Alkane oxidation by the H2O2-NaVO3-H2SO4 system in acetonitrile and water

Article abstract of DOI:10.1016/j.tet.2009.01.088

A simple system is described, which oxidizes saturated hydrocarbons either in acetonitrile or (less efficiently) in water. The system consists of 50% aqueous hydrogen peroxide as an oxidant, sodium metavanadate, NaVO₃, as a catalyst and sulfuric (or oxalic) acid as a co-catalyst. The reactions were carried out at 20-50 °C. In the oxidation of cyclohexane in acetonitrile, the highest yield (37% based on cyclohexane) and turnover number (TON=1700) were attained after 3 h at 50 °C. The corresponding parameters were 16% and 1090 for n-heptane oxidation under the same conditions. The oxidation of higher alkanes, RH, in acetonitrile gives almost exclusively the corresponding alkyl hydroperoxides, ROOH. Light alkanes (n-butane, propane, ethane, and methane) have been also oxygenated by the system under consideration. The highest TON (200) was attained for ethane and the highest yield (19%) was obtained in the case of n-butane. The selectivity parameters measured for the oxidation of linear and branched alkanes are low, the reaction with cis- and trans-1,2-dimethylcyclohexanes is not stereoselective. These facts lead us to conclude that the oxidation occurs with the formation of hydroxyl radicals in the crucial step.

Full text of DOI:10.1016/j.tet.2009.01.088

Tetrahedron 65 (2009) 2424–2429
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Alkane oxidation by the H O –NaVO –H SO system in acetonitrile and water
2
2
3
2
4
Lidia S. Shul’pina , Marina V. Kirillova , Armando J.L. Pombeiro ,*, Georgiy B. Shul’pin
a
b
b
c,
*
a
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Ulitsa Vavilova, dom 28, Moscow 119991, Russia
Centro de Qu ´ı mica Estrutural, Complexo I, Instituto Superior T e´ cnico, TU Lisbon, Av. Rovisco Pais, 1049–001 Lisbon, Portugal
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
A simple system is described, which oxidizes saturated hydrocarbons either in acetonitrile or (less
efficiently) in water. The system consists of 50% aqueous hydrogen peroxide as an oxidant, sodium
Received 13 November 2008
Received in revised form 8 January 2009
Accepted 22 January 2009
Available online 29 January 2009
3
metavanadate, NaVO , as a catalyst and sulfuric (or oxalic) acid as a co-catalyst. The reactions were
ꢀ
carried out at 20–50 C. In the oxidation of cyclohexane in acetonitrile, the highest yield (37% based on
ꢀ
cyclohexane) and turnover number (TON¼1700) were attained after 3 h at 50 C. The corresponding
parameters were 16% and 1090 for n-heptane oxidation under the same conditions. The oxidation of
higher alkanes, RH, in acetonitrile gives almost exclusively the corresponding alkyl hydroperoxides,
ROOH. Light alkanes (n-butane, propane, ethane, and methane) have been also oxygenated by the system
under consideration. The highest TON (200) was attained for ethane and the highest yield (19%) was
obtained in the case of n-butane. The selectivity parameters measured for the oxidation of linear and
branched alkanes are low, the reaction with cis- and trans-1,2-dimethylcyclohexanes is not stereo-
selective. These facts lead us to conclude that the oxidation occurs with the formation of hydroxyl
radicals in the crucial step.
Keywords:
Alkanes
Alkyl hydroperoxides
Cyclohexane
Homogeneous catalysis
Hydrogen peroxide
Oxidation
Vanadium complexes
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
has been recently oxygenated (TON up to 150) with H
2
O
2
in water
in the reaction catalyzed by KVO
in low concentration.
3
in the presence of perchloric acid
7
Soluble and solid derivatives of transition metals are known to
1
catalyze oxidations of hydrocarbons with hydrogen peroxide. It
should be emphasized that alkanes are very inert organic com-
pounds, and yields and selectivity in their oxidations are usually
low. For example, in the commercial oxidation of cyclohexane by air
2
. Results and discussion
In the present work, we have found that heating a solution of
cyclohexane, CyH, in acetonitrile with 50% aqueous hydrogen per-
oxide in the presence of NaVO and H SO leads to the efficient
oxygenation of the alkane. Examples of the kinetic curves are
shown in Figure 1. Since NaVO is almost insoluble even in aqueous
acetonitrile we used the catalyst as a stock solution prepared by
dissolution of the vanadium salt and H SO in water (see Experi-
mental). In the experiments shown in graphs B–F (Fig. 1) some
amounts of sulfuric acid were added to the reaction solution,
whereas in the experiment shown in graph A only H
stock solution was used.
