European Journal of Organic Chemistry
10.1002/ejoc.201701253
FULL PAPER
the presence of K
2
CO
3
(0.066 g, 0.48 mmol) in dry DMF at room
NaHCO
3
and finally with saturated NaCl solution. The collected
temperature for a period of 30 min. The crude conjugate was
purified by column chromatography using 30% EtOAc in pet ether
to give the product 5a. To a solution of 5a (0.100 g, 0.23 mmol) and
2 4
organic layer dried over Na SO and solvent was removed under
vaccum. The crude product was purified by column chromatography
using 40% EtOAc in pet ether to give the product. White solid
1
Et
3
N (0.035 g, 0.34 mmol) in dry DCM (10 mL), was added a
(0.174 g, 93%). mp: 72-73 ºC. H NMR (400 MHz, chloroform-d) δ
solution of phenyl chloroformate (0.036 g, 0.23 mmol) in DCM
dropwise at 0°C . After stirring at room temperature for 30 minutes
the reaction mixture was diluted with DCM and washed with 1N HCl
8.68 (s, 1H), 8.66 (s, 1H), 8.13 (t, J = 8.4 Hz, 2H), 7.48 (d, J = 8.8
Hz, 2H), 5.56 (s, 2H), 5.49 (s, 1H), 5.41 (d, J=4.0 Hz, 1H), 5.19 (s,
1H), 4.59-4.43 (m, 1H), 4.39 (q, J = 7.0 Hz, 2H), 4.18 (d, J = 5.3 Hz,
2H), 2.49-2.46 (m, 2H), 2.02-1.09 (m, 23H), 1.48 (s, 9H), 0.95 (s,
followed by saturated NaHCO
3
and finally with saturated NaCl
SO and solvent
1
3
solution. The collected organic layer dried over Na
2
4
3
6H), 0.89-0.82 (m, 9H), 0.63 (s, 3H). C NMR (100 MHz, CDCl ) δ
was removed under vaccum. The crude product was purified by
column chromatography using 40% EtOAc in pet ether to give the
product. White solid (0.117 g, 92%). mp: 73-74 ºC. H NMR (600
191.2, 190.8, 170.4, 156.0, 154.6, 144.0, 143.97, 139.5, 126.9,
126.8, 126.7, 123.2, 123.2, 123.1, 121.6, 109.5, 80.2, 78.9, 68.6,
66.7, 56.9, 56.3, 50.2, 42.5, 39.9, 39.7, 38.5, 38.1, 37.1, 36.8, 36.4,
1
MHz, chloroform-d) δ 8.80 (s, 1H), 8.76 (s, 1H), 8.24 – 8.18 (m, 3H), 36.0, 32.1, 32.0, 28.5, 28.4, 28.2, 27.8, 24.5, 24.0, 23.0, 22.8, 21.3,
+
+
8
3
.16 (d, J = 8.6 Hz, 1H), 7.53 (d, J = 8.6 Hz, 2H), 7.41 (t, J = 7.8 Hz,
H), 7.31 – 7.27 (m, 2H), 7.16 (t, J = 8.4 Hz, 2H), 5.74 (s, 2H), 5.64
19.5, 18.9, 14.1, 12.1. HRMS (ESI ) calcd for C53
903.5136; found: 903.5138.
H
72
N
2
O
9
[M + Na] ,
1
3
(
(
s, 2H), 4.45 (q, J = 7.1 Hz, 2H), 1.51 (t, J = 7.2 Hz, 3H). C NMR
151 MHz, CDCl
1
3
) δ 191.3, 190.6, 166.2 (d,
65.4, 153.8, 151.4, 144.08, 144.0, 132.9, 132.8, 129.7, 127.04,
27.0, 126.8, 126.6, 126.4, 123.2, 123.1, 121.7, 121.7, 121.2, 115.9
JC−F = 252.7 Hz),
2
3
-(9-ethyl-6-(2-(((phenylthio)carbonyl)oxy)acetyl)-9H-carbazol-
-yl)-2-oxoethyl benzoate (11d): Treatment of (0.150 g, 0.40
mmol) with benzoic acid (4d) (0.048 g, 0.40 mmol) in the presence
of K CO (0.066 g, 0.48 mmol) in dry DMF at room temperature for
a period of 30 min. The crude conjugate was purified by column
chromatography using 30% EtOAc in pet ether to give the product
1
1
3
2
(
d, JC−F = 21.9 Hz), 109.5, 77.4, 77.2, 77.0, 69.4, 66.7, 38.5, 14.1.
