N. Amiri et al. / Tetrahedron 70 (2014) 8836e8842
8841
2
4H, CH
2
), 0.98 (m, 8H, CH
2
), ꢀ2.59 (s, 2H, NH pyrrole). UVevis
stirred for 20 min with 5 ml hydrochloric acid (5%). After phase
separation and evaporation of CHCl , the crude product was puri-
fied on silica gel column, using a mixture CHCl :CH OH (19:1) as
eluent, to give after evaporation 21 mg of a green solid. Yield: 65%.
ꢀ
1
ꢀ1
3
(
(
CHCl ),
3
l
max
3
,
nm
(
3 ,
M
cm
)
430 (245.200ꢁ10 ), 522
3
3
3
3
13.176ꢁ10 ), 560 (9.179ꢁ10 ), 596 (3.664ꢁ10 ), 652 (4.520ꢁ10 ).
3
3
þ
HRMS [ESI] m/z calcd for C84
83
H N
8
: 1203.6735 [MþH] , found:
ꢀ
1
ꢀ1
3
1203.6734.
UVevis (CHCl
3
),
l
max, nm (
3
, M cm ) 480 (103.453ꢁ10 ), 585
3
3
(
C
9.073ꢁ10 ), 620(8.775ꢁ10 ). HRMS [ESI]: m/z calcd for
þ
4.2.3. 5,10,15,20-Tetrakis-(10-dimethylamino-1,2,3,4,5,6,7,8-octahydro-
84
H
72MnN
8
O
8
1375.4848 [MꢀCl] , found: 1375.4848.
1
0
(
,4;5,8-dimethano-anthracen-9-yl)-porphyrin 4. Porphyrin 3 (100 mg,
.083 mmol) was dissolved in 10 ml DMF and excess iodomethane
354 mg, 2.5 mmol) and sodium hydride (20 mg, 0.83 mmol) were
4.2.7. Chloro(5,10,15,20-Tetrakis-(10-dimethylamino-1,2,3,4,5,6,7,8-
octahydro-1,4;5,8-dimethano-anthracen-9-yl)-porphyrin) man-
added. The reaction mixture was stirred for 15 min at room tem-
perature and heated at 140 C for 30 min. After DMF evaporation
ganese(III) 10. Porphyrin 4 (50 mg, 0.0379 mmol) in 10 ml DMF and
2,6-lutidine (12e13 mg, 0.11 mmol) were heated at 150 C under
ꢂ
ꢂ
under high vacuum, the crude product was purified on neutral alu-
2 2
argon. MnBr $4H O (109 mg, 0.38 mmol) was then added and the
minium oxide column, using CHCl
tion 84 mg of a red-brown solid. Yield: 77%.
3
as eluent, to give after evapora-
reaction mixture was stirred until disappearance of the starting
material controlled by UVevis spectroscopy (8 h). The reaction
mixture was allowed to cool to room temperature and DMF evap-
orated under high vacuum. The crude product was dissolved in 15 ml
1
H NMR (400 MHz, CDCl
CH), 3.10 (s, 24H, NMe ), 2.66 (s, 8H, CH), 1.90 (m, 8H, CH
), 1.40 (m, 8H, CH ), 1.25 (m, 16H, CH ), 1.01 (m, 8H, CH
2.59 (s, 2H, NH pyrrole). UVevis (CHCl ), max, nm (
3
):
d
8.66 (s, 8H,
b
pyrrole), 3.83 (s, 8H,
), 1.81 (m,
),
2
2
8
ꢀ
H, CH
2
2
2
2
CHCl
phase separation and evaporation of CHCl
purified on silica gel column, using a mixture CHCl
as eluent, to give after evaporation 37 mg of a green solid. Yield: 70%.
3
and stirred for 20 min with 5 ml hydrochloric acid (5%). After
, the crude product was
/CH OH (9.5:0.5)
ꢀ1
ꢀ1
3
l
3
, M cm
)
3
3
3
3
4
(
26 (266.797ꢁ10 ), 521 (15.299ꢁ10 ), 557(8.576ꢁ10 ), 593
3
3
3
3
4.325ꢁ10 ), 650 (3.782ꢁ10 ). HRMS [ESI]: m/z calcd for C92
99 8
H N :
þ
ꢀ1
ꢀ1
3
1
315.7987 [MþH] , found: 1315.7997.
UVevis (CHCl
3
),
l
max, nm ( , M cm ) 480 (70.782ꢁ10 ), 586
3
3
3
(
C
7.330ꢁ10 ), 624(7.871ꢁ10 ). HRMS [ESI]: m/z calcd for
þ
4.2.4. Chloro(5,10,15,20-Tetrakis-(10-nitro-1,2,3,4,5,6,7,8-octahydro-
92
H
96MnN
8
1367.7133 [MꢀCl] , found: 1367.7136.
