Metalloporphyrin/Iodine(III)-Cocatalyzed oxygenation of aromatic hydrocarbons asc.wiley-vch.de

Article abstract of DOI:10.1002/adsc.201000172

Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol% of iodobenzene and 5 mol% of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.

Full text of DOI:10.1002/adsc.201000172

COMMUNICATIONS
DOI: 10.1002/adsc.201000172
Metalloporphyrin/Iodine
Aromatic Hydrocarbons
N
Akira Yoshimura,a Heather M. Neu,a Victor N. Nemykin,a,*
and Viktor V. Zhdankina,*
a
Department of Chemistry and Biochemistry, University of Minnesota Duluth, Duluth, MN 55812, USA
Fax : (+1)-218-726-7394; e-mail: vnemykin@d.umn.edu or vzhdanki@d.umn.edu
Received: March 5, 2010; Revised: May 11, 2010; Published online: June 8, 2010
Abstract: Hypervalent iodine species have a pro-
nounced catalytic effect on the metalloporphyrin-
mediated oxygenations of aromatic hydrocarbons.
In particular, the oxidation of anthracene to anthra-
quinone with Oxone readily occurs at room temper-
ature in aqueous acetonitrile in the presence of 5–
20 mol% of iodobenzene and 5 mol% of a water-
(PhIO)n, is the most efficient source of oxygen in the
oxygenation of hydrocarbons in the presence of iron-
AHCTUNGTRENNUNG
(III) porphyrin complexes,[2a] and since then iodosylar-
enes and other hypervalent iodine reagents have been
widely used as stoichiometric oxidants in the reactions
mimicking natural oxidations performed by the heme-
containing cytochrome P-450 class of enzymes.[1,2]
It is generally agreed that the intermediate high
valent metal oxo-complexes are responsible for the
oxygen transfer from (PhIO)n to the organic substrate.
However, the details of the initial interaction of
soluble ironACHTUNGTRENNUNG(III)-porphyrin complex. 2-tert-Butylan-
thracene and phenanthrene also can be oxygenated
under similar conditions in the presence of
50 mol% of iodobenzene. The oxidation of styrene
in the presence of 20 mol% of iodobenzene leads to
a mixture of products of epoxidation and cleavage
of the double bond. Partially hydrogenated aromat-
ic hydrocarbons (e.g., 9,10-dihydroanthracene,
1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H-
indene) afford under these conditions products of
oxidation at the benzylic position in moderate
yields. The proposed mechanism for these catalytic
oxidations includes two catalytic redox cycles: 1) in-
itial oxidation of iodobenzene with Oxone produc-
iodineACHTNUTRGNE(UNG III) species with the metal complex are still
unclear. In particular, it has been shown that iodosyl-
benzene reacts with metalloporphyrins with the for-
mation of unstable adducts, which can serve as the
actual oxidants in catalytic oxygenations and thus ex-
plain the unusual reactivity of hypervalent iodine re-
agents as terminal oxidants.[3] Herein we report our
study on the catalytic application of iodine
cies in the metalloporphyrin-mediated oxygenation of
aromatic hydrocarbons with Oxone
ACHTUNGTRENN(UNG III) spe-
ing the hydroxy
iodosylbenzene, and 2) the oxidation of iron
porphyrin to the oxoiron(IV)-porphyrin cation-radi-
cal complex by the intermediate iodine(III) species.
A
(2KHSO5·KHSO4·K2SO4) as terminal oxidant. The re-
sults of this study indicate that hypervalent iodine
species have a pronounced catalytic effect on the bio-
AHCTUNGTRENNUNG
N
mimetic ironACTHUNGETRNNU(G III) porphyrin-mediated oxygenations of
The oxoiron(IV)-porphyrin cation-radical complex
acts as the actual oxygenating agent toward aromat-
ic hydrocarbons.
aromatic hydrocarbons.
