Electrophilic fluoroalkylation of Ni(II) N -confused porphyrins with fluoroalkylarylsulfonium salts

Article abstract of DOI:10.1021/jo3000018

Experimental studies showed that Ni(II) N-confused porphyrins, treated with fluoroalkylarylsulfonium salts, can undergo an electrophilic fluoroalkylation at the inner 21-C position, leading to 21-fluoroalkylated Ni(II) N-confused porphyrins.

Full text of DOI:10.1021/jo3000018

Note
pubs.acs.org/joc
Electrophilic Fluoroalkylation of Ni(II) N-Confused Porphyrins
with Fluoroalkylarylsulfonium Salts
Fei Hao, Hua-Wei Jiang, Guoqiang Zong, Zhiguo Zhou, Ruo-Bing Du, Qing-Yun Chen,
and Ji-Chang Xiao*
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling
Road 200032, P. R. China
S
* Supporting Information
ABSTRACT: Experimental studies showed that Ni(II)
N-confused porphyrins, treated with fluoroalkylarylsulfonium
salts, can undergo an electrophilic fluoroalkylation at the inner
21-C position, leading to 21-fluoroalkylated Ni(II) N-confused
porphyrins.
he fluorinated porphyrin derivatives have been widely
investigated because of their unique properties.1 Im-
we observed the self-assembly and thermal behavior of 5-fluoroalkyl-
10,20-diarylporphyrins12 and documented the synthesis and unique
properties of the nonaromatic 20 π-electron β-tetrakis-
(trifluoromethyl)-meso-tetraphenylporphyrins.13 Then we extended
our research from normal porphyrins to N-confused porphyrins,
T
portantly, when localized to a tumor tissue, fluorinated porphyrin
derivatives can be used as a tracer by 19F NMR imaging.1g,2 What
is more, the introduction of fluorine substituent to the porphyrin
macrocycle might give additional stability and lipophilicity and
therefore increase their antitumor activity.3 These advantages over
ordinary porphyrins make fluorinated porphyrin derivatives
potential candidates for photodynamic therapy (PDT). The
fluorinated porphyrin derivatives have also been proven to be
effective catalysts. In 1989, Tsuchiya’s group found that
perfluorinated Fe(III) porphyrin, which could resist the porphyrin
skeleton to oxidative degradation, effectively catalyzed the
cyclooxidation of alkenes and the hydroxylation of benzene.4
There is a special advantage of fluorinated porphyrins over the
common porphyrins in organometallic catalysis field. That is,
(β-perfluoroalkylated tetraphenylporphyrin)cobalt complex, which
could dissolve in the perfluorinated solvents, could catalyze the
epoxidation of different alkenes with atmospheric air under
fluorous biphasic system other than pure oxygen or high pressure
air.5 Besides these advantages in catalysis, the fluorine-containing
porphyrins have also been applied in semiconductor materials,
molecular devices, etc.6 However, the synthesis of fluorine-
containing metalloporphyrins was very challenging. The traditional
method,7 starting from fluorinated pyrrole or aldehyde, usually
took several steps, leading to very low yields.
In 1999, the Tsudzuki group realized the direct electrophilic
trifluoromethylation of porphyrins with Umemoto’s reagent,
S-(trifluoromethyl)-3,7-dinitrobenzothiophenium trifluorometh-
anesulfonate.8 Introduction of a fluoroalkyl group onto the por-
phyrin macrocycle through direct fluoroalkylation was much more
effective than the traditional procedure. We have been interested in
fluorine-containing porphyrin chemistry. Several efficient methods
for direct fluoroalkylation of porphyrins such as modified
sulfinatodehalogenation,9 copper-induced fluoroalkylation,10 and
Pd-catalyzed fluoroalkylation11 have been developed. Some of the
fluoroalkylated porphyrins showed interesting properties and
potential application in catalysis and material science. For example,
́
which were first reported by Furuta14 and Latos-Grazynski15 in
̇
1994, respectively, focusing on the application of fluoroalkylated
N-confused metalloporphyrins in catalysis. In 2008, we successfully
synthesized the inner fluoroalkylated Ni(II) N-confused porphyr-
ins.16 However, perfluoroalkyl iodides should be added in large
excess, and high temperature (100 °C) was required for the
fluoroalkylation. Moreover, trifluoromethyl Ni(II) N-confused
porphyrins could not be obtained from this procedure.