ꢀ
at 160 C with the participation of Co(II) as a catalyst the reaction is
1
e
run only to 4% conversion. The desired compounds constitute only
5% of the products. These compounds are cyclohexanol and cy-
3
2
4
8
clohexanone, both of which are also susceptible to further oxidation.
Oxidations of alkanes with hydrogen peroxide proceed usually more
selectively. However, even in this case yields of products around 30%
3
1
d,f
2
4
based on the alkane can be considered as high.
Various vanadium compounds induce transformation of organic
compounds 2 including hydrocarbon oxidations with peroxides.3,4
It has been previously shown that oxovanadium derivatives are
good catalysts for hydrogen peroxide oxygenation (i.e., insertion of
the oxygen atom into the C–H bond) of saturated hydrocarbons in
acetonitrile solution.5,6 These reactions occur in the presence of
2 4
SO from the
Samples of the reaction solutions were analyzed by GC. We used
8
a simple method developed earlier by some of us. The oxygenation
of alkanes usually gives rise to the formation of the corresponding
alkyl hydroperoxides as the main products. If an excess of solid
5
6
pyrazine-2-carboxylic acid or nitric acid as co-catalysts. Methane
3
PPh is added to a sample of the reaction 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 subjected to the reduction (the alcohol
peak rises, while the intensity of the ketone peak decreases).
*
Corresponding authors. Fax: þ7 495 9397417/6512191 (G.B.S.); fax: þ351 21
8
464455 (A.J.L.P.).
E-mail addresses: pombeiro@ist.utl.pt (A.J.L. Pombeiro), shulpin@chph.ras.ru,
gbsh@mail.ru (G.B. Shul’pin).
0
040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.01.088

L.S. Shul’pina et al. / Tetrahedron 65 (2009) 2424–2429
2425
A
D
0
0
0
.12
.08
.04
0
0.12
1
1
-
2
[
H SO ] = 0.07 x 10
M
2
4
0.08
-2
[
H SO ] = 3.4 x 10 M
2
2 4
0.04
2
0
1
2
3
4
5
6
0
0
0
0
1
2
3
3
3
B
E
0
0
0
.12
.08
.04
0
0
0
0
0
.16
.12
.08
.04
0
1
1
-
2
[
H SO ] = 0.34 x 10
M
2
4
2
-2
[
H SO ] = 6.8 x 10 M
2 4
0
1
2
3
2
C
0
0
0
0
0
.20
.16
.12
.08
.04
0
1
2
F
0.16
0.12
1
1
0.08
0.04
0
-
2
[H2SO4] = 10.0 x 10-2
M
[
H SO ] = 1.0 x 10
M
2
4
2
2
0
1
2
3
Time / hours
4
5
6
1
2
Time / hours
G
5
3
4
3
2
1
4
40
20
0
0
0
2
4
[
6
H SO ] x 10 /M
8
10
12
2
2 4
Figure 1. Accumulation of the products (cyclohexyl hydroperoxide, curve 1 as well as the sum cyclohexanolþcyclohexanone, curve 2, graphs A–F) in the oxidation of cyclohexane
ꢀ
(
0.46 M) with hydrogen peroxide (50% aqueous; 1.47 M) catalyzed by NaVO
3
(0.1 mM) in MeCN at 50 C at various total concentrations of H
2
SO
4
(these concentrations are written in
graphs A–F). Dependencies of the initial reaction rate W
0
and the product yield after 3 h on the concentration of H
2
4
SO are shown in graph G. Concentrations of cyclohexanone and
cyclohexanol were determined twice, before and after reduction of the aliquots with solid PPh
3
(for this method, see Ref. 8).
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. We demonstrate in the present
work with this method that the vanadium-catalyzed reaction af-
fords predominantly the cyclohexyl hydroperoxide, CyOOH,
whereas cyclohexanone and cyclohexanol are formed in very small
amounts (Fig. 1, graphs A–F).

2426
L.S. Shul’pina et al. / Tetrahedron 65 (2009) 2424–2429
It follows from Figure 1 that the highest yield of the cyclohexyl
hydroperoxide (37% based on cyclohexane) and turnover number
A
B
C
0
0
0
0
.20
.16
.12
.08
(
1700) can be attained at [NaVO
3
]¼0.1 mM and [H
2
SO
4
]¼0.01 M
ꢀ
after 3 h at 50 C (Fig. 1, graph C). Some decomposition of CyOOH
occurs after 3 h under these conditions. Graph G demonstrates that
there is no substantial increase in yield if the concentration of the
sulfuric acid is higher than 0.01 M. However, the initial reaction rate
W
0
grows four times when the concentration of the sulfuric acid is
1
ꢂ2
changed from 0.07ꢁ10 M to 0.1 M. The data on the n-heptane
oxidation with the system under consideration are summarized in
Table 1. It can be seen that the highest TON¼1090 can be attained
after 3 h.