Our approach involves the use of iodineACTHNURGTNE(UNG III) spe-
cies, generated in situ from iodobenzene and Oxone
in aqueous acetonitrile, as the efficient source of
oxygen in the oxygenation of aromatic hydrocarbons
in the presence of water-soluble metalloporphyrin
complexes 1 (Figure 1). At the initial stage of our
study, we have investigated and optimized a water-
based oxidizing system utilizing metalloporphyrin cat-
alysts and a water-soluble stoichiometric hypervalent
Keywords: catalysis; hypervalent iodine; iodine; ox-
idation; porphyrinoids
The catalytic properties of transition-metal porphyr- iodine oxidant that can be generated from iodoben-
ins, phthalocyanines, and related compounds in the zene and Oxone in aqueous solutions.
biomimetic oxygenations of organic substrates are
First of all, several preliminary experiments were
well-documented in the literature.[1] Various terminal performed in order to identify the most active catalyst
oxidants (e.g., O2, hydrogen peroxide and organic per- 1 and to ensure that Oxone alone cannot serve as a
oxides) have been used in these oxygenations. In 1979 source of oxygen in the metalloporphyrin-mediated
Groves and co-workers reported that iodosylbenzene, oxygenations (Table 1). We have tested the catalytic
Adv. Synth. Catal. 2010, 352, 1455 – 1460
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1455

Akira Yoshimura et al.
COMMUNICATIONS
Figure 1. Water-soluble metalloporphyrin complexes 1.
Scheme 1. Metalloporphyrin-catalyzed oxygenations using
iodosylbenzene sulfate 2 as a stoichiometric oxidant.
activity of water-soluble metalloporphyrins 1a–f using
the water-soluble oligomeric iodosylbenzene sulfate 2
as a terminal stoichiometric oxidant in the oxygena-
tion of anthracene 3.[4] Reagent 2 was generated in that the treatment of anthracene 3 with complex 1a
situ from (diacetoxyiodo)benzene and sodium bisul- (5 mol%) and 8.2 mol equiv. of Oxone in a 1:1 mix-
fate (Scheme 1) according to the known procedure.[5] ture acetonitrile-water does not lead to any significant
The results of these oxidations (Table 1, entries 1–7) oxidation of the substrate (entry 8, Table 1). The addi-
clearly indicate that FeACTHNUTRGNEU(GN III)-porphyrin 1a is the most tion of a phase-transfer catalyst, NBu4HSO4, to im-
active catalyst under these conditions (entry 2), while prove the solubility of Oxone in acetonitrile, also did
the Zn(II)-porphyrin 1f does not show any catalytic not have any noticeable effect (entry 9).
effect as expected from the inability of Zn(II) to par-
ticipate in oxygen-transfer processes. Based on these metalloporphyrin-catalyzed oxygenation in aqueous
results, we have used the Fe(III)-porphyrin complex solution, we have developed a Fe(III)-porphyrin/
1a in all following experiments. iodine(III) co-catalytic system utilizing iodobenzene,
Based on the optimized reaction conditions for the
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
In the next set of preliminary experiments, we have PhI, as a pre-catalyst. The actual source of oxygen in
tested the ability of Oxone to serve as a source of the metalloporphyrin-mediated oxygenations shown
oxygen in the metalloporphyrin-mediated oxygena- in Scheme 1 are the iodineACTHNUTRGNE(NUG III) species formed in
tions. In particular, separate experiments have shown aqueous solution upon dissociation of the oligomeric
iodosylbenzene sulfate 2. A previously reported mass
spectrometry study of the aqueous solution of 2 has
Table 1. Catalytic effect of metalloporphyrins 1 and PhI on
shown that these species are represented mainly by
the oxygenation of anthracene 3 to anthraquinone 4.[a]
hydroxy
iodosylbenzene, PhI(OH)2.[5a,b] We have found that
the same iodine(III) species can be generated in solu-
(phenyl)iodonium ion, PhI+OH, and hydrated
ACHTUNGTRENNUNG
Entry Catalyst[b] Oxidant[c] PhI
(mol%) [h]
Time Yield of 4
[%]
AHCTUNGTRENNUNG
tion by simple treatment of iodobenzene with Oxone
in aqueous acetonitrile at room temperature
(Scheme 2).
1
2
3
4
5
6
7
8
none
1a
1b
1c
1d
1e
1f
1a
1a
none
1a
1a
1a
2
2
2
2
2
2
2
0
0
0
0
0
0
0
0
3
1
3
5
3
3
3
1
24
24
1
1
1
8
100,[d] 88[e]
5[d]
The presence of the [PhIO+H]+ and [PhI(OH)2 +
H]+ species in such solutions (Scheme 2) is supported
by mass spectrometry (see Experimental Section).
