Hydroperoxidation of alkanes with hydrogen peroxide catalyzed by aluminium nitrate in acetonitrile

Article abstract of DOI:10.1016/j.tetlet.2008.09.058

The first example of alkane oxygenation with hydrogen peroxide catalyzed by a non-transition metal derivative (aluminium) is reported. Heating (70 °C) a solution of an alkane, RH, hydrogen peroxide (70% aqueous) and a catalytic amount of Al(NO₃)₃·9H₂O in air for a few hours afforded the corresponding alkyl hydroperoxide, ROOH. With cyclooctane, the hydroperoxide yield attained 31% and the maximum turnover number was 150. It is proposed on the basis of measurements of the selectivity parameters for the oxidation of linear and branched alkanes and a kinetic study that the oxidation occurs with the participation of hydroxyl radicals.

Full text of DOI:10.1016/j.tetlet.2008.09.058

Tetrahedron Letters 49 (2008) 6693–6697
Contents lists available at ScienceDirect
Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Hydroperoxidation of alkanes with hydrogen peroxide catalyzed
q
by aluminium nitrate in acetonitrile
a
a
b
b,*
Dalmo Mandelli , Karyna C. Chiacchio , Yuriy N. Kozlov , Georgiy B. Shul’pin
a
Pontifícia Universidade Católica de Campinas, Faculdade de Química, Rod. D. Pedro I, km 136, Pq. das Universidades, Campinas, SP 13086-900, Brazil
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 June 2008
Revised 3 September 2008
Accepted 10 September 2008
Available online 15 September 2008
The first example of alkane oxygenation with hydrogen peroxide catalyzed by a non-transition metal
derivative (aluminium) is reported. Heating (70 °C) a solution of an alkane, RH, hydrogen peroxide
(
70% aqueous) and a catalytic amount of Al(NO
3
)
3
ꢀ9H
2
O in air for a few hours afforded the corresponding
alkyl hydroperoxide, ROOH. With cyclooctane, the hydroperoxide yield attained 31% and the maximum
turnover number was 150. It is proposed on the basis of measurements of the selectivity parameters for
the oxidation of linear and branched alkanes and a kinetic study that the oxidation occurs with the
participation of hydroxyl radicals.
Keywords:
Alkanes
Catalysis
Ó 2008 Elsevier Ltd. All rights reserved.
Hydrogen peroxide
Aluminium salts
Oxygenation
The oxidations of hydrocarbons with donors of an oxygen atom
such as hydrogen peroxide, alkyl hydroperoxides and peroxy acids
constitute an important field of contemporary catalytic chemistry,
Al(NO
ide (‘Peróxidos do Brasil’) were used as received. A stock solution of
Al(NO O in 70% aqueous H (prepared at room tempera-
ꢀ9H
3
)
3
ꢀ9H
2
O (98% Aldrich) and 70% aqueous hydrogen perox-
3
)
3
2
2 2
O
1
and some industrial processes are based on these reactions. Deriv-
ture) was used in order to avoid introducing additional water into
the reaction mixture. The oxidations of saturated hydrocarbons in
acetonitrile were carried out in air in thermostated Pyrex cylindri-
cal vessels with vigorous stirring. The total volume of the reaction
solution was usually 5 mL. Typically, the reaction started when a
portion of the catalyst stock solution in hydrogen peroxide was
added in one portion to the solution of the substrate in MeCN.
2
atives of transition metals usually catalyze the oxygenations. Only
a few examples of catalysis by derivatives of non-transition metals
have been reported. Thus, bismuth compounds, BiCl
catalyze the oxidation of activated weak C–H bonds with TBHP.
3
and NaBiO
3
3
Solid aluminium oxide has been demonstrated to catalyze olefin
4
epoxidation with hydrogen peroxide in ether or ethyl acetate.
Wet alumina catalyzes the oxidation of phenyl sulfides to sulfox-
2 2
(Caution: the combination of air and H O with organic compounds
at elevated temperatures may be explosive!)
5
a
5b
ides or sulfones, and alicyclic ketones to lactones and second-
ary alcohols to ketones5 with Oxone. Diols are oxidized with
c
Samples of the reaction solutions were analyzed by GC. The
oxygenation of alkanes gives rise to the formation of the corre-
sponding alkyl hydroperoxides as the main products. To demon-
strate the formation of alkyl hydroperoxides during this
oxidation and to estimate their concentrations in the course of
sodium bromite in the presence of alumina.6 Soluble aluminium
7
nitrate catalyzes olefin epoxidation with H
2
O
2
in THF. Aluminium
8
a
8b
oxide and aluminium trichloride have been used to promote
the Baeyer–Villiger oxidation of ketones with H . In the present
work, we demonstrate for the first time that a soluble aluminium
salt, Al(NO O, is an efficient catalyst of alkane oxidation with
2 2
O
the reaction, we used a simple method developed earlier by some
9
3
)
3
ꢀ9H
2
of us. If an excess of solid PPh
3
is added to a sample of the reaction
hydrogen peroxide under relatively mild conditions.