Recently, we investigated the synthesis of fluoroalkylar-
ylsulfonium salts and their electrophilic fluoroalkylations.17
Considering the electronic properties of N-confused porphyr-
ins, we assumed that the electrophilic fluoroalkylation of Ni(II)
N-confused porphyrins with fluoroalkylarylsulfonium salts
would similarly happen. Herein, we report our results.
We initiated this study with the reaction of Ni(II)
N-confused porphyrins (Ni1) with 5 equiv of trifluoromethyl-
+
diphenylsulfonium salt (CF3SPh2 OTf−, a) in anhydrous THF
for 3 days. Ni1 disappeared completely and afforded a purple
compound in 60% yield after flash chromatography. The
chemical shift at −58.73 ppm observed in 19F NMR and the
[M + H]+ peak at 739.2 in MALDI-MS implied that the
trifluoromethyl group linked to the Ni(II) NCP macrocycle.
1
The chemical shift at δ 10.07 ppm in H NMR indicated that
C(3)H was retained and the six β-pyrrole protons could be
1
observed at δ 8.44−8.70 ppm in the H NMR. These data
together showed that the trifluoromethyl group was intro-
duced into the inner 21-C of Ni1 (Scheme 1). The inner
trifluoromethyl Ni(II) N-confused porphyrins was not obtained
previously from the copper-induced fluoroalkylation, as the
Received: January 5, 2012
Published: March 6, 2012
© 2012 American Chemical Society
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The Journal of Organic Chemistry
Note
of the perfluoroalkyl halide from alkyl halide. The work further
showed that fluoroalkylarylsulfonium salts were effective
fluoroalkylation reagents17 and could be applied in the syn-
thesis the fluoroalkylated NiNCPs.
Scheme 1. Synthesis of Inner 21-C Trifluoromethyl
Ni(II)NCP (Ni1a)
The reaction conditions were optimized by screening the
amount of CF3SPh2 OTf−, temperature, concentration, and
+
solvents (Table 2). It was found that 10 equiv of
Table 2. Fluoroalkylation of Ni1 with CF3SPh2 OTf− under
+
a
Various Conditions
trifluoromethyl iodide is a gas at 100 °C and therefore escaped
from the reaction mixture.
The single-crystal X-ray structure (CCDC 833912) further
confirmed that the trifluoromethyl group was attached to the
inner 21-C. From the side view, it was observed that the
trifluoromethyl group was almost perpendicular to the
macrocycle plane (Figure 1). Selected bond lengths of inner
+
solvent CF3SPh2 O-
b
entry
(mL)
Tf− (equiv) temp (°C), time
yield (%)
1
2
THF (10)
THF (10)
THF (10)
THF (10)
THF (10)
THF (10)
THF (10)
THF (10)
THF (5)
5
10
15
20
30
5
rt, 3 d
60
61
43
40
39
44
61
51
75
53
52
11
55
rt, 3 d
3
rt, 3 d
4
rt, 2 d
5
rt, 2 d
6
reflux, 8 h
reflux, 8 h
reflux, 8 h
reflux, 8 h
reflux, 8 h
reflux, 8 h
reflux, 8 h
7
10
30
10
10
10
10
10
8
9
10
11
12
13
THF (20)
dioxane (5)
toluene (5)
DCE (5)
reflux, 8 h
a
b
33.6 mg (0.05 mmol) of Ni1 was used. Isolated yield.