Based on this observation, we have tested the metal-
loporphyrin/PhI-cocatalyzed oxygenations and were
pleased to find that the oxidation of anthracene 3 to
anthraquinone 4 selectively proceeds in aqueous ace-
tonitrile at room temperature in the presence of Fe-
48[d]
85[d]
5[d]
2[d]
Oxone
Oxone[f]
Oxone
Oxone
Oxone
Oxone
0[d]
9
0
1.5[d]
0[d]
10
11
12
13
20
20
10
5
100[d]
39[d,g]
35[d,g]
AHCTUNGTREGUN(NN III)-porphyrin 1a (5 mol%) and PhI (20 mol%) with
Oxone as terminal oxidant (Table 1, entry 11). The
use of smaller amounts of PhI led to a lower conver-
sion (Table 1, entries 12 and 13). In the absence of
[a]
All reactions were performed at room temperature in
MeCN/H2O (1:1 v/v) under stirring.
5 mol% of catalyst 1 were used.
2 mol equiv. of reagent 2 (6 equiv. of active O) or 8.2
mol equiv. of Oxone (16.4 equiv. of active O) were used.
GC yield.
[b]
[c]
[d]
[e]
[f]
Isolated yield.
NBu4HSO4 (20 mol%) as a phase-transfer catalyst was
added.
Also contains unreacted 3.
Scheme 2. Active iodine
ACHTUNGTRNE(NUNG III) species generated in solution
[g]
by treatment of iodobenzene with Oxone.
1456
asc.wiley-vch.de
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1455 – 1460

Metalloporphyrin/IodineACTHNUTRGNE(NUG III)-Cocatalyzed Oxygenation of Aromatic Hydrocarbons
Scheme 3. FeACHTUNGTRENNUNG(III)-porphyrin-catalyzed and iodineCAHTUNGTERN(NUGN III)-mediated oxygenations using Oxone as a stoichiometric oxidant.
catalyst 1 this system does not lead to any significant in the presence of iron-porphyrin complexes was pre-
oxidation of the substrate (Table 1, entry 10).
viously reported in the literature.[2a] Partially hydro-
In order to demonstrate the general character of
this catalytic reaction, we performed the iodine
mediated oxidation of aromatic hydrocarbons 5 and 7
in the presence of Fe(III)-porphyrin 1a (Scheme 3).
ACHTUNGTRNE(NUNG III)-
Table 2. Oxidation of styrene, partially hydrogenated aro-
matic hydrocarbons, and adamantane using Fe
ACHTUNGTREN(NUNG III)-porphy-
rin/PhI catalytic system.[a]
AHCTUNGTRENNUNG
Compared to the oxidation of anthracene 3, the reac-
tion of 2-tert-butylanthracene 5 was slower, probably
due to steric hindrance caused by the tert-butyl group.
However, the use of larger amounts of PhI (50 mol%)
allowed us to reach a 100% conversion in 3 h at room
temperature. The GC analysis of the reaction mixture
indicated the presence of a single product of oxida-
tion, 2-tert-butylanthraquinone 6, along with some io-
dobenzene. The pure 2-tert-butylanthraquinone 6 was
isolated from the reaction mixture by preparative
TLC chromatography on silica gel as yellow needles
in 80% yield and identified by comparison with an au-
thentic sample. The previously reported oxidation of
2-tert-butylanthracene using stoichiometric oxidant 2
Entry Substrate
Conversion Products
after 1 h
[%]
Yield
[%][b,c]
1
99
40
39
10
2
38
38
in the FeACHTUNGTRENNUNG(III)-phthalocyanine-catalyzed oxygenations
in toluene proceeded more slowly (20 h at room tem-
perature) and afforded 2-tert-butylanthraquinone 6 in
72% isolated yield.[4a] Phenanthrene 7 is even less re-
active, producing phenanthrene-9,10-dione 8 under
these conditions only in 14% yield after 7 days at
room temperature. The low reactivity of phenan-
threne is in agreement with the previously reported
3
4
17
65
17
19
FeACHTUNGTRENNUNG(III)-phthalocyanine-catalyzed oxygenations using
oxidant 2.[4b]
46
2
Preliminary studies have shown that the FeACTHNUGRTNEUNG(III)-
porphyrin/PhI catalytic system can be effectively ap-
plied toward the oxidation of alkenes; however, these
reactions in general lack selectivity. In particular, the
oxidation of styrene in the presence of 20 mol% of io-
dobenzene proceeds with 99% conversion after 1
hour leading to a mixture of products of epoxidation,
ring hydroxylation, and cleavage of the double bond
(Table 2, entry 1). No oxidation of styrene is observed
under these conditions in the absence of PhI even
after 24 h. The formation of epoxides in moderate
yields in the reaction of alkenes with iodosylbenzene
5
2
[a]
All reactions were performed at room temperature in
MeCN/H2O (1:1 v/v) using 5 mol% of catalyst 1a,
20 mol% of PhI and 8.2 mol equiv. of Oxone; product
composition after 1 h of reaction is shown.