solution, ca. 10 min before GC analysis, the alkyl hydroperoxide
present is completely reduced to the corresponding alcohol. As a
result, the chromatogram differs from that of a sample not sub-
jected to the reduction (the alcohol peak rises, while the intensity
of the ketone peak decreases). Comparing the intensities of peaks
attributed to the alcohol and ketone before and after the reduction,
it is possible to estimate the real concentrations of the alcohol,
ketone and alkyl hydroperoxide present in the reaction solution.
q
Parts of this work were presented at the 21st Ibero-American Symposium of
Catalysis (Málaga, Spain, 2008) and the 16th International Symposium on Homo-
geneous Catalysis (Florence, Italy, 2008).
*
Corresponding author. Fax: +7 495 1376130.
E-mail addresses: Shulpin@chph.ras.ru, gbsh@mail.ru (G. B. Shul’pin).
URL: http://shulpin.fortunecity.com/ (G. B. Shul’pin).
0
040-4039/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2008.09.058

6
694
D. Mandelli et al. / Tetrahedron Letters 49 (2008) 6693–6697
0
0
.12
.10
4
A
1
1
B
3
1
0
.0
0
.08
.5
0
0
.06
2
1
0
.04
.02
4
0
0
0
5
10
/ M
-
1
1/[cyclooctane]
0
×
×
0
×
×
×
2
2
2
0
× ×
×
25
×
30
0
0
3
0
5
10
15
Time / h
20
0
0.2
0.4
0.6
0.8
1.0
[cyclooctane]0 / M
Figure 1. Accumulation of the products (cyclooctyl hydroperoxide, curve 1;
cyclooctanol, curve 2; cyclooctanone, curve 3) in the oxidation of cyclooctane
Figure 3. Oxidation of cyclooctane with hydrogen peroxide (70% aqueous; 1.0 M;
3 3
the content of water in the reaction mixture was 1.3 M) catalyzed by Al(NO )
(
0.5 M) with hydrogen peroxide (70% aqueous; 1.0 M; the total concentration of
water in the reaction mixture was 1.3 M) catalyzed by Al(NO (1.0 mM) in MeCN
at 70 °C. Concentrations of cyclooctanone and cyclooctanol were determined twice,
(
1.0 mM) in MeCN at 70 °C. Graph A: Dependencies of the initial rate of oxygenate
3 3
)
0
formation W (curve 1) and total yield (%) of oxygenates (based on cyclooctane)
after 32 h (curve 2) on initial concentration of cyclooctane are shown. Concentra-
tions of cyclooctanone and cyclooctanol were determined after reduction of
3
before and after reduction of the aliquots with solid PPh (for this method, see
Ref. 9).
aliquots with solid PPh
B: Linear dependence of 1 using coordinates 1/W
3
. For the original full kinetic curves, see Figure S2. Graph
ꢁ 1/[cyclooctane]
0
0
.
Our method has been employed by other chemists for the analysis
of reaction products and detection of alkyl hydroperoxides during
oxidations of C–H compounds by molecular oxygen, hydrogen per-
oxide and other peroxides.10 In the kinetic study of the cyclooctane
oxidation, we measured the concentrations of cyclooctanone and
cyclooctanol only after reduction with PPh , because this reduction
3
gives the most precise values of total concentrations of the
products.
affords the cyclooctyl hydroperoxide, whereas cyclooctanone and
cyclooctanol are formed in minor amounts (Fig. 1). Only negligible
concentrations of the oxygenates were found in the absence of alu-
minium nitrate. The dependences of the oxygenation initial rate
and the oxygenate yield on the initial concentration of the catalyst,
cyclooctane and hydrogen peroxide are shown in Figures 2–4. The
yield of cyclooctyl hydroperoxide attained 31% and the maximum
Heating a solution of cyclooctane in acetonitrile with 70% aque-
ous hydrogen peroxide in the presence of 1 mM Al(NO
3
)
3 2
ꢀ9H O
4
1
0
A
30
×
×
×
3
2
1
0
8
6
4
25
20
15
10
5
.8
B
×
2
0.4
0
W
×
0
2
4
1
1
0
/ M-1
2
30
1/[H
0.8
2 2 0
O ]
×
×
20
×
×
×
10
0
2
0
×
×
×
×
0
0
0.