2
3
+
+
7
HRMS (ESI ) calcd for C32H24FNO [M + H] , 554.1615; found:
5
54.1634.
3
5d. To a solution of 5d (0.100 g, 0.24 mmol) and Et N (0.036 g,
2
2
0
-(6-(2-((ethoxycarbonyl)oxy)acetyl)-9-ethyl-9H-carbazol-3-yl)-
-oxoethyl 4-methoxybenzoate (8b): Treatment of (0.150 g,
.40 mmol) with p-anisic acid (4b) (0.060 g, 0.40 mmol) in the
CO (0.066 g, 0.48 mmol) in dry DMF at room
0.36 mmol) in dry DCM (10 mL), was added a solution of S-phenyl
carbonochloridothioate (0.041 g, 0.24 mmol) in DCM dropwise at
0°C. After stirring at room temperature for 30 minutes the reaction
mixture was diluted with DCM and washed with 1N HCl followed by
3
presence of K
2
3
temperature for a period of 30 min. The crude conjugate was
purified by column chromatography using 30% EtOAc in pet ether
to give the product 5b. To a solution of 5b (0.100 g, 0.22 mmol) and
saturated NaHCO
collected organic layer dried over Na
under vaccum. The crude product was purified by column
chromatography using 40% EtOAc in pet ether to give the product.
White solid (0.115 g, 87%). mp: 70-71 ºC. H NMR (600 MHz,
chloroform-d) δ 8.78 (s, 1H), 8.71 (s, 1H), 8.19 (d, J = 7.3 Hz, 3H),
8.12 (d, J = 8.7 Hz, 1H), 7.64 – 7.58 (m, 3H), 7.50 (q, J = 9.4, 8.0
Hz, 4H), 7.45 – 7.38 (m, 3H), 7.26 (s, 1H), 5.74 (s, 2H), 5.61 (s, 2H),
3
and finally with saturated NaCl solution. The
SO and solvent was removed
2
4
3
Et N (0.034 g, 0.33 mmol) in dry DCM (10 mL), was added a
1
solution of ethyl chloroformate (0.024 g, 0.22 mmol) in DCM
dropwise at 0°C . After stirring at room temperature for 30 minutes
the reaction mixture was diluted with DCM and washed with 1N HCl
followed by saturated NaHCO
solution. The collected organic layer dried over Na
3
and finally with saturated NaCl
SO and solvent
1
3
2
4
4.43 (q, J = 6.7, 6.3 Hz, 2H), 1.49 (t, J = 7.2 Hz, 3H). C NMR (151
MHz, CDCl ) δ 191.5, 190.6, 170.2, 166.4, 144.1, 144.0, 135.1,
was removed under vaccum. The crude product was purified by
column chromatography using 40% EtOAc in pet ether to give the
3
133.6, 130.2, 129.9, 129.7, 129.4, 128.7, 127.6, 127.2, 127.0, 126.9,
126.7, 123.2, 123.18, 121.8, 109.5, 68.7, 66.7, 38.5, 14.1. HRMS
1
product. White solid (0.103 g, 89%). mp: 64-65 ºC. H NMR (600
+
+
MHz, chloroform-d) δ 8.80 (s, 1H), 8.74 (s, 1H), 8.20 (d, J = 8.5 Hz,
6
(ESI ) calcd for C32H25NO S [M + H] , 552.1481; found: 552.1481.