Product composition and yields were determined by GC-
MS.
[b]
[c]
For all substrates, no significant oxidation was observed
in the absence of PhI.
Adv. Synth. Catal. 2010, 352, 1455 – 1460
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1457

Akira Yoshimura et al.
COMMUNICATIONS
genated aromatic hydrocarbons (e.g., 9,10-dihydroan- sylbenzene as a common source of oxygen in the reac-
thracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihy- tions mimicking natural oxidations performed by cy-
dro-1H-indene) afford under these conditions prod- tochrome P-450 class of enzymes. At the same time,
ucts of oxidation at the benzylic position in moderate this new catalytic system can serve as a basis for new
to low conversions (Table 2, entries 2–4). The oxida- efficient synthetic methodologies. The new metallo-
tion of adamantane under these conditions proceeds porphyrin/iodine
very slowly (entry 5, 2% conversion after 1 hour). plement the recently reported iodine(V)/Ru
The previously reported oxidation of adamantane catalyzed benzylic oxidations[7] and bring a new di-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
using FeACHTUNGTRENNUNG(III)-porphyrin and stoichiometric iodosyl- mension to the emerging field of hypervalent iodine
benzene afforded 1-adamantanol in 12% yield; the catalysis.[8,9]
lower yields of the less reactive hydrocarbons were
explained by oxidative degradation of the catalyst.[2a]
Our results clearly indicate that PhI has a pro- Experimental Section
nounced catalytic effect on the metalloporphyrin-
mediated oxygenations and thus support previous ob- General Methods
servations about the high reactivity of iodineACTHNUTRGENUG(N III) spe-
All reactions were performed under dry nitrogen atmos-
phere with flame-dried glassware. All commercial reagents
were ACS reagent grade and used without further purifica-
tion. GC-MS analysis was carried out with an HP 5890A
Gas Chromatograph using a 5970 Series mass selective de-
tector. Mass spectrometric (ESI-MS) analyses were obtained
at the University of Minnesota Minneapolis Mass Spectrom-
etry Facility, using a BioTOF II mass spectrometer.
cies as the source of oxygen.[2,3] It was suggested pre-
viously that a direct transfer of oxygen from iodosyl-
benzene to an organic substrate is possible in the
presence of transition metal ions,[6] which may acti-
vate an iodine
sults of our study support the special role of iodine-
(III) in these oxygenations; however, the observation
ACHTUNGTRENNUNG
(III) species as a Lewis acid.[6a] The re-
ACHTUNGTRENNUNG
that Zn(II)-porphyrin 1f does not show any catalytic
effect (Table 1, entry 7) indicates that the high valent
metal oxo-complexes are responsible for the oxygen
transfer to the substrate.
Typical Procedure for Metalloporphyrin-Catalyzed
Oxygenation of Anthracene using Iodosylbenzene
Sulfate 2 (in situ) as a Stoichiometric Oxidant
A simplified mechanism for these catalytic oxida-
tions is shown in Scheme 4 that includes two catalytic
redox cycles. We propose that the intermediate
A solution of anthracene 3 (0.05 mmol) in a 1:1 mixture of
acetonitrile/water (2 mL) was mixed with the appropriate
catalyst 1 (0.0025 mmol, 0.05 mol equiv.), (diacetoxyiodo)-
benzene (0.25 mmol, 5 mol equiv.), and sodium bisulfate
(0.25 mmol, 5 mol equiv.), with stirring, at room tempera-
ture. Samples of the reaction mixture (100 mL) were collect-
ed every hour, filtered through 2–3 cm of silica gel suspend-
ed in a Pasteur pipette, washed with a mixture of ethyl ace-
tate and hexane (2:3 v:v), and analyzed using GC-MS.
iodine
ACHTUNGTRENNUNG
of the Fe
ACHTUNGTRENNUNG
rin complex. The oxoiron(IV) porphyrin complex acts
as the actual oxygenating agent according to the pre-
viously discussed mechanisms.[1–3] Our results are in
agreement with previous observations[3] that iodosyl-
benzene can react with metalloporphyrins with the
formation of highly reactive adducts, which can serve
as the actual oxidants in catalytic oxygenations.