2
0.4
0.6
1.0 1.2
1.4
0
[
H O ] / M
2 2 0
1
2
[
3
4
5
6
Al(NO ) ] / mM
3
3
3 3
Figure 4. Oxidation of cyclooctane with hydrogen peroxide catalyzed by Al(NO )
(
1.0 mM) in MeCN at 70 °C. Graph A: Dependencies of the initial rate of oxygenate
Figure 2. Oxidation of cyclooctane (0.5 M) with hydrogen peroxide (70% aqueous;
.0 M; the content of water in the reaction mixture was 1.3 M) catalyzed by
Al(NO in MeCN at 70 °C. Dependencies of the initial rate of oxygenate formation
(curve 1) and total yield (%) of oxygenates (based on cyclooctane) after 10 h
curve 2) on the initial concentration of catalyst Al(NO are shown. Concentrations
of cyclooctanone and cyclooctanol were determined after reduction of aliquots with
solid PPh . For the original full kinetic curves, see Figure S1.
0
formation W (curve 1) and total yield (%) of oxygenates (based on cyclooctane)
1
after 32 h (curve 2) on initial concentration of hydrogen peroxide are shown. The
content of water in the reaction mixture was maintained constant (1.3 M) by
adding water. Concentrations of cyclooctanone and cyclooctanol were determined
3 3
)
W
(
0
)
3 3
after reduction of the aliquots with solid PPh
see Figure S3. Graph B: Linear of dependence of 1 using coordinates 1/W
[H
3
. For the original full kinetic curves,
0
ꢁ 1/
3
2 2 0
O ] .

D. Mandelli et al. / Tetrahedron Letters 49 (2008) 6693–6697
6695
turnover number was 150. It is interesting that in the initial period
of the reaction, the catalyst exhibits some ‘catalase’ activity.
n-Octane can be hydroperoxidized by the system under discus-
sion. The selectivity parameters for n-octane calculated from data
in Table 1 and for n-heptane are low, C(1):C(2):C(3):C(4) ꢂ 1:5:5:5
compete for the oxidizing species, which is apparently a hydroxyl
radical:
Å
H
2
O
2
=AlðNO
3
Þ ! H—O
W
i
ð0Þ
ð1Þ
ð2Þ
ð3Þ
ð4Þ
3
Å
H—O þ MeCN ! products
k
1
Å
Å
(
see Table 2). These values are close to the parameters determined
H—O þ RH ! R þ H
2 2
O k
Å
Å
previously for systems which oxidize alkanes with participation of
hydroxyl radicals (compare with the parameters summarized in
entries 2–6 of Table 2). It is clear that the corresponding selectivity
parameters for the systems that do not involve active oxygen-cen-
tred radicals (entries 7–10) are noticeably higher. Bond-selectivity
parameters in the Al-catalyzed reaction with branched alkanes
R þ O ! ROO
2
Å
þ
ꢁ
ROO þ H þ e ! ROOH
where W is the rate of the oxidizing species generation by the
i
H O –Al(NO ) system, and steps (3) and (4) are not rate-limiting
2
2
3 3
processes. Analysis of the above scheme in steady-state approxima-
tion relative to the hydroxyl radical led to the following equation for
the RH oxidation rate:
(Table 3, entry 1), as in the case of linear alkanes, are close to the
parameters found for the systems oxidizing alkanes with participa-
tion of hydroxyl radicals (compare with the parameters summa-
rized in entries 2–6 of Table 3). The reaction proceeds non-
stereoselectively: for the oxidation of both cis- and trans-1,2-di-
methylcyclohexanes, the ratios of isomeric alcohols trans/cis (after
d½RHꢃ d½ROOHꢃ
W
i
ꢁ
¼
¼
ð5Þ
k
1
½MeCNꢃ
dt
dt
1
þ
2
k ½RHꢃ
Our experimental data are in good agreement with this equa-
ꢁ
1
reduction with PPh
3
) were 0.8 (Table 3).
tion: we found the linear dependence of (d[ROOH]/dt)
and
ꢁ1
Thus, the data summarized in Tables 2 and 3 show that the
selectivity parameters for oxidizing species generated by the
½cyclooctaneꢃ , as shown in Figure 3, Graph B. It follows from this
0
dependence that under the conditions described in the caption of
H
2
O
2
–Al(NO
3
)
3
system are close to the corresponding parameters
Figure 3, the rate of active species generation W
i
is equal to
ꢁ6
ꢁ1
found for the oxidation reaction with participation of hydroxyl
radicals. It should be noted that the data shown in Figure 3 also
support the assumption regarding the participation of hydroxyl
radicals in alkane oxidation by the system under discussion.