1
8
H), 8.18 – 8.10 (m, 3H), 7.52 (dd, J = 8.6, 4.5 Hz, 2H), 6.97 (d, J =
.8 Hz, 2H), 5.71 (s, 2H), 5.52 (s, 2H), 4.45 (q, J = 7.2 Hz, 2H), 4.31
2
-(9-ethyl-6-(2-(((p-tolylthio)carbonyl)oxy)acetyl)-9H-carbazol-3-
yl)-2-oxoethyl 4-methylbenzoate (11e): Treatment of (0.150 g,
.40 mmol) with p-toluic acid (4e) (0.054 g, 0.40 mmol) in the
presence of K CO (0.066 g, 0.48 mmol) in dry DMF at room
(
q, J = 7.1 Hz, 2H), 3.89 (s, 3H), 1.50 (t, J = 7.2 Hz, 3H), 1.38 (t, J =
3
1
3
7
1
1
3
.1 Hz, 3H). C NMR (151 MHz, CDCl ) 191.6, 191.0, 165.9, 163.7,
0
55.0, 143.8, 132.1, 127.0, 126.8, 126.6, 122.9, 121.9, 121.5, 121.4,
2
3
+
13.7, 109.2, 68.5, 66.3, 64.7, 55.5, 38.3, 14.3, 13.9. HRMS (ESI )
temperature for a period of 30 min. The crude conjugate was
purified by column chromatography using 30% EtOAc in pet ether
to give the product 5e. To a solution of 5e (0.100 g, 0.23 mmol) and
+
calcd for C29
H
27NO
8
[M + H] , 518.1815; found: 518.1824.
2-(6-(2-(((((8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-
3
Et N (0.035 g, 0.34 mmol) in dry DCM (10 mL), was added a
methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-
tetradecahydro-1H-cyclopenta[a]phenanthren-3-
yl)oxy)carbonyl)oxy)acetyl)-9-ethyl-9H-carbazol-3-yl)-2-
oxoethyl 2-((tert-butoxycarbonyl)amino)acetate (8c): Treatment
solution of S-p-tolyl carbonochloridothioate (0.043 g, 0.23 mmol) in
DCM dropwise at 0°C. After stirring at room temperature for 30
minutes the reaction mixture was diluted with DCM and washed
with 1N HCl followed by saturated NaHCO
saturated NaCl solution. The collected organic layer dried over
Na SO and solvent was removed under vaccum. The crude
3
and finally with
of
acetic acid (4c) (0.070 g, 0.40 mmol) in the presence of K
0.066 g, 0.48 mmol) in dry DMF at room temperature for a period
3
(0.150 g, 0.40 mmol) with 2-((tert-butoxycarbonyl) amino)
2
CO
3
2
4
(
product was purified by column chromatography using 40% EtOAc
in pet ether to give the product. White solid (0.112 g, 83%). mp: 74-
of 30 min. The crude conjugate was purified by column
chromatography using 30% EtOAc in pet ether to give the product
1
75 ºC. H NMR (600 MHz, chloroform-d) δ 8.79 (s, 1H), 8.71 (s, 1H),
5
c. To a solution of 5c (0.100 g, 0.21 mmol) and Et
3
N (0.032 g, 0.31
8.19 (d, J = 8.5 Hz, 2H), 8.12 (d, J = 8.6 Hz, 2H), 8.07 (d, J = 7.9 Hz,
2H), 7.52 – 7.47 (m, 4H), 7.28 (d, J = 7.9 Hz, 2H), 7.21 (d, J = 7.8
Hz, 2H), 5.71 (s, 2H), 5.59 (s, 2H), 4.43 (q, J = 7.2 Hz, 2H), 2.44 (s,
mmol) in dry DCM (10 mL), was added a solution of cholesteryl
chloroformate (0.095 g, 0.21 mmol) in DCM dropwise at 0°C. After
stirring at room temperature for 30 minutes the reaction mixture was
diluted with DCM and washed with 1N HCl followed by saturated
1
3
3H), 2.36 (s, 3H), 1.49 (t, J = 7.2 Hz, 3H). C NMR (151 MHz,
CDCl ) δ 191.5, 190.5, 170.3, 166.3, 144.1, 143.8, 143.8, 140.1,
3
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