2
The kinetic curves of the CyH oxidations catalyzed by NaVO
3
at
0.04
0
its higher concentration (1.0 mM) are shown in Figure 2, graphs A,
B. The oxidation of cyclohexane carried out at a lower concentra-
tion [NaVO
3
]¼0.1 mM is demonstrated in Figure 2, graph. C.
The oxidation in the absence of sulfuric acid proceeds noticeably
slower. Thus, under the experimental conditions shown in Figure 2,
0
0.5
1.0
1.5
2.0
2.5
3.0
graph B (viz at [NaVO
3
]¼1.0 mM, [CyH]
0
¼0.46 M, [H
2
O
2
]
0
¼1.47 M,
ꢀ
5
0 C) only 0.015 M of cyclohexyl hydroperoxide was formed after
0.20
5
h. The reaction in the presence of sulfuric acid (0.01 M) but in the
ꢀ
absence of NaVO
3
gave only 0.004 M of CyOOH after 4 h at 50 C. At
0.16
0.12
0.08
the same time, the full catalytic system(which contains both sodium
vanadate and sulfuric acid) efficiently oxidizes cyclohexane even at
room temperature with the TON attaining 1600 after 48 h (Fig. 3).
Other strong inorganic and carboxylic acids can be used in the
combination with sodium vanadate for the efficient alkane oxida-
tion. For example, the cyclohexane oxygenation co-catalyzed by
1
ꢀ
oxalic acid occurs with TON¼1200 after 2 h at 50 C (Fig. 4).
Alkanes can be oxidized by this system in water solution in a bi-
phasic system. Thus, cyclohexane (1.15 mmol) after the reaction
0.04
2
with NaVO
3
(0.0005 mmol),
H
2
SO
4
2 2
(0.01 mmol), and H O
(
7.3 mmol) gave cyclohexanol (0.45 mmol after reduction with
3
PPh ) with TON 90. We have alsofound thatthe systemoxidizes light
0
alkanes both in acetonitrile and water. The results are summarized
in Table 2. It can be seen that the oxidation of n-butane occurs in 19%
yield and the TONs in the oxidation of propane and ethane are ca.
0
0.5
1.0
1.5
2.0
2.5
3.0
2
00. The oxidation in water is noticeably less efficient.
0.12
The regioselectivity parameters determined for the oxidation of
n-heptane (Tables 1 and 3, entries 1,2) and n-octane (Table 3, en-
tries 1,2) are low, C(1):C(2):C(3):C(4)z1:(5–10):(5–10):(5–10).
These values are close to the parameters determined previously for
systems, which oxidize alkanes with participation of hydroxyl
radicals (compare with the parameters summarized in entries 3–8
of Table 3). It is clear that the corresponding selectivity parameters
for the systems that do not involve active oxygen-centered radicals
1
0
0
.08
.04
0
2
(
entries 9–12) are noticeably higher. The bond-selectivity
0
1
2
3
Time / hours
4
5
6
Table 1
2 2 3 2 4
Oxidation of n-heptane with the H O –NaVO –H SO
systema
Figure 2. Accumulation of the products (cyclohexyl hydroperoxide, curve 1 as well as
Regioselectivityb
the sum cyclohexanolþcyclohexanone, curve 2) in the oxidation of cyclohexane with
Time (h) Concentration (mM)
ꢀ
hydrogen peroxide (50% aqueous; 1.47 M) catalyzed by NaVO
3
in MeCN at 50 C at
one-2 one-3 one-4 ol-1 ol-2 ol-3 ol-4
various initial concentrations of the components. Graph A: NaVO
3
(1.0 mM);
(1.0 mM);
(0.1 mM);
ꢂ3
[
[
[
H
H
H
2
2
2
SO
SO
SO
4
4
4
]
]
]
total¼7ꢁ10 M; cyclohexane (0.46 M). Graph B: NaVO
3
0
0
1
2
3
5
.25
.50
0.2
0.5
1.3
3.0
4.0
6.0
0.2
0.5
1.3
3.0
5.0
8.0
0.0
0.0
0.4
2.0
4.0
6.0
2.1
3.0
5.0
6.0
8.0
4.5
8.5
16.2 16.6
25.0 25.0 11.0 1.0:7.5:7.5:6.6
34
36
29
8.8
3.6 1.0:6.1:6.3:5.1
7.0 1.0:8.1:8.3:7.0
ꢂ2
total¼1ꢁ10 M; cyclohexane (0.46 M). Graph C: NaVO
3
ꢂ2
total¼1ꢁ10 M; cyclohexane (0.23 M). Concentrations of cyclohexanone and
cyclohexanol were determined twice, before and after reduction of the aliquots with
solid PPh (for this method, see Ref. 8).
