88
A.A. Kaya et al. / Tetrahedron 70 (2014) 83e91
aromatic, 1H), 8.42 (dd, A part of AB system, J¼9.0, 2.5 Hz, aromatic,
H), 7.73 (d, B part of AB system, J¼9.0 Hz, aromatic, 1H), 4.62 (br s,
BrCH, 2H), 4.42 (dt, J¼10.5, 4.2 Hz, ClCH, 1H), 4.08 (dt, J¼10.8,
.9 Hz, SCH, 1H), 3.05e2.94 (m, ClCHCH , 1H), 2.85e2.75 (m,
SCHCH
, 1H), 2.70 (dm, B part of AB system, J¼15.2 Hz, ClCHCH
H), 2.53 (dm, B part of AB system, J¼15.6 Hz, SCHCH
NMR (100 MHz, CDCl 146.4 (C), 144.7 (C), 143.8 (C), 128.1 (CH),
27.5 (CH), 121.9 (CH), 56.9, 50.4, 49.70, 48.6, 39.6, 35.8; IR (CH Cl
cm ): 3092, 2957, 1588, 1524, 1429, 1339, 1250, 1177, 1090, 1046,
again. The reaction mixture was poured into ice (15 g) and was
1
extracted with EtOAc (2ꢂ30 mL). The combined extracts were
washed with cold NaHCO
(50 mL), and dried over Na SO . The solvent was evaporated and
2 4
3
(saturated, 2ꢂ100 mL) and water
3
2
2
2
,
C
the residue was submitted to silica gel (100 g) column chroma-
tography with EtOAc/hexane (1/9) elution. Compounds 15 (110 mg,
17%) and 16 (350 mg, 54%) were isolated, respectively. Both of them
13
1
2
, 1H);
3
) d
1
2
2
,
were crystallized from CH
2 2
Cl /hexane as yellow crystals.
ꢀ
1
9
5
73, 914. Anal. Calcd for C12
.90; S, 6.76. Found: C, 30.29; H, 2.31; N, 5.88; S, 6.71%.
2 2 4
H11Br ClN O S: C, 30.37; H, 2.34; N,
4.1.3.1. 1R(S),2R(S),4R(S),5R(S)-2,5-Dichloro-4-(2,4-
ꢁ
1
dinitrophenylthio)cyclohexyl acetate (15). Mp 148e150 C; H NMR
400 MHz, CDCl
(
3
)
d
9.07 (d, J¼2.49 Hz, aromatic, 1H), 8.46 (dd, A
4.1.2.2. Synthesis of 1R(S),2R(S),4R(S),5R(S)-4,5-dibromo-2-(2,4-
part of AB system, J¼9.0, 2.5 Hz, aromatic, 1H), 7.72 (d, B part of AB
system, J¼9.0 Hz, aromatic, 1H), 5.24e5.19 (m, OCH, 1H), 4.30e423
(m, ClCH, 2H), 4.03 (dt, J¼9.10, 4.00 Hz, SCH, 1H), 2.64e2.57 (m,
dinitrophenylthio)cyclohexyl acetate (9). The standard procedure
described above for bromination was applied. Acetate 7 (0.6 g,
1
(
.77 mmol) and Br
0.81 g, 91%) was obtained as pale red crystals. Mp 115e117 C; H
NMR (400 MHz, CDCl
2
(0.56 g, 3.55 mmol) were used. Dibromide 9
3
methylenic, 2H), 2.29e2.40 (m, methylenic, 2H), 2.15 (s, CH , 3H);
ꢁ
1
13
3
C NMR (100 MHz, CDCl ) d 169.3 (CO), 146.1 (C), 144.6 (C), 143.4
3
)
d
9.03 (d, J¼2.5 Hz, aromatic, 1H), 8.43 (dd,
(C), 127.7 (CH), 127.4 (CH), 121.9 (CH), 71.2 (OCH), 56.8, 54.9, 47.3,
ꢀ
1
J¼9.0, 2.5 Hz, aromatic, 1H), 7.91 (d, B part of AB system, J¼9.0 Hz,
35.4, 35.3, 20.9; IR (CH
1523, 1341, 1227, 1132, 1093, 1049, 986, 914, 832. Anal. Calcd for
14 2 2 6
C H14Cl N O S: C, 41.09; H, 3.45; N, 6.85; S, 7.84. Found: C, 41.03;
2 2
Cl , cm ): 3092, 2957, 2857, 1741, 1595,
aromatic, 1H), 5.35e5.27 (m, OCH, 1H), 4.59 (br s, BrCH, 2H), 4.05
(
dt, J¼9.7, 4.0 Hz, SCH, 1H), 2.81 (ddd, A part of AB system, J¼15.20,
0.20, 3.04 Hz, methylenic, 1H), 2.66 (ddd, A part of AB system,
J¼14.5, 9.0, 3.4 Hz, methylenic, 1H), 2.60e2.48 (m, methylenic, 2H),
.02 (s, OCCH 169.8 (CO), 1461
, 3H); 13C NMR (100 MHz, CDCl
C), 144.6 (C), 144.2 (C), 128.1 (CH), 127.4 (CH), 121.9 (CH), 70.4
1
H, 3.43; N, 6.88; S, 7.81%.