Indeed, the mode of dependence of the initial reaction rate on
cyclooctane, RH, concentration indicates that RH and acetonitrile
7.5 ꢄ 10 M s and the ratio k
1 2
[MeCN]/k = 0.83 M. We should
note that under the conditions of our experiments, competition be-
tween cyclooctane and hydrogen peroxide for the hydroxyl radical
is not very probable because it is suspicious that the decrease of
Å
the rate constant for the interaction between HO and RH is more
than 30-fold when the temperature is increased from 298 to
Table 1
Oxidation of n-octanea
Time (h)
Products, concentration after reduction with PPh
3
(mM)
TON
Yield (based on n-octane)
(
%)
al-1
one-2
one-3
one-4
ol-1
ol-2
ol-3
ol-4
2
0.02
0.11
0.19
0.23
0.00
0.49
0.49
1.17
1.52
0.00
0.52
0.58
1.43
1.95
0.00
0.30
0.50
1.24
1.60
0.00
1.9
3.8
4.7
6.8
0.00
3.7
14.2
18.3
19.9
0.0
3.8
14.1
17.7
19.1
0.0
3.4
12.8
15.8
16.9
0.0
14
47
61
68
—
3
9
12
14
1
2
3
3
0
4
2
8
b
0.3
a
Conditions: Al(NO
In the absence of Al(NO
3
)
3
, 1 mM; n-octane, 0.5 M; H
) .
3 3
2
O
2
, 1.0 M; 70 °C.
b
Table 2
Selectivity parameters in the oxidation of linear alkanes by the ‘H
/MeCN’ system as well as (for comparison) by certain other oxidizing systemsa
Parameter C(1):C(2):C(3):C(4)
2
O
2
/Al(NO
3
)
3
Entry
System
n-Hexane
n-Heptane
n-Octane
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
2
2
2
2
2
2
O
O
O
O
O
O
2
2
2
2
2
2
–Al(NO
–h (MeCN, 20 °C)
–FeSO (MeCN, 20 °C)
–n-Bu NVO –PCA (MeCN, 40 °C)
–Ni(ClO –TMTACN (MeCN, 70 °C)
–1 (MeCN, 60 °C)
3
)
3
(MeCN, 70 °C)
1:5.3:5.4:4.9
1:7:6:7
1:5:5:4.5
1:5.7:7.2:5.0
1:6.3:7.2:6.1
1:5.5:5.0:4.6
1:5.6:5.6:5.0
1:10.2:6.8:6.3
m
1:10:7
4
b
4
3
1:6.9:7.0
1:6.7:7.5:5.3
c
4 4
)
d
1:6.2:7.1
1:36:36.5
1:364:363
m-Chloroperoxybenzoic acid (MeCN, 25 °C)
e
H
H
H
2
O
2
O
2
O
2
2
2
in CF
–NaAuCl
–2–MeCO
3
COOH
(MeCN, 75 °C)
H (MeCN, 25 °C)
f
4
1:35:25:23
1:46:35:34
1:14:13:12
g
1
1
0
1
2
1:29:25:24
1:17:12:15
g
TBHP–2–oxalic acid (MeCN, 50 °C)
a
Parameters C(1):C(2):C(3):C(4) are relative normalized (i.e., calculated taking into account the number of hydrogen atoms at each carbon) reactivities of the hydrogen
atoms at carbons 1, 2, 3 and 4, of the chain of linear alkanes. All parameters were measured after reduction of the reaction mixtures with triphenylphosphine before GC
analysis and calculated based on the ratios of isomeric alcohols.
b
For this system, which is believed to oxidize substrates via formation of hydroxyl radicals, see Ref. 12.
TMTACN is 1,4,7-trimethyl-1,4,7-triazacyclononane. For this system, see Ref. 13.
c
d
Compound 1 is the complex (2,3-
For this system, see Ref. 15.
For this system, see Ref. 16.
g-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium. For this system, see Ref. 14.
e
f
g
2 2 2
Compound 2 is the complex [Mn L (l-O)
]2+ where L is 1,4,7-trimethyl-1,4,7-triazacyclononane. For this system, see Ref. 17.

