Baeckvall J.-E. (ed.) Modern Oxidation Methods
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OH
R
O
t
-BuOO R
t
-BuOOH
57
RuCl
2
(PPh
3
)
3
(cat.)
C
6
H
6
85%
86%
91%
Me
i
-Pr
Ph
R =
R =
=R
a:
b:
c:
ð7:73Þ
The reaction can be rationalized by assuming the mechanism which involves an
oxo-ruthenium complex (Eq. (7.74)). Hydrogen abstraction with oxo-ruthenium
species gives the phenoxyl radical 58, which undergoes fast electron transfer to the
ruthenium to give a cationic intermediate, 59. Nucleophilic reaction with the second
molecule of t-BuOOH gives the product, 57.
OH
R
O
t
-BuOO R
O
Ru
n+2
R
OH
Ru
n
OH
Ru
n+1
O
R
– Ru
n
– H
2
O
57
58
SET
+
+
+
t
-BuOOH
59
ð7:74Þ
The 4-( tert-butyldioxy)-4-alkylcyclohexadienones 57 thus obtained are versatile
synthetic intermediates. The TiCl
4
-promoted transformation of 60, obtained from
the oxidation of 3-methyl-4-isopropylphenol, gives 2,6-disubstituted quinones 61,
which is derived from rearrangement of the i-Pr group (93%) (Eq. (7.75)).
O
t
-BuOO
i
-Pr
O
O
i
-P
r
Me
Me
TiCl
4
CH
2
Cl
2
6160
OH
Me
i
-Pr
t
-BuOOH
RuCl
2
(PPh
3
)
3
EtOAc
92%
(cat.)
93%
ð7:75Þ
Interestingly, sequential migration-Diels–Alder reactions of tert-butyldioxy die-
none 63 in the presence of cis-1,3-pentadiene gave cis-fused octahydroanthraquinone
64 stereoselectively (73%) (Eq. (7.76)).
OH
O
t
-BuOO
O
O
H
H
t
-BuOOH
RuCl
2
(PPh
3
)
3
EtOAc
73%
85%
(cat.)
62
63
64
TiCl
4
CH
2
Cl
2
ð7:76Þ
7.3 Oxidation with Low-Valent Ruthenium Catalysts and Oxidants
j
263
Ruthenium-catalyzed oxygenation of catechols gives muconic acid anhydride and
2H-pyran-2-one [123].
Oxidation of an aromatic ring bearing methoxy groups was performed using
a ruthenium porphyrin catalyst. The Ru(TPP)(O)
2
-catalyzed (TPP ¼ 5,10,15,20-tetra-
phenylporphyrinato) oxidation of polymethoxybenzene with 2,6-dichloropyridine
N-oxide gives the corresponding p-quinone derivatives (Eq. (7.77)) [124].
18
O labeling
experiments showed that the reaction proceeds via selective hydroxylation of the
aromatic ring by oxo-ruthenium porphyrins to give phenol derivatives, which
undergo subsequent oxidation to afford the corresponding quinones. Oxidation of
anisole to p-benzoquinone can be performed by ruthenium complex of 1,4,7-
trimethyl-1,4,7-triazacyclononane with tert-butyl hydroperoxide [125].
OMe
OMeMeO
O
OMeMeO
O
Ru(TPP)(O)
2
(cat.)
2,6-dichloropyridine
N
-oxide
HBr, MS4A
benzene, 30 C
o
97%
ð7:77Þ
Oxidation of naphthalene derivatives gave naphthoquinones (Eq. (7.78)) [126].
Oxidative coupling can be carried out with supported ruthenium catalyst, Ru(OH)
2
/
Al
2
O
3
(Eq. (7.79)) [127].
Ru(terpy)(pyridine-2,6-dicarboxylate)
+
O
O
O
O
56% (2.8:1)
(cat.)
H
2
O
2
, C
12
H
25
SO
3
Na, H
2
O, 40
o
C
ð7:78Þ
OH
Ru(OH)
x
/Al
2
O
3
O
2
, toluene, 80
o
C
(cat.)
OH
OH
84%
ð7:79Þ
264
j
7 Ruthenium-Catalyzed Oxidation for Organic Synthesis
7.3.6
Oxidation of Hydrocarbons
The catalytic oxidation of unactivated hydrocarbons remains a challenging topic.