2
(
(
3
3
)
d
4.1.3.2. 1R(S),2S(R),4R(S),5R(S)-4-(2,4-Dinitrophenylthio)cyclo-
ꢁ
1
hexane-1,2,-diyl diacetate (16). Mp 158e159 C; H NMR (400 MHz,
CDCl
ꢀ
1
OCH), 50.8, 49.5, 44.6, 35.3, 20.9; IR (CH
734, 1594, 1523, 1429, 1341, 1225, 1180, 1046, 990, 959, 914; Anal.
Calcd for C14 S: C, 33.76; H, 2.83; N, 5.62; S, 6.44. Found:
C, 33.73; H, 2.82; N, 5.61; S, 6.41.
2
Cl
2
, cm ): 3086, 2957,
3
)
d
9.02 (d, J¼2.4 Hz, aromatic, 1H), 8.40 (dd, A part of AB
1
system, J¼9.0, 2.4 Hz, aromatic, 1H), 7.65 (d, B part of AB system,
J¼9.0 Hz, aromatic, 1H), 5.15 (dt, J¼6.4, 3.7 Hz, OCH, 1H), 5.06 (dt,
J¼6.0, 3.6 Hz, OCH, 1H), 4.26 (dt, J¼7.9, 4.0 Hz, ClCH, 1H), 3.88 (dt,
J¼8.0, 4.4 Hz, SCH, 1H), 2.49e2.33 (m, methylenic, 2H), 2.34 (ddd, B
part of AB system, J¼14.6, 8.3, 3.7 Hz, methylenic, 1H), 2.21 (ddd, B
2 2 6
H14Br N O
4
.1.2.3. Standard procedure for epoxidation: synthesis of epoxide
2.1 A solution of m-CPBA (75%, 12.6 g, 55 mmol) in CH
e
Cl
2
part of AB system, J¼14.7, 8.6, 3.6 Hz, methylenic, 1H), 2.13 (s, CH
1
2
3
,
ꢁ
13
(
400 mL) was cooled to 0 C and then 1,4-cyclohexadiene (5.84 g,
3H), 2.08 (s, CH
3 3
, 3H); C NMR (100 MHz, CDCl ) d 169.7 (2CO),
7
3
3 mmol) and NaHCO (9.0 g, 0.11 mol) were directly added. After
146.5 (C), 144.9 (C), 143.4 (C), 128.3 (CH), 127.4 (CH), 121.9 (CH), 68.9
ꢀ
1
stirring at the same temperature for 1 h, the cold bath was removed
and then it was stirred for 1 h the mixture was filtered and the
(OCH), 68.7 (OCH), 57.6, 47.9, 35.7, 31.6, 21.2, 21.1; IR (CH
3098, 2957, 2862, 1751, 1595, 1523, 1434, 1341, 1227, 1049, 917, 833.
Anal. Calcd for C16 17ClN S: C, 44.40; H, 3.96; N, 6.47; S, 7.41.
Found: C, 44.45; H, 3.91; N, 6.51; S, 7.43%.
2 2
Cl , cm ):
liquid phase (organic) washed with NaHCO
ꢂ1500 mL) and water (100 mL), and dried over Na
vent was evaporated and the residue (liquid) was distilled. The
3
(saturated,
H
2 8
O
2
2
SO . The sol-
4
epoxide 121 (4.2 g, 60%) was obtained as liquid. H NMR (400 MHz,
e
1
4.1.4. Reaction of epoxide 13 with NaN
(0.32 g, 6.06 mmol) and NaN (0.79 g, 12.12 mmol) in water (20 mL)
was added solution of epoxide 13 (1.0 g, 3.03 mmol) in methanol
40 mL) for 30 min, and the mixture was then refluxed for 3 days.
3 4
. To solution of NH Cl
0
0
CDCl
3
)
d
5.21 (s, olefin, 2H), 2.97 (s, 2H), 2.29 (AA BB system, 4H);
3
1
3
C NMR (100 MHz, CDCl 123.3 (CH), 52.2 (OCH), 26.9 (CH ).