6
696
D. Mandelli et al. / Tetrahedron Letters 49 (2008) 6693–6697
Table 3
Selectivity parameters in the oxidation of branched and cyclic alkanes by the ‘H
2
O
2
/Al(NO
3
)
3
/MeCN’ system as well as (for comparison) by certain other oxidizing systemsa
b
trans/cisc
Entry
System
1°:2°:3°
2
,2,4-TMP
MCH
2-MH
3-MH
cis-DMCH
trans-DMCH
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
2
2
2
2
2
2
O
O
O
O
O
O
2
2
2
2
2
2
–Al(NO
–h (MeCN, 20 °C)
–FeSO (MeCN, 20 °C)
–n-Bu NVO –PCA (MeCN, 40 °C)
–Ni(ClO –TMTACN (MeCN, 70 °C)
–1 (MeCN, 60 °C)
3
)
3
(MeCN, 70 °C)
1:4.3:7.4
1:2:6
1:3:6
1:1.5:10
1:2.3:4.5
1:5:8.5
1:20:520
1:52:0
1:6:23
1:2:6
0.8
0.9
1.3
0.75
0.8
1.0
1.2
0.8
m
1:6:20
1:14:64
1:6:19
1:4:12
4
b
4
3
1:9:37
1:7:15
1:4:10
1:89:750
c
4
)
4
1:5.3:55
1:22:200
d
0.9
0.65
RC
m-Chloroperoxybenzoic acid (MeCN, 25 °C)
e
H
H
H
2
O
2
O
2
O
2
2
2
in CF
–NaAuCl
–2–MeCO
3
COOH
(MeCN, 75 °C)
H (MeCN, 25 °C)
RC
f
4
1:10:240
1:5:55
1:0.4:32
1:116:255
1:26:200
1:0.3:0.6
1:13:100
1:19:204
g
1
1
0
1
2
0.34
0.2
4.1
7.3
g
TBHP–2–oxalic acid (MeCN, 50 °C)
a
Parameters 1°:2°:3° are relative normalized reactivities of the hydrogen atoms at primary, secondary and tertiary carbons of branched alkanes. Abbreviations: 2,2,4-TMP,
,2,4-trimethylpentane (isooctane); MCH, methylcyclohexane; 2- and 3-MH, 2- and 3-methylhexanes. Parameter trans/cis is the ratio of trans- and cis-isomers of tert-alcohols
2
formed in the oxidation of dimethylcyclohexanes (cis-DMCH and trans-DMCH). All parameters were measured after reduction of the reaction mixtures with triphenyl-
phosphine before GC analysis and calculated based on the ratios of isomeric alcohols.
b
For this system, which is believed to oxidize substrates via formation of hydroxyl radicals, see Ref. 12.
TMTACN is 1,4,7-trimethyl-1,4,7-triazacyclononane. For this system, see Ref. 13.
Compound 1 is the complex (2,3-g-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium. For this system, see Ref. 14.
For this system, see Ref. 15. RC, retention of configuration.
c
d
e
f
For this system, see Ref. 16.
g
2 2 2
Compound 2 is the complex [Mn L (l-O)
]2+ where L is 1,4,7-trimethyl-1,4,7-triazacyclononane. For this system, see Ref. 17.
3
43 K. This could be probable but only if the activation energy is
The efficient rate constant for hydroxyl radical generation was
determined at [cyclooctane] = 0.7 M, where in accord with data
shown in Figure 3, ca. 50% of all the generated hydroxyl radicals
are accepted by the substrates present in the reaction solution.
equal to 64 kJ/mol which is not typical for reactions with participa-
tion of hydroxyl radicals. The ratio k
our experiments is in satisfactory agreement with calculated con-
0
ꢁ2
/k
1 2
= 4.5 ꢄ 10 obtained in
stants at 298 K previously measured in independent experiments.
As a consequence, we can calculate the true value of the constant
Å
ꢁ3 ꢁ1
Thus in accord with Ref. 11 the k
1
(MeCN + HO )/k
2
(cyclooc-
k
i
= 2ki-eff = 7.6 ꢄ 10
s .
Å
ꢁ2
tane + HO ) ratio is equal to 1.3 ꢄ 10 , and we can conclude that
our kinetic data also support the assumption about the participa-
tion of hydroxyl radicals in the reaction under discussion.
The details of scheme presented by Eqs. 7, 8, 2–4 at the moment
are unclear. We cannot also exclude the transient formation of alu-
minium derivatives in ‘exotic’ valent state. For example, the couple
Al(III)/Al(II) could be responsible for hydroxyl radical generation.
Previously, we proposed a similar mechanism with the V(V)/
V(VI) manifold which generates hydroperoxyl and hydroxyl radi-
Additional information on the reaction mechanism can be ob-
tained from analysis of the dependence of the initial oxidation rate
on the initial hydrogen peroxide concentration. This dependence,
as illustrated inFigure 4, is in good agreement with the assumption
1
2
cals from hydrogen peroxide.