FeACTHNUGRTENUNG(III)-Porphyrin/PhI-Cocatalyzed Oxygenation of
Anthracene
In conclusion, the results of our study indicate that
hypervalent iodine species have a pronounced catalyt-
ic effect on the ironACHTNUGRTENUNG(III) porphyrin-mediated oxygena-
tions of aromatic hydrocarbons. This effect should be
taken into consideration by researchers utilizing iodo-
A solution of anthracene 3 (89 mg, 0.5 mmol) in a 1:1 mix-
ture of acetonitrile/water (2 mL) was mixed with FeACHTUNGTRENNUNG(III)
porphyrin 1a (22 mg, 0.025 mmol), iodobenzene (20 mg,
0.1 mmol), and Oxone (2.52 g, 4.1 mmol), with stirring, at
room temperature. The reaction mixture (100 mL samples)
was analyzed using GC-MS. Upon completion of the reac-
tion, the reaction mixture was concentrated and separated
using TLC plate and ethyl acetate/hexane (2:3 v:v) mixture
as the eluent to afford analytically pure anthraquinone 4;
yield: 59.4 mg (57%).
FeACTHNUGRTENUNG(III)-Porphyrin/PhI-Cocatalyzed Oxygenation of
2-tert-Butylanthracene
A solution of 2-tert-butylanthracene 5 (117 mg, 0.5 mmol) in
a 1:1 mixture of acetonitrile/water (2 mL) was mixed with
Scheme 4. Tandem catalytic cycles for the Fe
A
FeACHTNGUTERN(UNG III) porphyrin 1a (22 mg, 0.025 mmol), iodobenzene
(51 mg, 0.25 mmol), and Oxone (2.52 g, 4.1 mmol), with stir-
iodine
N
bons.
ring, at room temperature. The reaction mixture (100 mL
1458
asc.wiley-vch.de
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1455 – 1460

Metalloporphyrin/IodineACTHNUTRGNE(NUG III)-Cocatalyzed Oxygenation of Aromatic Hydrocarbons
Figure 2. ESI mass spectrum of PhI-Oxoneꢁ mixture in aqueous acetonitrile.
samples) was analyzed using GC-MS every hour. Upon
completion of the reaction, the reaction mixture was con-
centrated and products were separated using TLC plate and
ethyl acetate/hexane (2:3 v:v) mixture as the eluent to
afford analytically pure 2-tert-butylanthraquinone as yellow
needles; yield: 107 mg (80%), mp 103–1048C.[10]
rin 1a (0.0025 mmol, 0.05 mol equiv.), iodobenzene
(0.025 mmol, 0.5 mol equiv.), and Oxone (0.41 mmol, 8.2
mol equiv.), with stirring, at room temperature. Samples of
the reaction mixture (100 mL) were collected every hour, fil-
tered through 2–3 cm of silica gel suspended in a Pasteur
pipet, washed with a mixture of ethyl acetate and hexane
(2:3 v:v), and analyzed using GC-MS.
FeACHTUNGTRENNUNG(III)-Porphyrin/PhI-Cocatalyzed Oxygenation of
Phenanthrene
A solution of phenanthrene 7 (0.05 mmol) in a 1:1 mixture
of acetonitrile/water (2 mL) was mixed with FeACHTNUTRGNE(NUG III) porphy-
Adv. Synth. Catal. 2010, 352, 1455 – 1460
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1459

Akira Yoshimura et al.
COMMUNICATIONS
12; d) Y. Moro-oka, M. Akita, Catal. Today 1998, 41,
327–338; e) R. Noyori, Asymmetric Catalysis in Organ-
ic Synthesis Wiley, New York, 1994.