3
)
d
2
(
4
.1.2.4. Synthesis of 1R(S),3R(S),4R(S),6S(R)-3-chloro-4-(2,4-
After cooling to room temperature, the methanol in the mixture
was removed and then water (10 mL) was added. The mixture was
extracted with ether (3ꢂ30 mL) and the combined extracts were
dinitrophenylthio)-7-oxabicyclo[4.1.0]heptane (13). The standard pro-
cedure described above for addition of 2,4-dinitrobenzenesulfenyl
chloride in 1,2-dicholoroethane was applied. 2,4-Dinitroben-
zenesulfenyl chloride (1.3 g, 5.54 mmol), epoxide 12 (0.53 g,
.54 mmol) and 1,2-dicholoroethane (50 mL in total) were used.
Epoxide 13 (1.56 g, 85%) was obtained as yellow amorphous solid. Mp
29e130 C; H NMR (400 MHz, CDCl
H), 8.38 (dd, A part of AB system, J¼9.0, 2.5 Hz, aromatic,1H), 7.62 (d,
A part of AB system, J¼9.0 Hz, aromatic, 1H), 4.24e4.19 (m, ClCH, 1H),
.71e3.65 (m, SCH, 1H), 3.33 (t, J¼3.2, Hz, OCH, 1H), 3.30 (t, J¼3.7, Hz,
OCH, 1H), 2.93e2.83 (m, methylenic, 2H), 2.41e2.33 (m, methylenic,
2 4
dried over Na SO . The solvent was evaporated and the residue was
1e
submitted to silica gel (100 g) column chromatography with EtOAc/
hexane (1/4) elution.
5
ꢁ
1
1
1
3
)
d
8.99 (d, J¼2.5 Hz, aromatic,
4.1.4.1. 1R(S),2R(S),4R(S),5R(S)-2,5-Diazido-4-(2,4-dinitrophenyl-
thio)cyclohexanol (18). Compound 18 (790 mg, 70%) was obtained
ꢁ
1
3
as yellow amorphous. Mp 98e100 C; H NMR (400 MHz, CDCl )
3
d
9.04 (d, J¼2.5 Hz, aromatic, 1H), 8.42 (dd, A part of AB system,
J¼9.0, 2.5 Hz, aromatic, 1H), 7.73 (d, B part of AB system, J¼9.0 Hz,
aromatic,1H), 4.05 (br s, HOCH, 1H), 3.92 (dt, J¼8.3, 4.1 Hz,1H), 3.77
1
3
2
(
(
H); C NMR (100 MHz, CDCl
CH), 127.3 (CH), 121.8 (CH), 55.6, 50.5, 50.2, 45.9, 32.6 (CH
3
)
d
146.4 (C), 145.1 (C), 144.6 (C), 127.9
), 28.5
, cm ): 3086, 3014, 2963, 2918, 2851, 1594, 1521,
2
(dd, J¼9.6, 5.7 Hz, 1H), 3.63 (dt, J¼8.2, 4.8 Hz, 1H), 2.78e2.06 (m,
ꢀ1
13
CH
2
); IR (CH
Cl
2 2
methylenic and OH, 5H); C NMR (100 MHz, CDCl
3
)
d
146.3 (C),
1
C
420, 1341, 1258, 1152, 1090, 1048, 1012, 917, 830. Anal. Calcd for
144.7 (C), 143.8 (C), 128.1 (CH), 127.4 (CH), 121.9 (CH), 68.1 (OCH),
ꢀ1
12 2 5
H11ClN O S: C, 43.58; H, 3.35; N, 8.47; S, 9.69. Found: C, 43.57; H,
61.5, 59.8, 45.2, 34.1, 30.6; IR (CH
2105, 1700, 1594, 1522, 1440, 1341, 1253, 1132, 1093, 1051, 1018, 993,
11, 830. Anal. Calcd for C12 S: C, 37.89; H, 3.18; N, 29.46; S,
2 2
Cl , cm ): 3394, 3098, 2929,
3.37; N, 8.48; S, 9.68.
9
12 8 5
H N O
4
.1.3. Reaction of epoxide 13 with Ac
2
O in the presence of sulfuric
8.43. Found: C, 37.84; H, 3.23; N, 29.40; S, 8.48.
acid. A solution of the epoxide 13 (0.5 g,1.51 mmol) in Ac
2
O (10 mL)
ꢁ
was cooled to 0 C by stirring magnetically. After H
2
SO
4
(concd, ten
4.1.4.2. Synthesis of 1R(S),2R(S),4R(S),5R(S)-2,5-diazido-4-(2,4-
drops) were added, it was stirred for 24 h without cooling the bath
dinitrophenylthio)cyclohexyl acetate (19). To solution of alcohol 18