1
8
3+
that a peroxo complex of Al with H
2
O
2
(conventionally denoted
3
+
below as ‘Al ꢀH
2
O
2
’) takes part in the active species generation
step. Indeed, assuming that in a polar medium the salt Al(NO
Acknowledgements
3 3
)
is present in completely dissociative form, and based on Eq. 6
This work was supported by the State of São Paulo Research
Foundation (Fundação de Amparo a Pesquisa do Estado de São Pau-
lo, FAPESP; Grant Nos. 2005/51579-2, 2006/03996-6), the Brazilian
National Council on Scientific and Technological Development
3
þ
ꢁ
AlðNO
3
Þ3 ! Al
þ 3NO3
ð6Þ
we can propose the following mechanism for the active species
generation:
(
Conselho Nacional de Desenvolvimento Cientifico e Tecnológico,
CNPq, Brazil; Grant Nos. 300984/2004-9, 478165/2006-4,
05014/2007-2) and the Russian Foundation for Basic Research
Grant No. 06-03-32344-a). G.B.S. expresses his gratitude to the
FAPESP (grant No. 2006/03984-8), the CNPq (Grant No. 300601/
1-8), and the Faculdade de Química, Pontifícia Universidade
3
þ
3þÅ
Al þ H
2
O
2
ꢀ ‘A1
H
2
O
2
’
Å
K
7
ð7Þ
ð8Þ
3
(
3
þÅ
3þ
‘
Al
H
2
O
2
’ ! Al þ 2HO
k
i
Using this proposal in the quasi-equilibrium approximation for
the peroxo complex, we can deduce the following equation for the
rate WROOH of ROOH formation at [cyclooctane] = 0.7 M:
0
0
Católica de Campinas for making it possible for him to stay at this
University as invited Professor and to perform part of the present
work.
ꢃ ½A1 þꢃ
3
k
7
½H
2
O
2
0
0
W
ROOH ¼ 2ki-eff
ð9Þ
1
þ k
7
½H
2
O
2
ꢃ
0
Supplementary data
We introduce here the effective constant value ki-eff which is
different from the true value k because under the conditions of
our experiments at [cyclooctane] = 0.7 M, the hydrocarbon does
i
Supplementary data (Figs. S1–S3) associated with this article
can be found, in the online version, at doi:10.1016/j.tetlet.2008.
09.058.
0
not accept all the hydroxyl radicals generated in reaction (8).
The experimental data shown in Figure 4 are in good agreement
ꢁ1
ꢁ1
with Eq. 9: we found a linear dependence of (WROOH
)
on [H
2
O
2
]
References and notes
(
see Fig. 4, Graph B). This dependence allowed us to determine ki-
ꢁ3 ꢁ1
1
2
.
.
Catalytic Oxidations with Hydrogen Peroxide as Oxidant; Strukul, G., Ed.; Kluwer
Academic: Dordrecht, The Netherlands, 1992.
(a) Shilov, A. E.; Shul’pin, G. B. Chem. Rev. 1997, 97, 2879–2932; (b) Shilov, A. E.;
Shul’pin, G. B. Activation and Catalytic Reactions of Saturated Hydrocarbons in the
Presence of Metal Complexes; Kluwer Academic: Dordrecht/Boston/London,
eff = 3.8 ꢄ 10
s
from the segment which is cut on the y-axis. The
ꢁ1
7
equilibrium constant for peroxo complex formation K = 1.4 M
was also measured from the tangent of this straight line slope
taking into account the value of the segment mentioned above.

D. Mandelli et al. / Tetrahedron Letters 49 (2008) 6693–6697
6697
2
000; (c) Shul’pin, G. B. In Transition Metals for Organic Synthesis, 2nd ed.; Beller,
M., Bolm, C., Eds.; Springer: Weinheim/New York, 2004; Vol. 2, Chapter 2.2, pp
15–242.
Kirillov, A. M.; Reis, P. M.; Silva, J. A. L.; Fraústo da Silva, J. J. R.; Pombeiro, A. J. L.
J. Catal. 2007, 248, 130–136; (l) Kirillova, M. V.; Silva, J. A. L.; Fraústo da Silva, J.
J. R.; Pombeiro, A. J. L. Appl. Catal. A 2007, 332, 159–165; (m) Silva, T. F. S.;
Alegria, E. C. B. A.; Martins, L. M. D. R. S.; Pombeiro, A. J. L. Adv. Synth. Catal.
2008, 350, 706–716; (n) Karabach, Y. Y.; Kirillov, A. M.; Haukka, M.; Kopylovich,
M. N.; Pombeiro, A. J. L. J. Inorg. Biochem. 2008, 102, 1190–1194; (o) Mishra, G.
S.; Alegria, E. C. B.; Martins, L. M. D. R. S.; Fraústo da Silva, J. J. R.; Pombeiro, A. J.
L. J. Mol. Catal. A: Chem. 2008, 285, 92–100; (p) Wang, H.; Li, R.; Zheng, Y.; Chen,
H.; Wang, F.; Ma, J. Catal. Lett. 2008, 122, 330–337; (q) Kirillova, M. V.; Kirillov,
A. M.; da Silva, M. F. C. G.; Pombeiro, A. J. L. Eur. J. Inorg. Chem. 2008, 3423–
3427.