CF3SPh2 OTf− was needed to facilitate the reaction (Table 2,
+
entries 1−5). A smaller amount of CF3SPh2 OTf− would slow
+
the reaction, while a larger excess of CF3SPh2 OTf− would lead
+
to the degradation of the product Ni1. When the reaction was
conducted at reflux temperature (Table 2, entries 6−8), the
reaction time was shortened to only 8 h. The concentration
also had great influence on the yield. Thus, suitable amounts of
solvent were necessary for the reaction (Table 2, entries 7, 9,
and 10). Then, different solvents such as dioxane, toluene, and
DCE were examined, but no obvious improvement was
observed. On the basis of these results, the optimized reaction
conditions were 33.6 mg (0.05 mmol) of Ni1 and 10 equiv of
sulfonium salt in 5 mL of refluxing THF.
Figure 1. Molecular structure of compound Ni1a. The solvent CDCl3
was omitted for clarity: (a) top view; (b) side view.
With the optimal reaction conditions in hand, the scope of
this reaction was then examined. As shown in Table 3, the
desired fluoroalkylated NiNCPs were obtained smoothly for
each substrate. It is worth mentioning that the substituent at
the para-position of the phenyl moiety had a great influence on
the reaction yield. The yield for Ni3a−c (Table 3, entries 3, 6,
and 9) was lower than that for Ni1a−c (Table 3, entries 1, 4,
and 7), which might be due to the decreased electron density of
the porphyrin macrocycle with a para electron-withdrawing
group (-Cl) in Ni3a−c. It might be expected that the yields for
Ni2a−c with a methyl group at the para-position on the phenyl
ring would be higher. However, the yields for Ni2a−c (Table 3,
entries 2, 5, and 8) were much lower compared to those for
Ni1a−c and Ni3a−c. This might be because of the higher
susceptibility of Ni2 to oxidation20 and the fluoroalkyl
21-C are shown in Table 1. It was found that the C(21)−Ni
bond length (2.015 Å) is in the length range of a Ni(II)−C
Table 1. Length of C21-Linked Four Bonds
bond
C(21)−C(1) C(21)−C(4) C(21)−C(49) C(21)-Ni
1.478 1.526 2.015
bond length (Å) 1.505
single bond (1.81−2.02 Å).18 That is to say, C(21) has been
linked with four single bonds. This structure was very similar to
the methylation product of NiNCP.19a Though the alkylation
of the NiNCPs has been well established,19 however, the
fluoroalkylation could not be achieved by the reaction of
NiNCP and perfluoroalkyl iodide under the alkylation reaction
conditions because of the totally different chemical properties
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Note
a
Table 3. Fluoroalkylation of Ni(II) NCPs with Fluoroalkylarylsulfonium Salts
b
entry
Ni(II) NCP
sulfonium salt
time (h)
product
yield (%)
1
2
3
4
5
6
7
8
9
Ni1
Ni2
Ni3
Ni1
Ni2
Ni3
Ni1
Ni2
Ni3
a
a
a
b
b
b
c
c
c
8
Ni1a
Ni2a
Ni3a
Ni1b
Ni2b
Ni3b
Ni1c
Ni2c
Ni3c
75
60
65
43
36
39
38
33
35
5
9
2.5
2
3
2.5
2
3
a
b
General conditions: 0.05 mmol of NiNCP, 0.5 mmol of fluoroalkylarylsulfonium salt, 5 mL of THF. Isolated yield.
Scheme 2. Proposed Mechanism
sulfonium salts a−c used in the reaction are somewhat
oxidative.17a The substituents on the phenyl ring affected the
electrophilic fluoroalkylation through their effects on the
electron density of the macrocyclic system, and also influenced
the oxidizability of NiNCPs. Compared with our previous
copper-induced fluoroalkylation method, in which 100 equiv of
fluoroalkyl iodide is necessary when preparing Ni1c−Ni3c,16
much smaller amounts of fluoroalkylation reagent (10 equiv)
were needed for the completion of the reaction according to
the present procedure (Table 3, entries 7−9).
A possible mechanism was proposed as shown in Scheme 2.
First, 21-C attacks the fluoroalkyl group of the sulfonium salt,
leading to the opening of the carbon−carbon double bond.
