanol and 5 mL
of Et2O, was extracted with 2 M HCl. The aqueous layer
was neutralised with Na2CO3 then extracted with CH2Cl2.
33 mg <0.19 mmol, 70%) of the title compound were
4,7-dimethoxy-thiabicyclo[4.1.0]eptane-S,S-oxide
+7).
200 mg <0.50 mmol) of the dimesyl derivative 5 were
dissolved in DMSO <2.5 mL) then 160 mg <24.6 mmol) of
NaN3 were added. After 19 h at 1208C the reaction mixture,
diluted with 70 mL of EtOAc, was washed twice with H2O
<2£15 mL) then with brine <20 mL). The organic layer,
dried and evaporated, gave 130 mg of a mixture of 6 and
7 in a 2:1 ratio, respectively. These products were separated
by ¯ash chromatography <SiO2; CH2Cl2, EtOAc 0.5%)
obtaining 90 mg <0.31 mmol, 62%) of 6 as a yellow oil
and 30 mg <0.12 mmol, 24%) of 7 as a white crystalline
product, mp 72±748C.
1
obtained as viscous oil. H NMR: d 6.05±5.82 <m, 2H,
2CHv), 3.67 <m, 1H, CHO), 3.55 <d, 1H, CHO, J
8.12 Hz), 3.32 <s, 3H, CH3), 3.30 <s, 3H, CH3), 2.95 <bs,
4H, 2NH2), 2.85 <m, 1H, CHN), 2.72 <dd, 1H, CHN,
J11.16, 3.86 Hz). 13C NMR d: 130.5 <CHv), 126.6
<CHv), 82.4 <CHOH), 75.5 <CHOH), 57.5 <CH3O), 56.0
25
Spectroscopic data for 6. 1H NMR: d 3.72 <m, 6H),
3.60 <s, 3H, OCH3), 3.42 <s, 3H, OCH3), 3.17 <m,
2H). 13C NMR: d 78.9 <CHO), 75.1 <CHO), 66.8 <CHN),
65.2 <CHN), 58.2 <CH3O), 57.7 <CH3O), 55.3 <CH2SO2),
<CH3O), 53.9 <CHN), 52.5 <CHN). [a]D 187.4
<c1.31, CHCl3). m/z: 182 <62), 151 <18), 114 <100) 99
<55), 71 <22). IR <CHCl3) nmax <cm21): 3420, 2910, 1720,
1640. Anal. Calcd for C8H16N2O2: C, 55.77; H, 9.37; N,
16.27. Found: C, 55.80; H, 9.41; N, 16.31.
25
53.5 <CH2SO2). [a]D 26.3 <c0.71, CHCl3). m/z: 176
<7), 121 <5), 91 <24), 85 <18), 58 <100). IR <neat) nmax
<cm21): 2950, 2120, 1460, 1315, 1140. Anal. Calcd for
C8H14N6O4S: C, 33.10; H, 4.86, N; 28.95. Found: C,
33.12; H, 4.90; N, 28.95.
4.1.5.
+2)-1,6-Dideoxy-2,5-di-O-benzyl-3,4-isopropyl-
idene-1,6-thia-d-mannitol +13). To 150 mg <3.12 mmol)
of 50% NaH, washed with light petroleum, was added
under nitrogen 7 mL of THF and 568 mg <2.58 mmol) of
the thiepane derivative 12.16,17 The reaction mixture was
stirred for 30 min and treated with a solution of 0.3 mL of
benzyl bromide and 2 mg <0.012 mmol) of KI in 1.8 mL of
THF. After 7 h, 150 mg <3.12 mmol) of 50% NaH and
0.3 mL <2.71 mmol) of benzyl bromide were added. Stirring
was continued for 12 h, then H2O was added and the mixture
extracted with Et2O <3£30 mL). The organic layer was dried
and evaporated to give 0.99 g <2.39 mmol, 96%) of 13 as a
yellow solid which was puri®ed by ¯ash chromatography
<SiO2; CH2Cl2/light petroleum 3:1), giving a solid with mp
The chemical shifts of 7 were assigned by means of
2D-NMR experiments: COSY, HETCOR and HET2DJ.
1H NMR: d 3.82 <dd, 1H, C5H, J9.82, 7.11 Hz,), 3.62
<dd, 1H, C7H, J4.70, 3.05 Hz), 3.41 <s, 3H, CH3), 3.37
<s, 3H, CH3), 3.24 <m, 2H, C4H and C3HH), 2.77 <2dd,
2H, C1H and C3HH superimposed; irradiating at
d2.15 ppm the J10.79, 3.05 Hz were assigned to C1H
and the J13.39, 12.03 Hz were assigned to C3HH), 2.15
<ddd, 1H, C6H, J10.80, 7.11, 4.74 Hz). 13C NMR, d: 77.2
<C4), 61.8 <C7), 59.6 <C5), 58.6 <CH3), 57.8 <CH3), 53.8 <C3),
1
42.9 <C1), 27.8 <C6). HET2DJ: JC H177.42 Hz, JC7H
55±578C. H NMR: d 7.40 <m, 10H, ArH), 4.90 <d, 2H,
1
25
187.05 Hz, JC6H168.33 Hz. [a]D 233.8 <c0.94,
CHCl3). m/z: 220 <,1), 173 <4), 140<3), 97 <53), 82 <60),
70 <75), 58 <94). IR <KBr) nmax <cm21): 2948, 2118, 1313,
1141. Anal. Calcd for C8H13N3O4S: C, 38.86; H, 5.30; N,
16.99. Found: C, 38.89; H, 5.33; N, 17.01.
2CHHPh, J12.09 Hz), 4.70 <m, 2H, 2CHO, irradiating at
4.18 ppm a singlet was obtained), 4.69 <d, 2H, 2CHHPh,
J12.09 Hz), 4.18 <m, 2H, 2CHOBn), 2.90 <dd, 2H,
2CHHS, irradiating at 4.18 ppm a doublet was obtained;
J15.01 Hz), 2.63 <dd, 2H, 2CHHS, irradiating at