34
35
29
15
17
15
1.0:8.5:8.5:7.5
1.0:6.8:6.6:6.4
1.0:9.7:9.7:9.9
3
ꢀ
ꢀ
ꢀ
parameter (1 :2 :3 ) in the oxidation of methylcyclohexane by the
–NaVO –H SO system, as in the case of linear alkanes, is close
a
Reaction conditions: n-heptane, 0.7 M; H
.01 M; solvent MeCN; homogeneous solution at 50 C. Concentrations of the
2
O
2
, 1.5 M; NaVO
3
2
, 0.1 mM; H SO
4
,
ꢀ
H
2
O
2
3
2
4
0
products were measured after reduction with PPh
TON, moles of the products per mol of catalyst) 1090 was attained after 3 h. Con-
centration of heptanal was <0.1 mM.
Relative reactivities of hydrogen atoms at carbons 1, 2, 3, and 4,
C(1):C(2):C(3):C(4), of the n-heptane chain. The calculated reactivities from the
3
. The maximum turnover number
to the values of parameters found for the systems oxidizing alkanes
with participation of hydroxyl radicals (compare with the param-
eters summarized in entries 3–8 of Table 3). The oxidation of
cis- and trans-1,2-dimethylcyclohexanes proceeds non-stereo-
selectively as the trans/cis ratios of isomeric alcohols (after
(
b
3
concentrations of alcohols after reduction with PPh parameters were normalized,
i.e., calculated taking into account the number of hydrogen atoms at each carbon.
3
reduction with PPh ) were ca. 1 (Table 3).

L.S. Shul’pina et al. / Tetrahedron 65 (2009) 2424–2429
2427
On the basis of the selectivity parameters (which are low), we
can assume that the alkane oxidation reaction proceeds via the
formation of hydroxyl radicals. Vanadate anion under the action
of acid is transformed into oligomeric oxovanadates.1 The yellow
color of the initial stock solution indicates the formation of pol-
yvanadates when sulfuric acid is added to the suspension of
0
0
0
0
.16
.12
.08
.04
4
1
3 2 2
NaVO in water. Under the action of the first H O molecule,
vanadium(V) ion in the oligomer is reduced to vanadium(IV) (Eq.
5
1
), as it has been proposed previously for another system. The
second hydrogen peroxide molecule reacts with the V(IV) de-
rivative to generate the hydroxyl radical (Eq. 2). The hydroxyl
radical attacks the alkane molecule, RH (Eq. 3), and the formed
alkyl radical reacts rapidly with the oxygen molecule (Eq. 4). The
2
ꢃ
alkyl peroxy radical, ROO , is further transformed into the alkyl
0
hydroperoxide, which is the primary and main product of our
ꢃ
reaction. The perhydroxyl radical, HOO , is known to react with
0
10
20
30
Time / hours
40
50
15
the V(IV) and V(V) complexes.
Figure 3. Accumulation of the products (cyclohexyl hydroperoxide, curve 1 as well as
the sum cyclohexanolþcyclohexanone, curve 2) in the oxidation of cyclohexane
ꢃ
D
VðVÞDH O /VðIVÞDHOO DH
(1)
(2)
2
2
(
0.46 M) with hydrogen peroxide (50% aqueous; 1.47 M) catalyzed by NaVO
3
(0.1 mM)
ꢀ
in MeCN at 20 C in the presence of H
2
SO
4
(0.01 M). Concentrations of cyclohexanone
ꢃ
—
VðIVÞDH O /VðVÞDHO DHO
and cyclohexanol were determined twice, before and after reduction of the aliquots
with solid PPh (for this method, see Ref. 8).
2
2
3
ꢃ
ꢃ
HO DRH/H ODR
(3)
2
ꢃ
ꢃ
R DO /ROO
(4)
2
In the presence of CCl
4
or CBr
4
the rate of cyclohexane oxy-
genation is noticeably lower, and RCl or RBr is formed, respectively.
This testifies that alkyl radicals R take part in the oxidation process
0.16
0.12
0.08
0.04
0
ꢃ
1
as it was shown for other systems operating via the formation of
5
a
hydroxyl radicals.
. Conclusions
The system described in the present work can be employed for
3
the hydroperoxidation of alkanes by a cheap green reagent (hy-
drogen peroxide) at low temperature and in acetonitrile or water
2
(less efficiently), which is believed to occur via formation of the
hydroxyl radical. The hydroxyl radical attacks the alkane molecule,
and the formed alkyl radical reacts rapidly with the oxygen mole-
cule to generate the corresponding alkyl peroxy radical, which is
further transformed into the alkyl hydroperoxide.