Subsequently, the release of the proton yields the inner
fluoroalkylated Ni(II) NCP. This direct electrophilic fluo-
roalkylation was quite different from the previous fluoroalkyl-
copper mechanism.16
approach. The interesting substitution effect at the para-
position of the phenyl moiety was found. Further studies on the
properties and applications of fluoroalkylated N-confused porphyr-
ins are now underway.
EXPERIMENT SECTION
■
THF was distilled over sodium with benzophenone as oxygen
presence indicator in argon atmosphere. NiNCPs and fluoroalkylar-
ylsulfonium salts were prepared according to the reported literatur-
es.15,17a,b,21 Other chemicals were used without purification.
Typical Procedure for the Synthesis of 21-Fluoroalkylated
Ni(II) N-Confused Porphyrins. A mixture of Ni1 (33.6 mg,
0.05 mmol) and a (202.3 mg, 0.5 mmol) was heated in 5 mL of THF
under reflux for 3−8 h. The reaction course was monitored by TLC.
When Ni1 was totally consumed, the reaction mixture was evaporated by
rotary evaporator to dryness. After column chromatography on silica gel
using CH2Cl2 as an eluent (the first band was collected) and
crystallization from CH2Cl2/hexane, a purple solid Ni1a was obtained.
Ni1a: amorphous solid, 27.8 mg, yield 75%, melting point over
300 °C. A single crystal of Ni1a was obtained by recrystallization from
CDCl3. 1H NMR (400 MHz, CDCl3): δ 10.06 (s, 1H), 8.68 (d, J = 4.8
Hz, 1H), 8.65 (d, J = 5.6 Hz, 1H), 8.54 (d, J = 2.8, 1H), 8.53 (d, J =
2.8, 1H), 8.48 (d, J = 5.2 Hz, 1H), 8.44 (d, J = 4.8 Hz, 1H), 7.66 - 8.12
In conclusion, the direct and mild electrophilic fluoroalky-
lation of Ni(II) N-confused porphyrins was realized by using
fluoroalkylarylsulfonium salts. The inner trifluoromethyl Ni(II)
N-confused porphyrins was successfully obtained through this
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The Journal of Organic Chemistry
Note
(m, 20H). 13C NMR (100 MHz, CDCl3): δ172.9, 160.0, 157.5, 155.6,
149.6, 148.7, 147.9, 146.9, 146.8, 140.7, 140.6, 140.3, 140.2, 136.1,
135.4, 135.2, 135.0, 134.1, 134.0, 133.9, 133.8, 133.7, 133.6, 133.6,
133.5, 133.4, 133.4, 133.1, 133.0, 132.6, 132.0, 129.2, 129.1, 128.9,
128.3, 128.2, 128.2, 128.2, 127.97, 127.6, 126.9, 126.9, 126.7, 124.9,
121.4 (q, J = 281 Hz, CF3). 19F NMR (376 MHz, CDCl3): δ −58.73
(s, 3F). UV/vis (CH2Cl2): λmax (relative intensity) = 318 (2.8), 434
(8.8), 551 (1.0) nm. HRMS (MALDI): calcd for [C45H27N4F3Ni +
H]+ 739.1614, found 739.1606.
Ni1b: amorphous solid, 17.0 mg, yield 43%, melting point over
300 °C. 1H NMR (400 MHz, CDCl3): δ 9.89 (s, 1H), 8.58−8.61 (m, 2H),
8.49−8.50 (m, 2H), 8.45−8.47 (m, 1H), 8.42−8.43 (m, 1H), 7.68−
8.12 (m, 20H). 13C NMR (100 MHz, CDCl3): δ 173.9, 160.3, 157.2,
156.4, 156.1, 149.9, 148.9, 148.8, 148.1, 148.0, 147.8, 146.8, 140.8,
140.7, 140.5, 140.4, 135.7, 135.6, 134.7, 134.6, 134.0, 133.8, 133.1,
133.0, 132.4, 132.2, 132.1, 129.8, 129.1, 129.1, 128.4, 128.3, 128.2,
128.2, 128.1, 127.9, 127.9, 126.9, 126.5, 124.7. 19F NMR (376 MHz,
CDCl3): δ −80.83 (s, 3F), −99.12, −100.26 (AB, JAB = 256.4 Hz, 2F).