FeACHTUNGTRENNUNG(III)-Porphyrin/PhI-Cocatalyzed Oxidations of
Styrene, 9,10-Dihydroanthracene, 1,2,3,4-Tetrahydro-
naphthalene, 2,3-Dihydro-1H-indene, and
Adamantane (Table 2)
[3] a) R. Jin, C. S. Cho, L. H. Jiang, S. C. Shim, J. Mol. Cat.
A: Chem. 1997, 116, 343–347; b) J. P. Collman, A. S.
Chien, T. A. Eberspacher, J. I. Brauman, J. Am. Chem.
Soc. 2000, 122, 11098–11100; c) D. Feichtinger, D. A.
Plattner, J. Chem. Soc. Perkin Trans. 2 2000, 1023–
1028; d) K. P. Bryliakov, E. P. Talsi, Chem. Eur. J. 2007,
13, 8045–8050; e) K. P. Bryliakov, E. P. Talsi, Angew.
Chem. 2004, 116, 5340–5342; Angew. Chem. Int. Ed.
2004, 43, 5228–5230; f) K. P. Bryliakov, D. E. Babush-
kin, E. P. Talsi, J. Mol. Catal. A: Chem. 2000, 158, 19–
35.
A solution of the organic substrate (0.05 mmol) in a 1:1 mix-
ture of acetonitrile/water (2 mL) was mixed with FeACTHUNTGRNEUNG(III)
porphyrin 1a (0.0025 mmol, 0.05 mol equiv.), iodobenzene
(0.01 mmol, 0.2 mol equiv.), and Oxone (0.41 mmol, 8.2 mo-
l equiv.), and stirred at room temperature for 1 hour. The re-
action mixture was filtered through 2–3 cm of silica gel sus-
pended in a Pasteur pipet, washed with a mixture of ethyl
acetate and hexane (2:3 v:v), and analyzed using GC-MS.
[4] Oligomeric iodosylbenzene sulfate 2 was previously
shown to be the most reactive oxygenating reagent in
Mass Spectra of Aqueous Mixture PhI-Oxone
A solution of Oxone and iodobenzene in a 1:1, 8:1 and 16:1
ratio in a 1:1 mixture of acetonitrile/water (2 mL) was
stirred at room temperature. Samples of the reaction mix-
ture were collected every hour and analyzed by MS. A typi-
cal mass spectrum is shown in Figure 2.
the FeACTHNURGTNE(NUG III) phthalocyanine-catalyzed oxygenations in
non-aqueous solutions; see: a) I. M. Geraskin, O. Pav-
lova, H. M. Neu, M. S. Yusubov, V. N. Nemykin, V. V.
Zhdankin, Adv. Synth. Catal. 2009, 351, 733–737;
b) H. M. Neu, M. S. Yusubov, V. V. Zhdankin, V. N.
Nemykin, Adv. Synth. Catal. 2009, 351, 3168–3174.
[5] a) A. Y. Koposov, B. C. Netzel, M. S. Yusubov, V. N.
Nemykin, A. Y. Nazarenko, V. V. Zhdankin, Eur. J.
Org. Chem. 2007, 4475–4478; b) V. N. Nemykin, A. Y.
Koposov, B. C. Netzel, M. S. Yusubov, V. V. Zhdankin,
Inorg. Chem. 2009, 48, 4908–4917; c) M. S. Yusubov,
R. Y. Yusubova, T. V. Funk, K.-W. Chi, V. V. Zhdankin,
Synthesis 2009, 2505–2508.
Acknowledgements
This work was supported by research grants from the Nation-
al Science Foundation (NSF-CHE-1009038, VVZ) and Petro-
leum Research Fund, administered by the American Chemi-
cal Society (VNN).
[6] a) R. M. Moriarty, R. Penmasta, I. Prakash, Tetrahe-
dron Lett. 1985, 26, 4699–4702; b) S. J. Kim, R. Latifi,
H. Y. Kang, W. Nam, S. P. de Visser, Chem. Commun.
2009, 1562–1564.