0
20
40
60
Time / min
80
100
120
Figure 4. Accumulation of the products (cyclohexyl hydroperoxide, curve 1 as well as
the sum cyclohexanolþcyclohexanone, curve 2) in the oxidation of cyclohexane
4
. Experimental section
(
0.46 M) with hydrogen peroxide (50% aqueous; 1.47 M) catalyzed by NaVO
3
(0.1 mM)
ꢀ
The catalyst and co-catalyst were used in the form of a stock
in MeCN at 50 C at the presence of oxalic acid (0.02 M). Concentrations of cyclo-
hexanone and cyclohexanol were determined twice, before and after reduction of the
solution prepared by the following procedure. Concentrated
aliquots with solid PPh
3
(for this method, see Ref. 8).
2
H SO
(0.1 mL; 1.7 mmol) was slowly added to a mixture of
4
Table 2
2
O
2
–NaVO
3
–H
, (mmol) Products, (mmol)
MeCOEt (0.125), EtCH(OH)Me (0.105), EtCH
2 4
SO
systema
Oxidation of light alkanes with the H
Alkane, (pressure, bar; mmol) Solvent NaVO
3
TON Yield, %b
n-Butane (1; 1.4)
Propane (8; 11)
Propane (8; 11)
Propane (8; 11)
Ethane (30; 41)
Methane (35; 48)
Methane (35; 48)
MeCN
MeCN
0.005
0.005
0.005
0.005
0.005
2
CHO (0.03)
52
19c
14
1
0.3
13
0.3
0.3
Acetone (0.35), isopropanol (0.4), n-propanol (0.19), propanal (0.026), propionic acid (0.04) 200
Acetone (0.035), isopropanol (0.006), propanal (0.009), propionic acid (0.009)
Acetone (0.017), isopropanol (0.006)
Ethanol (0.48), acetaldehyde (0.30), acetic acid (0.16)
Methanol (0.03)
Methanol (0.025)
d
H
H
2
O
O
12
5
e
2
MeCN
MeCN
MeCN
190
60
5
0.0005
0.005
a
ꢀ
Reaction conditions: H
2
O
2
, 7.3 mmol; H
2
SO
4
, 0.01 mmol; 4 h at 50 C. Total volume of the reaction solution was 5 mL. Volume of the autoclave was 39 mL. Concentrations of
3
the products were measured after reduction with PPh (for this method, see Ref. 8).
b
2 2
Based on H O .
Based on n-butane.
Water was added to the total volume of the reaction solution 5 mL.
Total volume of the reaction solution was 0.6 mL.
c
d
e

2428
L.S. Shul’pina et al. / Tetrahedron 65 (2009) 2424–2429
Table 3
Selectivity parameters in oxidation of linear and branched alkanes by certain oxidizing systems
a
ꢀ
ꢀ
ꢀ
Entry
System
C(1):C(2):C(3):C(4)
1 :2 :3
trans/cis
n-Heptane
n-Octane
MCH
cis-DMCH
trans-DMCH
ꢀ
1
2
3
4
5
6
7
8
9
NaVO
NaVO
3
–H
–H
2
SO
SO
4
–H
–H
2
O
O
2
2
(MeCN, 50 C)
1:6.9:6.6:6.5
1:8:7:8
1:5.7:7.2:5.0
1:7:6:7
1.0:10.1:10.7:8.4
1:7:6:5
1:6.7:7.5:5.3
1:10.2:6.8:6.3
1:7:26
1:7:18
1:9:37
1:2:6
0.86
1.0
0.75
0.9
0.90
1.0
0.8
1.0
ꢀ
3
2
4
2
(H
2
O, 50 C)
(MeCN, 40 C)b
ꢀ
n-Bu
–H
FeSO
Ni(ClO
4
NVO
3
–PCA–H
2
O
2
ꢀ
h
n
2
O
2
(MeCN, 20 C)
ꢀ
4
–H
2
O
2
(MeCN, 20 C)
1:5:5:4.5
1.3
1.2
(MeCN, 70 C)c
ꢀ
1:6.3:7.2:6.1
1:5.5:5.0:4.6
1:5.3:5.4:4.9
1:7:15
1:4:10
1:6:23
4
)
4
–TMTACN–H
2
O
2
ꢀ
d
1–H
2
O
2
(MeCN, 60 C)
0.9
0.8
(MeCN, 70 C)e
ꢀ
1:5.6:5.6:5.0
0.8
RCg
4.1
H
2
O
2
–Al(NO
3
)
3
ꢀ
f
m-CPBA (MeCN, 25 C)
1:36:36.5
1:89:750
0.65
f
g
1
0
H
2
O
2
in CF
NaAuCl –H
2–MeCO H–H
3
COOH
1:364:363
RC
ꢀ
h
1
1
4
2
O
2
(MeCN, 75 C)
1:35:25:23
1:46:35:34
1:116:255
1:26:200
(MeCN, 25 C)i
ꢀ
1:29:25:24
0.34
12
2
2
O
2
a
ꢀ
ꢀ
ꢀ
Parameters C(1):C(2):C(3):C(4) are relative reactivities of hydrogen atoms at carbons 1, 2, 3, and 4 of the n-heptane or n-octane chain. Parameters 1 :2 :3 are relative
normalized reactivities of the hydrogen atoms at primary, secondary, and tertiary carbons of branched alkanes. The calculated reactivities from the concentrations of alcohols
after reduction with PPh parameters were normalized, i.e., calculated taking into account the number of hydrogen atoms at each carbon. Parameter trans/cis is determined as
3
the ratio of the formed tertiary alcohol isomers with mutual trans and cis orientation of the methyl groups. Abbreviations: MCH is methylcyclohexane; cis-DMCH and trans-
DMCH are isomers of 1,2-dimethylcyclohexane.