UV/vis (CH2Cl2): λmax = 435 nm. HRMS (MALDI): calcd for
[C46H27N4F5Ni + H]+ 789.1582, found 789.1558.
138.9, 138.8, 138.7, 138.6, 138.6, 138.6, 136.1, 136.0, 135.7, 135.6,
135.2, 135.2, 134.9, 134.9, 134.8, 134.7, 134.6, 134.3, 133.2, 133.0,
132.7, 132.5, 132.2, 132.2, 128.6, 128.6, 128.4, 128.3, 127.3, 125.2,
123.5. 19F NMR (376 MHz, CDCl3): δ −80.99 (s, 3F), −99.35,
−100.42 (AB, JAB = 145.1 Hz, 2F). UV/vis (CH2Cl2): λmax = 418 nm.
HRMS (MALDI): calcd for [C46H23N4F5Cl4Ni + H]+ 925.0023, found
925.0023.
Ni3c: amorphous solid, 16.5 mg, yield 35%, melting point over
1
300 °C. H NMR (400 MHz, CDCl3): δ = 9.79 (s, 1H), 8.58 (d, J =
4.8 Hz, 2H), 8.47 (d, J = 5.2 Hz, 2H), 8.45 (d, J = 4.8 Hz, 1H), 8.41
(d, J = 5.2 Hz, 1H), 7.67−8.04 (m, 16H). 19F NMR (376 MHz,
CDCl3): δ = −63.64, −65.75 (AB, JAB = 169.6 Hz, 2F), −92.33 (m,
2F). HRMS (MALDI): calcd for [C46H23N4F4Cl5Ni + H]+ 940.9728,
found 940.9711.
ASSOCIATED CONTENT
* Supporting Information
■
S
X-ray crystal structure of compound Ni1a and characterization
of new compounds. This material is available free of charge via
the Internet at http://pubs.acs.org.
Ni1c: amorphous solid, 15.3 mg, yield 38%, melting point over
300 °C. 1H NMR (400 MHz, CDCl3): δ 9.82 (s, 1H), 8.61 (m, 2H), 8.43−
8.50 (m, 4H), 7.69−8.12 (m, 20H). 19F NMR (376 MHz, CDCl3): δ
−63.30, −65.38 (AB, JAB = 167.7 Hz, 2F), −92.18 to −92.14 (m, 2F).
HRMS (MALDI): calcd for [C46H27N4F4ClNi + H]+ 805.1287, found
805.1289.
AUTHOR INFORMATION
Corresponding Author
*E-mail: jchxiao@sioc.ac.cn.
■
Ni2a: amorphous solid, 23.9 mg, yield 60%, melting point over 300
°C. H NMR (400 MHz, CDCl3): δ 10.03 (s, 1H), 8.68−8.65 (m,
Notes
1
The authors declare no competing financial interest.
2H), 8.53 (d, J = 5.2 Hz, 2H), 8.48 (d, J = 4.4 Hz, 1H), 8.44 (d, J =
4.4 Hz, 1H), 7.48−8.12 (m, 16H), 2.62−2.66 (m, 12H). 13C NMR
(100 MHz, CDCl3): δ 173.5, 160.0, 157.5, 155.7, 149.7, 148.7, 147.9,
147.1, 146.8, 139.1, 138.2, 138.0, 137.9, 137.9, 137.8, 137.7, 137.6,
135.8, 135.4, 135.3, 134.8, 133.7, 133.1, 132.8, 132.4, 131.8, 128.9,
128.9, 128.7, 127.7, 127.6, 127.6, 126.6, 124.8, 21.6, 21.5. 19F NMR
(376 MHz, CDCl3): δ −58.78 (s, 3F). UV/vis (CH2Cl2): λmax (relative
intensity) = 338 (9.4), 437 (2.8), 551 (1.0) nm. HRMS (MALDI):
calcd for [C49H35N4F3Ni + H]+ 795.2240, found 795.2215.