Ruthenium porphyrins, such as Ru(OEP)(PPh
3
)
3
, show catalytic activity for the
oxidation of alkanes with PhIO [38]. The oxidation of alkanes with 2,6-dichloropyr-
idine N-oxide in the presence of Ru(TMP)(O)
2
(3) and HBr [128] and Ru(TPFPP)(CO)
(TPFPP ¼ tetrakis(pentafluorophenyl)porphyrinato) (4) [40a] gives the correspond-
ing oxidized compounds. Hydroxylation of adamantane was achieved with high
selectivity and high efficiency (12 300 turnovers) (Eq. (7.80)). Ru-porphyrin-catalyzed
amidation of hydrocarbons can be performed with PhI ¼ NTs [129]. Zeolite-encap-
sulated perfluorinated ruthenium phthalocyanines catalyze the oxidation of cyclo-
hexane with t-BuOOH [130]. The addition of Lewis acids such as ZnCl
2
greatly
accelerated the reaction rates in the stoichiometiric oxidation of alkanes by BaRu
(O)
2
(OH)
3
[131]. A dioxoruthenium complex with a D
4
-chiral porphyrin ligand has
been used for the enantioselective hydroxylation of ethylbenzene to give a-pheny-
lethyl alcohol with 72% ee [132].
OHOH
O
HO
N
O
ClCl
+
HBr, C
6
H
6
, rt
61%
Ru(TMP)(O)
2
(3)
(cat.)
+
4%13%
14005100TON=12300
ð7:80Þ
Non-porphyrin ruthenium complexes can be used for the catalytic oxidation of
alkanes with peroxides. BaRuO
3
(OH)
2
-catalyzed oxidation of cyclohexane with PhIO
gives oxidation products [131a]. [RuCl(dpp)
2
]
þ
can be used for the oxidation of
alkanes with PhIO or LiClO [45]. The combinations cis-[Ru(dmp)
2
(MeCN)
2
]
2 þ
/H
2
O
2
[50a] (Eq. (7.81)), cis-[Ru(Me
3
tacn)(O)
2
(CF
3
CO
2
)]
þ
/t-BuOOH (Me
3
tacn ¼ N,N
0
,N
00
-
1,4,7-trimethyl-1,4,7-triazacyclononane) [46c], and cis-[Ru(6,6-Cl
2
bpy)
2
(OH
2
)
2
]
2 þ
/t-
BuOOH [46b] are efficient for the oxidation of cyclohexane.
OHOH
O
HO
+
H
2
O
2
15%
cis
-[Ru(dmp)
2
(H
2
O)
2
](PF
6
)
2
(cat.)
+
2%4%
ð7:81Þ
Ruthenium(III) complexes such as [RuCl
2
(TPA)]
þ
and [RuCl(Me
2
SO)(TPA)]
þ
bearing tripodal ligand TPA (TPA ¼ tris(2-pyridylmethyl)amine) were synthesized,
and catalytic oxidation of adamantane with m-chloroperbenzoic acid [133, 134a] or
2,6-dichloropyridine N-oxide [134b] was reported. Polyoxometalate [SiRu(H
2
O)
W
11
O
39
]
5
also works as an oxidation catalyst using KHSO
5
[135a] and H
2
O
2
[135b].
7.3 Oxidation with Low-Valent Ruthenium Catalysts and Oxidants
j
265
The oxidation of hydrocarbons with ruthenium catalysts bearing a simple ligand
is highly effective. The oxidations of hydrocarbons with peroxides such as t-BuOOH
and peracetic acid in the presence of ruthenium catalysts such as RuCl
2
(PPh
3
)
3
[136a,b] or Ru/C [136a,c] gave the corresponding ketones and alcohols. For example,
RuCl
2
(PPh
3
)
3
-catalyzed oxidation of fluorene with t-BuOOH gives fluorenone in
87% yield (Eq. (7.82)). The Ru/C-catalyzed oxidation of cyclohexane with peracetic
acid in ethyl acetate gives cyclohexanone and cyclohexanol with 67% conversion
[136c].
RuCl
2
(PPh
3
)
3
87%
t
-BuOOH
C
6
H
6
, rt
O
(cat.)
ð7:82Þ
It is expected that more reactive species will be generated in the presence of
a strong acid. Indeed, the RuCl
3
nH
2
O-catalyzed oxidation of cyclohexane in tri-
fluoroacetic acid and dichloromethane (5 : 1) with peracetic acid gives cyclohexyl
trifluoroacetate in 77% (Eq. (7.83)) [136a].
OCCF
3
O
O
RuCl
3
•nH
2
O (cat.)
+
CH
3
CO
3
H
CF
3
CO
2
H
CH
2
Cl
2
, rt
conv. 90%
13%77%
ð7:83Þ
The ruthenium-catalyzed oxidation of nitriles takes place at the a -position to
nitriles. For example, the RuCl
3
nH
2
O-catalyzed oxidation of benzylcyanide with
t-BuOOH gives benzoylcyanide in 94% yield [137].
The allylic position of steroidal alkene can be oxidized with t-BuOOH in the
presence of RuCl
3
catalyst (Eq. (7.84)) [138].