b
For this system, which is believed to oxidize substrates via formation of hydroxyl radicals, see Ref. 5.
TMTACN is 1,4,7-trimethyl-1,4,7-triazacyclononane. For this system, see Ref. 9.
c
d
1
is complex (2,3-h-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium. For this system, see Ref. 10.
e
f
For this system, see Ref. 11.
n-Hexane was used instead of n-heptane.
RC, retention of configuration.
g
h
i
For this system, see Ref. 12.
2þ
2
is complex [Mn
2 2
L (
m
-O)
2
]
where L is 1,4,7-trimethyl-1,4,7-triazacyclononane. For these systems, see Ref. 13.
NaVO
temperature. The formed mixture was stirred during approx.
0 min until a yellow homogeneous solution was formed. The
stock solution containing oxalic acid was prepared analogously.
Aliquots of these solutions were added to the reaction mixtures in
alkane oxidations.
3
$4H
2
O (48.5 mg; 0.25 mmol) and H
2
O (4.9 mL) at room
2004; Vol. 2, pp 215–242; (e) Ingold, K. U. Aldrichimica Acta 1989, 22, 69–74; (f)
Shul’pin, G. B. Mini-Rev. Org. Chem. (Bentham) 2009, 6.
2
. (a) Vanadium Compounds: Chemistry, Biochemistry, and Therapeutic Applications;
Tracey, A. S., Crans, D. C., Eds.; Oxford University Press: New York, NY, 1998; (b)
Bolm, C. Coord. Chem. Rev. 2003, 237, 245–256; (c) Br e´ geault, J.-M. J. Chem. Soc.,
Dalton Trans. 2003, 3289–3302; (d) Crans, D. C.; Smee, J. J.; Gaidamauskas, E.;
Yang, L. Chem. Rev. 2004, 104, 849–902; (e) Br e´ geault, J.-M.; Vennat, M.; Salles,
L.; Piquemal, J.-Y.; Mahha, Y.; Briot, E.; Bakala, P. C.; Atlamsani, A.; Thouvenot, R.
J. Mol. Catal. A: Chem. 2006, 250, 177–189; (f) Tracey, A. S.; Willsky, G. R.;
Takeuchi, E. S. Vanadium Chemistry, Biochemistry, Pharmacology and Practical
Applications; CRC: Boca Raton, FL, 2007; (g) Vanadium: the Versatile Metal;
Kustin, K., Pessoa, J. C., Crans, D. C., Eds.; ACS Symposium Series 974; ACS:
Washington, DC, 2007; (h) Rehder, D. Bioinorganic Vanadium Chemistry; Wiley:
Chichester, UK, 2008.
1
The reactions of alkanes were typically carried out in air in
ꢀ
thermostated (50 C) Pyrex cylindrical vessels with vigorous stirring
2 2
(CAUTION: the combination of air or molecular oxygen and H O
with organic compounds at elevated temperatures may be explo-
sive!). The reactions were stopped by cooling, and analyzed twice,
3
. (a) Butler, A.; Clague, M. J.; Meister, G. E. Chem. Rev. 1994, 94, 625–638; (b)
Conte, V.; Di Furia, F.; Licini, G. Appl. Catal., A: General 1997, 157, 335–361; (c)
Pombeiro, A. J. L. ACS Symp. Ser. 2007, 974, 51–60.
3
i.e., before and after the addition of an excess of solid PPh . This
8
method was developed and used previously by some of us for the
analysis of reaction mixtures obtained from various alkane oxida-
tions. A Fisons Instruments GC 8000 series gas chromatograph with
4
. (a) Gekhman, A. E.; Stolyarov, I. P.; Ershova, N. V.; Moiseeva, N. I.; Moiseev, I. I.
Dokl. Akad. Nauk 2001, 378, 639–643 (in Russian); (b) Pokutsa, A. P.; Le Bras, J.;
Muzart, J. Izv. Akad. Nauk, Ser. Khim. 2005, 307–310 (in Russian); (c) Reis, P. M.;
Silva, J. A. L.; Palavra, A. F.; Fra u´ sto da Silva, J. J. R.; Pombeiro, A. J. L. J. Catal.