ACKNOWLEDGMENTS
■
We thank the Chinese Academy of Sciences and the National
Natural Science Foundation (21032006, 21172240) and the
973 Program of China (2012CBA01200, 2012CB821600) for
financial support.
REFERENCES
■
Ni2b: amorphous solid, 15.2 mg, yield 36%, melting point over 300
1
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°C. H NMR (400 MHz, CDCl3): δ 9.84 (d, J = 0.8 Hz, 1H), 8.58−
8.61 (m, 2H), 8.50 (d, J = 5.2 Hz, 2H), 8.45−8.47 (m, 1H), 8.41−8.43
(m, 1H), 7.49−8.00 (m, 16H), 2.61−2.65 (m, 12H). 13C NMR (100
MHz, CDCl3): δ 174.2, 160.2, 156.9, 156.2, 149.9, 149.0, 147.8, 146.9,
139.2, 139.1, 138.3, 138.2, 138.0, 138.0, 137.9, 137.9, 137.8, 137.8,
135.4, 135.3, 134.4, 134.3, 133.9, 133.0, 132.8, 132.3, 131.9, 129.7,
129.0, 128.9, 128.8, 128.7, 127.7, 127.6, 126.4, 124.7, 21.5, 21.5, 21.5.
19F NMR (376 MHz, CDCl3): δ −80.92 (s, 3F), −99.28, −100.45
(AB, JAB = 186.1 Hz, 2F). UV/vis (CH2Cl2): λmax (relative intensity) =
338 (2.7), 438 (8.2), 562 (1.0) nm. HRMS (MALDI): calcd for
[C50H35N4F5Ni + H]+ 845.2208, found 845.2187.
Ni2c: amorphous solid, 14.2 mg, yield 33%, melting point over
1
300 °C. H NMR (400 MHz, CDCl3): δ 9.78 (s, 1H), 8.9 (m, 2H),
8.42−8.50 (m, 4H), 7.48−8.00 (m, 16H), 2.61−2.64 (m, 12H). 19F
NMR (376 MHz, CDCl3): δ = −63.70, −65.79 (AB, JAB = 225.2 Hz,
2F), −92.73 to −92.67 (m, 2F). HRMS (MALDI): calcd for
[C50H35N4F4ClNi + H]+ 861.1913, found 861.1924.
Ni3a: amorphous solid, 28.5 mg, yield 65%, melting point over
300 °C. 1H NMR (400 MHz, CDCl3): δ 10.04 (s, 1H), 8.65 (m, 2H),
8.44−8.52 (m, 4H), 7.68−8.02 (m, 16H). 13C NMR (100 MHz,
CDCl3): δ 174.9, 161.5, 159.2, 157.2, 151.3, 150.3, 149.5, 148.7, 148.4,
140.6, 140.4, 140.2, 140.1, 138.2, 137.8, 137.7, 137.7, 136.9, 136.8,
136.8, 136.7, 136.6, 135.1, 134.7, 134.4, 134.1, 133.8, 130.3, 130.0,
129.6, 129.0, 129.0, 127.2, 125.4. 19F NMR (376 MHz, CDCl3): δ
−58.68 (s, 3F). UV/vis (CH2Cl2): λmax (relative intensity) = 330 (2.8),
436 (8.7), 540 (1.0) nm. HRMS (MALDI): calcd for
[C45H23N4F3Cl4Ni + H]+ 875.0055, found 875.0066.
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Ni3b: amorphous solid, 18.1 mg, yield 39%, melting point over
1
300 °C. H NMR (400 MHz, CDCl3): δ 9.86 (d, J = 0.8 Hz, 1H),
8.58−8.62 (m, 2H), 8.41−8.50 (m, 4H), 7.68−8.05 (m, 16H). 13C
NMR (100 MHz, CDCl3): δ 174.0, 173.9, 160.0, 157.0, 156.2, 155.9,
149.9, 149.8, 148.9, 148.8, 148.1, 148.0, 147.7, 147.6, 146.7, 139.0,
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The Journal of Organic Chemistry
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