References
[7] M. S. Yusubov, A. A. Zagulyaeva, V. V. Zhdankin,
[1] Representatives books and reviews: a) P. R. Ortiz de
Montellano, Ed. Cytochrome P450: Structure, Mecha-
nism, and Biochemistry, Kluwer Academic/Plenum
Publishers, New York, 2005; b) R. A. Sheldon, (Ed.),
Metalloporphyrins in Catalytic Oxidations, M. Dekker,
New York, 1994; c) B. Meunier, Chem. Rev. 1992, 92,
1411–1456; d) E. Rose, B. Andrioletti, S. Zrig, M.
Quelquejeu-Etheve, Chem. Soc. Rev. 2005, 34, 573–
583; e) G. Simonneaux, P. Tagliatesta, J. Porphyrins
Phthalocyanines 2004, 8, 1166–1171; f) J. Bernadou, B.
Meunier, Adv. Synth. Catal. 2004, 346, 171–184; g) F. S.
Vinhado, P. R. Martins, Y. Iamamoto, Curr. Top. Catal.
2002, 3, 199–213; h) B. Meunier, A. Robert, G. Prat-
viel, J. Bernadou, Porphyrin Handbook 2000, 4, 119–
187; i) J. T. Groves, K. Shalyaev, J. Lee, Porphyrin
Handbook 2000, 4, 17–40; j) L. Ji, X. Peng, J. Huang,
Progress in Natural Science 2002, 12, 321–330; k) J. T.
Groves, J. Porphyrins Phthalocyanines 2000, 4, 350–
352; l) M. Kimura, H. Shirai, Porphyrin Handbook
2003, 19, 151–177; m) V. N. Nemykin, E. A. Lukyanets,
Handbook of Porphyrin Science 2010, Vol. 3, 1–323;
n) E. A. Lukyanets, V. N. Nemykin, J. Porphyrins
Phthalocyanines 2010, 14, 1–40; o) V. N. Nemykin,
E. A. Lukyanets, ARKIVOC, 2010, i, 136–208.
Chem. Eur. J. 2009, 15, 11091–11094.
[8] Reviews on hypervalent iodine catalysis: a) M. Uyanik,
K. Ishihara, Chem. Commun. 2009, 2086–2099; b) T.
Dohi, Y. Kita, Chem. Commun. 2009, 2073–2085;
c) R. D. Richardson, T. Wirth, Angew. Chem. 2006, 118,
4510–4512; Angew. Chem. Int. Ed. 2006, 45, 4402–
4404; d) V. V. Zhdankin, ARKIVOC 2009, i, 1–62;
e) M. Ochiai, K. Miyamoto, Eur. J. Org. Chem. 2008,
4229–4239.
[9] Recent books and general reviews on hypervalent
iodine: a) T. Wirth, (Ed.), Hypervalent Iodine Chemis-
try: Modern Developments in Organic Synthesis; Top.
Curr. Chem. Series 224, Springer, Berlin-Tokyo, 2003;
b) A. Varvoglis, Hypervalent Iodine in Organic Synthe-
sis, Academic Press, London, 1997; c) G. F. Koser, Adv.
Heterocycl. Chem. 2004, 86, 225–292; d) V. V. Zhdan-
kin, P. J. Stang, Chem. Rev. 2008, 108, 5299–5358;
e) V. V. Zhdankin, Science of Synthesis, Thieme, Stutt-
gart, 2007, Vol. 31a, pp 161–233; f) U. Ladziata, V. V.
Zhdankin, ARKIVOC 2006, ix, 26–58; g) M. Ochiai,
Chem. Rec. 2007, 7, 12–23; h) H. Tohma, Y. Kita, Adv.
Synth. Catal. 2004, 346, 111–124; i) S. Quideau, L.
Pouysegu, D. Deffieux, Synlett 2008, 467–495; j) Y.
Kita, H. Fujioka, Pure Appl. Chem. 2007, 79, 701–713;
k) R. M. Moriarty, J. Org. Chem. 2005, 70, 2893–2903.
[10] F. Effenberger, F. Buckel, A. H. Maier, J. Schmider,
Synthesis 2000, 1427–1430.
[2] a) J. T. Groves, T. E. Nemo, R. S. Myers, J. Am. Chem.
Soc. 1979, 101, 1032–1033; b) S. Mukerjee, A. Stassino-
poulos, J. P. Caradonna, J. Am. Chem. Soc. 1997, 119,
8097–8098; c) Y. Moro-oka, Catal. Today 1998, 45, 3–
1460
asc.wiley-vch.de
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2010, 352, 1455 – 1460