2
3
.
.
(a) Salvador, J. A. R.; Silvestre, S. M. Tetrahedron Lett. 2005, 46, 2581–2584; (b)
Bonvin, Y.; Callens, E.; Larrosa, I.; Henderson, D. A.; Oldham, J.; Burton, A. J.;
Barrett, A. G. M. Org. Lett. 2005, 7, 4549–4552.
(a) Rebek, J.; McCready, R. Tetrahedron Lett. 1979, 45, 4337–4338; (b) van Vliet,
M. C. A.; Mandelli, D.; Arends, I. W. C. E.; Schuchardt, U.; Sheldon, R. A. Green
Chem. 2001, 3, 243–246; (c) Mandelli, D.; van Vliet, M. C. A.; Sheldon, R. A.;
Schuchardt, U. Appl. Catal. A 2001, 219, 209–213; (d) Cesquini, R. G.; Silva, J. M.
S.; Woitiski, C. B.; Mandelli, D.; Rinaldi, R.; Schuchardt, U. Adv. Synth. Catal.
4
2
002, 344, 911–914; (e) Rinaldi, R.; Sepulveda, J.; Schuchardt, U. Adv. Synth.
Catal. 2004, 346, 281–285; (f) Rinaldi, R.; Schuchardt, U. J. Catal. 2004, 227, 109–
16; (g) Rinaldi, R.; Schuchardt, U. J. Catal. 2005, 236, 335–345; (h) Silva, J. M.
S.; Vinhado, F. S.; Mandelli, D.; Schuchardt, U.; Rinaldi, R. J. Mol. Catal. A: Chem.
006, 252, 186–193; (i) Rinaldi, R.; Schuchardt, U. J. Catal. 2006, 236, 335–345.
11. (a) Farhataziz; Ross A. B. Selected Specific Rates of Reactions of Transients from
Water in Aqueous Solution. III. Hydroxyl Radical and Perhydroxyl Radical and their
Radical Ions, NSRDS-NBS 59, Washington, DC, 1977; (b) Rudakov, E. S.; Volkova,
L. K.; Tretyakov, V. P. Soobscheniya po Kinetike i Katalizu 1981, 16, 333. in
Russian; (c) Khar’kova, T. V.; Arest-Yakubovich, I. L.; Lipes, V. V. Kinetika i
Kataliz 1989, 30, 954. in Russian.
12. (a) de la Cruz, M. H. C.; Kozlov, Y. N.; Lachter, E. R.; Shul’pin, G. B. New J. Chem.
2003, 27, 634–638; (b) Kozlov, Y. N.; Nizova, G. V.; Shul’pin, G. B. J. Mol. Catal. A:
Chem. 2005, 227, 247–253; (c) Khalliulin, R. Z.; Bell, A. T.; Head-Gordon, M. J.
Phys. Chem. B 2005, 109, 17984–17992; (d) Shul’pin, G. B.; Mishra, G. S.;
Shul’pina, L. S.; Strelkova, T. V.; Pombeiro, A. J. L. Catal. Commun. 2007, 8, 1516–
1520; (e) Kozlov, Y. N.; Romakh, V. B.; Kitaygorodskiy, A.; Buglyó, P.; Süss-Fink,
G.; Shul’pin, G. B. J. Phys. Chem. A 2007, 111, 7736–7752.
1
2
5
.
(a) Greenhalgh, R. P. Synlett 1992, 235–236; (b) Hirano, M.; Oose, M.;
Morimoto, T. Chem. Lett. 1991, 331–332; (c) Hirano, M.; Oose, M.; Morimoto,
T. Bull. Chem. Soc. Jpn. 1991, 64, 1046–1047.
Morimoto, T.; Hirano, M.; Iwasaki, K.; Ishikawa, T. Chem. Lett. 1994, 53–54.
Rinaldi, R.; Fujiwara, F. Y.; Schuchardt, U. Catal. Commun. 2004, 5, 333–337.
(a) Steffen, R. A.; Teixeira, S.; Sepulveda, J.; Rinaldi, R.; Schuchardt, U. J. Mol.
Catal. A: Chem. 2008, 287, 41–44; (b) Lei, Z.; Ma, G.; Wei, L.; Yang, Q.; Su, B.
Catal. Lett. 2008, 124, 330–333.
6.
7.
8.
9
.
(a) Shul’pin, G. B. J. Mol. Catal. A: Chem. 2002, 189, 39–66; (b) Shul’pin, G. B. C.R.