2005, 235, 333–340; (d) Kirillova, M. V.; da Silva, J. A. L.; Fra u´ sto da Silva, J. J. R.;
Pombeiro, A. J. L. Appl. Catal. A: General 2007, 332, 159–165; (e) Kirillova, M. V.;
Kuznetsov, M. L.; Reis, P. M.; da Silva, J. A. L.; Fra u´ sto da Silva, J. J. R.; Pombeiro,
A. J. L. J. Am. Chem. Soc. 2007, 129, 10531–10545; (f) Kirillova, M. V.; Kuznetsov,
M. L.; da Silva, J. A. L.; da Silva, M. F. C. G.; Fra u´ sto da Silva, J. J. R.; Pombeiro, A. J.
L. Chem.dEur. J. 2008, 14, 1828–1842.
a capillary column 30 mꢁ0.32 mmꢁ25
mm, DB-WAX (J&W) (helium
was the carrier gas; the internal standard was nitromethane) was
used. The reactions in water were analyzed analogously after addi-
tion of acetonitrile to the sample of the final reaction solution.
Acknowledgements
5
. (a) Shul’pin, G. B.; Attanasio, D.; Suber, L. J. Catal. 1993, 142, 147–152; (b)
Shul’pin, G. B.; Drago, R. S.; Gonzalez, M. Russ. Chem. Bull. 1996, 45, 2386–2388;
(
8
c) Shul’pin, G. B.; Ishii, Y.; Sakaguchi, S.; Iwahama, T. Russ. Chem. Bull. 1999, 48,
87–890; (d) Shul’pin, G. B.; Kozlov, Y. N.; Nizova, G. V.; S u¨ ss-Fink, G.; Stanislas,
The authors thank the Fundaç a˜ o para a Ci eˆ ncia e a Tecnologia
(
3
FCT) and its POCI 2010 programme (FEDER funded) (grant BPD/
4926/07 for M.V.K.), the MRTN-CT-2003-503864 (AQUACHEM)
project and the Russian Foundation for Basic Research (grant 06-
3-32344-a) for support. L.S.S. and G.B.S. express their gratitude to
the FCT for making it possible for them to stay at the Instituto Su-
perior T e´ cnico, TU Lisbon, as invited scientists and to perform a part
of the present work.
S.; Kitaygorodskiy, A.; Kulikova, V. S. J. Chem. Soc., Perkin Trans. 2 2001, 1351–
1371; (e) de la Cruz, M. H. C.; Kozlov, Y. N.; Lachter, E. R.; Shul’pin, G. B. New J.
Chem. 2003, 27, 634–638; (f) Kozlov, Y. N.; Nizova, G. V.; Shul’pin, G. B. J. Mol.
Catal. A: Chem. 2005, 227, 247–253; (g) Khaliullin, R. Z.; Bell, A. T.; Head-Gordon,
M. J. Phys. Chem. B 2005, 109, 17984–17992; (h) Kozlov, Y. N.; Romakh, V. B.;
Kitaygorodskiy, A.; Bugly o´ , P.; S u¨ ss-Fink, G.; Shul’pin, G. B. J. Phys. Chem. A 2007,
0
1
11, 7736–7752; (i) Shul’pin, G. B.; Mishra, G. S.; Shul’pina, L. S.; Strelkova, T. V.;
Pombeiro, A. J. L. Catal. Commun. 2007, 8, 1516–1520.
6
. (a) Reis, P. M.; Silva, J. A. L.; Fra u´ sto da Silva, J. J. R.; Pombeiro, A. J. L. Chem.
Commun. 2000, 1845–1846; (b) Kirillova, M. V.; Kirillov, A. M.; Reis, P. M.; Silva,
J. A. L.; Fra u´ sto da Silva, J. J. R.; Pombeiro, A. J. L. J. Catal. 2007, 248, 130–136; (c)
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.
References and notes
1
. (a) Catalytic Oxidations with Hydrogen Peroxide as Oxidant; Strukul, G., Ed.;
7. Romakh, V. B.; S u¨ ss-Fink, G.; Shul’pin, G. B. Pet. Chem. 2008, 48, 440–443.
8. (a) Shul’pin, G. B. J. Mol. Catal. A: Chem. 2002, 189, 39–66; (b) Shul’pin, G. B. C.R.
Acad. Sci., Ser. IIc: Chim. 2003, 6, 163–178 (in English).