1,4;5,8-dimethano-anthracen-9-yl)-porphyrin) iron(III) 6. Porphyrin
ꢂ
2
(50 mg, 0.037 mmol) in 10 ml THF was heated at 65 C under
4.3. Catalytic oxidation procedure
argon. FeBr $4H O (163 mg, 0.75 mmol) was then added and the
2
2
reaction mixture was stirred until disappearance of the starting
material controlled by UVevis spectroscopy (2 h). The reaction
mixture was allowed to cool to room temperature and THF evap-
orated under vacuum. The crude product was dissolved in 15 ml
4.3.1. General procedure for the catalytic epoxidation reaction of
olefins with iron porphyrin catalyst and hydrogen peroxide. Iron
porphyrin complex 5 (1.2 mg, 1
10 mol) were placed in a test tube under argon. Then, 1 ml of
distilled CH Cl /MeOH mixture (0.5:0.5) was added, followed by
styrene (104 mg, 1 mmol). Aqueous H (35%) (9.7 mg, 100 mol)
in 0.1 ml MeOH was added over a period of 1 h with a syringe-
pump. After the addition of all the H 2, the reaction mixture
was allowed to stir for an additional 1 h. The mixture was analyzed
by GC for oxidation yield based on H , 30%, and for epoxide en-
antiomeric excess, 39% (conditions used: 80 C (1 min), 1 C min
mmol) and imidazole (0.34 mg,
m
CHCl
phase separation and evaporation of CHCl
purified on silica gel column, using a mixture CHCl
3
and stirred for 20 min with 5 ml hydrochloric acid (5%). After
2
2
3
, the crude product was
2
O
2
m
3
3
/CH OH
(
9.5:0.5) as eluent, to give after evaporation 42 mg of a green-
2
O
brown solid. Yield: 84%.
UVevis (CHCl ), max, nm (
ꢀ1
ꢀ1
3
3
l
3
3
, M cm ) 424 (70.591ꢁ10 ), 509
2 2
O
3
ꢂ
ꢂ
ꢀ1
(
9.108ꢁ10 ), 579 (2.675ꢁ10 ). HRMS [ESI]: m/z calcd for
þ
ꢃ
ꢂ
ꢂ
ꢀ1
ꢂ
C
84
H72ClFeN
8
O
8
: 1411.4511 [M] , found: 1411.4509.
80e120 C, 2.5 C min 120e180 C). Polarimetric measurement of
the oxidation product determined that (S)-(ꢀ)-styrene epoxide was
formed in excess. Only traces of phenylacetaldehyde were detected.
The reaction and analysis of the other substrates and catalysts in
Table 1 were carried out in an identical manner with that used for
styrene epoxidation.
4
.2.5. Chloro(5,10,15,20-Tetrakis-(10-dimethylamino-1,2,3,4,5,6,7,8-
iron(III)
. Porphyrin 4 (40 mg, 0.030 mmol) in 10 ml THF was heated at
octahydro-1,4;5,8-dimethano-anthracen-9-yl)-porphyrin)
7
6
ꢂ
5 C under argon. FeBr $4H O (129 mg, 0.60 mmol) was then added
2 2
and the reaction mixture was stirred until disappearance of the
starting material controlled by UVevis spectroscopy (2 h). The re-
action mixture was allowed to cool to room temperature and THF
evaporated under vacuum. The crude product was dissolved in 15 ml
4.3.2. General procedure for the catalytic epoxidation reaction of
olefins with manganese porphyrin catalyst and hydrogen perox-
ide. Manganese porphyrin complex 8 (1.2 mg, 1
azole (0.14 mg, 4 mol) were placed in a test tube under argon. Then,
1 ml of distilled CH Cl was added, followed by styrene (4.16 mg,
40 mol). Aqueous H (35%) (19.4 mg, 200 mol) and imidazole
(0.68 mg, 20 mol) in 0.1 ml MeOH were added over a period of 1 h
with a syringe-pump. After the addition of all the H , the reaction
mmol) and imid-
CHCl
phase separation and evaporation of CHCl
purified on silica gel column, using a mixture CHCl
3
and stirred for 20 min with 5 ml hydrochloric acid (5%). After
, the crude product was
/CH OH (9.5:0.5)
m
3
2
2
3
3
m
O
2 2
m
as eluent, to give after evaporation 30 mg of a green-brown solid.
Yield: 68%.
m
2 2
O
ꢀ
1
ꢀ1
3
UVevis (CHCl
3
),
l
max, nm (
3
, M cm ) 421 (45.060ꢁ10 ), 510
mixture was allowed to stir for an additional 1 h. The mixture was
analyzed by GC for oxidation yield, 40%, and for epoxide enantio-
3
3
(
C
5.504ꢁ10 ), 583(1.686ꢁ10 ). HRMS [ESI]: m/z calcd for
þ
ꢂ
ꢂ
ꢀ1
92
H97ClFeN
8
: 1404.6874 [MþH] , found: 1404.6863.
meric excess, 45% (conditions used: 80 C (1 min), 1 C min
8
ꢂ ꢂ ꢂ
ꢀ1
0e120 C, 2.5 C min 120e180 C). Polarimetric measurement of
4
.2.6. Chloro(5,10,15,20-Tetrakis-(10-nitro-1,2,3,4,5,6,7,8-octahydro-
the oxidation product determined that (S)-(ꢀ)-styrene epoxide was
formed in excess. Only traces of phenylacetaldehyde were detected.
The reaction and analysis of the other substrates and catalysts in
Table 2 was carried out in an identical manner with that used for
styrene epoxidation.
1,4;5,8-dimethano-anthracen-9-yl)-porphyrin)
manganese(III)
9
. Porphyrin 2 (30 mg, 0.022 mmol) in 10 ml DMF and 2,6-lutidine
ꢂ
(
7e8 mg, 0.07 mmol) were heated at 150 C under argon.
2 2
MnBr $4H O (65 mg, 0.22 mmol) was then added and the reaction
mixture was stirred until disappearance of the starting material
controlled by UVevis spectroscopy (8 h). The reaction mixture was
allowed to cool to room temperature and DMF evaporated under
4.3.3. General procedure for the catalytic hydroxylation reaction of ar-
ylalkanes with iron porphyrin catalyst and iodobenzene diacetate. Iron
high vacuum. The crude product was dissolved in 10 ml CHCl
3
and
porphyrin complex 5 (1.2 mg 1 mmol) and imidazole (0.34 mg,