R
AcO
RuCl
3
(cat.)
t
-BuOOH
cyclohexane
R
AcO
O
R = CH(CH
3
)(CH
2
)
3
CH(CH
3
)
2
75%
ð7:84Þ
The catalytic oxidation of alkanes with molecular oxygen under mild conditions is
an especially rewarding goal, since direct functionalization of the unactivated CH
bonds of saturated hydrocarbons usually requires drastic conditions such as high
temperature.
Oxo-metal species can be generated by the reaction of a low valent ruthenium
complex with molecular oxygen in the presence of an aldehyde [119]. Thus,
the ruthenium-catalyzed oxidation of alkanes with molecular oxygen in the
presence of acetaldehyde gives alcohols and ketones efficiently [139a]. Typically,
266
j
7 Ruthenium-Catalyzed Oxidation for Organic Synthesis
RuCl
3
nH
2
O-catalyzed oxidation of cyclooctane with molecular oxygen in the pres-
ence of an aldehyde give the corresponding alcohols and ketones selectively
(Eq. (7.85)).
OHO
n
-C
6
H
13
CHO
O
2
(1 atm)
CH
2
Cl
2
, rt
21%63%conv. 8.4%
+
RuCl
3
•nH
2
O (cat.)
ð7:85Þ
These aerobic oxidations can be rationalized by assuming the sequence shown in
Scheme 7.5. The metal-catalyzed radical chain reaction of an aldehyde with molecular
oxygen affords the corresponding peracid. The reaction of metal catalyst with the
peracid thus formed would give an oxo-metal intermediate, followed by oxygen atom
transfer to afford the corresponding alcohols. The alcohol is further oxidized to the
corresponding ketone under these conditions.
A Ru(TPFPP)(CO) (4) complex has been prepared, and it was found that 4 is an
efficient catalyst for the aerobic oxidation of alkanes using acetaldehyde [140]. Thus,
the 4-catalyzed oxidation of cyclohexane with molecular oxygen in the presence of
acetaldehyde gave cyclohexanone and cyclohexanol in 62% yields based on acetal-
dehyde with high turnover numbers of 14 100 (Eq. (7.86)). It is worth to note that
iron [139] and copper [141] catalysts are also efficient for the oxidation of non-
activated hydrocarbons at room temperature under 1 atm of molecular oxygen.
OHO
excess
1 eq
8.1%54%
Ru(TPFPP)(CO)
turnover
number
(
4)
(cat.)
O
2
(1 atm)
+
EtOAc, 70°C
(based on acetaldehyde)
+
1.41 x 10
4
CH
3
CHO
ð7:86Þ
These oxidation reactions provide a powerful strategy for the synthesis of carbonyl
compounds such as cyclohexanone by combination of the Wacker oxidation of
ethylene with the present metal-catalyzed oxidation of cyclohexane (Scheme 7.6).
Very few methods for direct aerobic oxidation of alkanes have been reported using
a perfluorinated ruthenium catalyst [Ru
3
O(OCOCF
2
CF
2
CF
3
)
6
(Et
2
O)
3
]
þ
[50c],
a ruthenium substituted polyoxometalate [WZnRu
2
(OH)(H
2
O)(ZnW
9
O
34
)
2
]
11
(Eq. (7.87)) [[142, 143]], and Ru(OH)
x
/Al
2
O
3
catalyst [144].
M
n+2
=O
M
n+2
=O
RCHO
+
O
2
RCO
3
H
M
n
+
M cat.
ROH
M
n
+
RCO
3
RCOH
2
H+
RH
+
Scheme 7.5
7.3 Oxidation with Low-Valent Ruthenium Catalysts and Oxidants
j
267
OH
Na
11
[WZnRu
2
(OH)(H
2
O)(ZnW
9
O
34
)
2
]
O
2
(1 atm)
1,2-dichloroethane, 80 °C, 72 h
57%
TON = 568
(cat.)
ð7:87Þ
Recently enantioselective oxidative functionalization of CH bonds was reported.
Intramolecular CH amination proceeds in the presence of ruthenium pybox
catalyst with bis(acyloxy)iodobenzene (Eq. (7.88)) [145].
C
6
H
6
, 22 °C, 24 h
(cat.)
MeO
S
H
2
N
O
O
MeO
S
HN
O
O
68% (90%
ee
)
N
NN
O
O
Ru
Br
Br
AgOTf
PhI(O
2
C-
t
-Bu)
2
, MgO
ð7:88Þ
H
2
CHC
2
H
2
CHC
2
O
2
+
++
CH
3
CHO
cat.
+
O
2
O
2
+++
Pd / Cu cat.
CH
3
CO
2
H
CH
3
CHO
CH
3
CO
2
H
R
1
C
R
2
O
R
1
C
R
2
O
(R
3
=H)
22
222
+
H
2
O
232
+
H
2
O
R
1
C
R
2
HH
R
1
C
R
2
HH
Scheme 7.6
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