Kluwer Academic: Dordrecht, The Netherlands, 1992; (b) Shilov, A. E.; Shul’pin,
G. B. Chem. Rev. 1997, 97, 2879–2932; (c) Shilov, A. E.; Shul’pin, G. B. Activation
and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal
Complexes; Kluwer: Boston, 2000; (d) Shul’pin, G. B. Oxidations of C–H Com-
pounds Catalyzed by Metal Complexes. In Transition Metals for Organic Syn-
thesis, 2nd ed.; Beller, M., Bolm, C., Eds.; Wiley–VCH: Weinheim, New York, NY,
9. Shul’pin, G. B. J. Chem. Res., Synop. 2002, 351–353.
10. (a) Shul’pina, L. S.; Kudinov, A. R.; Petrovskaya, E. A.; Strelkova, T. V.; Shul’pin,
G. B. Pet. 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.

L.S. Shul’pina et al. / Tetrahedron 65 (2009) 2424–2429
2429
1
1. Mandelli, D.; Chiacchio, K. C.; Kozlov, Y. N.; Shul’pin, G. B. Tetrahedron Lett. 2008,
9, 6693–6697.
2. Shul’pin, G. B.; S u¨ ss-Fink, G.; Shilov, A. E. Tetrahedron Lett. 2001, 42, 7253–7256.
3. (a) Shul’pin, G. B.; S u¨ ss-Fink, G.; Shul’pina, L. S. J. Mol. Catal. A: Chem. 2001, 170,
7–34; (b) Woitiski, C. B.; Kozlov, Y. N.; Mandelli, D.; Nizova, G. V.; Schuchardt,
Chem. Soc. 1989, 111, 4518–4519; (f) Pope, M. T.; M u¨ ller, A. Angew. Chem., Int. Ed.
Engl. 1991, 30, 34–48; (g) Kats, M. M.; Shul’pin, G. B. Bull. Acad. Sci. USSR, Div.
Chem. Sci. 1990, 39, 2233; (h) Hou, D.; Hagen, K. S.; Hill, C. L. J. Am. Chem. Soc.
1992, 114, 5864–5866; (i) M u¨ ller, A.; Sessoli, R.; Krickemeyer, E.; B o¨ gge, H.;
Meyer, J.; Gatteschi, D.; Pardi, L.; Westphal, J.; Hovemeier, K.; Rohlfing, R.;
D o¨ ring, J.; Hellweg, F.; Beugholt, C.; Schmidtmann. Inorg. Chem. 1997, 36, 5239–
5250; (j) Livage, J. Coord. Chem. Rev. 1998, 178–180, 999–1018; (k) Ng, C. H.; Lim,
C. W.; Teoh, S. G.; Fun, H.-K.; Usman, A.; Ng, S. W. Inorg. Chem. 2002, 41, 2–3; (l)
Guzm a´ n, J.; Saucedo, I.; Navarro, R.; Revilla, J.; Guibal, E. Langmuir 2002, 18,
1567–1573; (m) Zainullina, V. M.; Volkov, V. L.; Podvalnaya, N. V.; Ivanovskii,
A. L. J. Struct. Chem. 2005, 46, 340–342; (n) Hao, N.; Qin, C.; Xu, Y.; Wang, E.; Li,
Y.; Shen, E.; Xu, L. Inorg. Chem. Commun. 2005, 8, 592–595; (o) Kurata, T.;
4
1
1
1
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.
2
006, 88, 339–348; (d) Romakh, V. B.; Therrien, B.; S u¨ ss-Fink, G.; Shul’pin, G. B.
Inorg. Chem. 2007, 46, 1315–1331; (e) Shul’pin, G. B.; Matthes, M. G.; Romakh, V.
B.; Barbosa, M. I. F.; Aoyagi, J. L. T.; Mandelli, D. Tetrahedron 2008, 64, 2143–
2
152; (f) Shul’pin, G. B.; Kozlov, Y. N.; Kholuiskaya, S. N.; Plieva, M. I. J. Mol.
Catal., A: Chem. 2009, 299, 77–87.
4. (a) Naumann, A. W.; Hallada, C. J. Inorg. Chem. 1964, 3, 70–77; (b) Evans, H. T., Jr.
Inorg. Chem. 1966, 5, 967–977; (c) Murmann, R. K.; Giese, K. C. Inorg. Chem.
978, 17, 1160–1166; (d) Day, V. W.; Klemperer, W. G.; Maltbie, D. J. J. Am. Chem.
Soc. 1987, 109, 2991–3002; (e) Day, V. W.; Klemperer, W. G.; Yaghi, O. M. J. Am.
1
Uehara, A.; Hayashi, Y.; Isobe, K. Inorg. Chem. 2005, 44, 2524–2530; (p)
Schwendt, P.; Tracey, A. S.; Tatiersky, J.; G a´ likov a´ , J.; Zˇ a´ k, Z. Inorg. Chem. 2007,
46, 3971–3983.
1
15. Rush, J. D.; Bielski, B. H. J. J. Phys. Chem. 1985, 89, 1524–1528.