Chim. 2003, 6, 163–178; (c) Shul’pin, G. B.; Attanasio, D.; Suber, L. J. Catal. 1993,
13. Shul’pin, G. B. J. Chem. Res. (S) 2002, 351–353.
14. (a) Shul’pina, L. S.; Kudinov, A. R.; Petrovskaya, E. A.; Strelkova, T. V.; Shul’pin,
G. B. Petrol. Chem. 2006, 46, 164–166; (b) Shul’pin, G. B.; Kudinov, A. R.;
Shul’pina, L. S.; Petrovskaya, E. A. J. Organomet. Chem. 2006, 691, 837–845.
15. Deno, N. C.; Jedziniak, E. J.; Messer, L. A.; Meyer, M. D.; Stroud, S. G.; Tomezsko,
E. S. Tetrahedron 1977, 33, 2503–2508.
1
2
42, 147–152; (d) Shul’pin, G. B.; Nizova, G. V.; Kozlov, Y. N. New J. Chem. 1996,
0, 1243–1256; (e) Shul’pin, G. B.; Guerreiro, M. C.; Schuchardt, U. Tetrahedron
1
996, 52, 13051–13062.
1
0. (a) Mishra, G. S.; Pombeiro, A. J. L. J. Mol. Catal. A: Chem. 2005, 239, 96–102; (b)
Mishra, G. S.; Pombeiro, A. J. L. Appl. Catal. A 2006, 304, 185–194; (c) Nesterov,
D. S.; Kokozay, V. N.; Dyakonenko, V. V.; Shishkin, O. V.; Jezierska, J.;
Ozarowski, A.; Kirillov, A. M.; Kopylovich, M. N.; Pombeiro, A. J. L. Chem.
Commun. 2006, 4605–4607; (d) Du, P.; Moulijn, J. A.; Mul, G. J. Catal. 2006, 238,
16. Shul’pin, G. B.; Süss-Fink, G.; Shilov, A. E. Tetrahedron Lett. 2001, 42, 7253–
7256.
17. (a) Shul’pin, G. B.; Süss-Fink, G.; Shul’pina, L. S. J. Mol. Catal. A: Chem. 2001, 170,
17–34; (b) Woitiski, C. B.; Kozlov, Y. N.; Mandelli, D.; Nizova, G. V.; Schuchardt,
U.; Shul’pin, G. B. J. Mol. Catal. A: Chem. 2004, 222, 103–119; (c) dos Santos, V.
A.; Shul’pina, L. S.; Veghini, D.; Mandelli, D.; Shul’pin, G. B. React. Kinet. Catal.
Lett. 2006, 88, 339–348; (d) Romakh, V. B.; Therrien, B.; Süss-Fink, G.; Shul’pin,
G. B. Inorg. Chem. 2007, 46, 1315–1331; (e) Kozlov, Y. N.; Nizova, G. V.; Shul’pin,
G. B. J. Phys. Org. Chem. 2008, 21, 119–126; (f) Shul’pin, G. B.; Matthes, M. G.;
Romakh, V. B.; Barbosa, M. I. F.; Aoyagi, J. L. T.; Mandelli, D. Tetrahedron 2008,
64, 2143–2152.
3
42–352; (e) de Castries, A.; Magnier, E.; Monmotton, S.; Fensterbank, H.;
Larpent, C. Eur. J. Org. Chem. 2006, 4685–4692; (f) Trettenhahn, G.; Nagl, M.;
Neuwirth, N.; Arion, V. B.; Jary, W.; Pöchlauer, P.; Schmid, W. Angew. Chem., Int.
Ed. 2006, 45, 2794–2798; (g) Di Nicola, C.; Karabach, Y. Y.; Kirillov, A. M.;
Monari, M.; Pandolfo, L.; Pettinari, C.; Pombeiro, A. J. L. Inorg. Chem. 2007, 46,
2
21–230; (h) Alegria, E. C. B.; Kirillova, M. V.; Martins, L. M. D. R. S.; Pombeiro,
A. J. L. Appl. Catal. A 2007, 317, 43–52; (i) Mishra, G. S.; Fraústo da Silva, J. J. R.;
Pombeiro, A. J. L. J. Mol. Catal. A: Chem. 2007, 265, 59–69; (j) Yuan, Q.; Deng, W.;
Zhang, Q.; Wang, Y. Adv. Synth. Catal. 2007, 349, 1199–1209; (k) Kirillova, M. V.;
18. (a) Leffler, J. E.; Miller, D. W. J. Am. Chem. Soc. 1977, 99, 480–483; (b) Rinaldi, R.;
Fujiwara, F. Y.; Hölderich, W.; Schuchardt, U. J. Catal. 2006, 244, 92–101.