Catalytic hypervalent iodine oxidation of alcohols to corresponding aldehydes or ketones using 2,2,6,6-tetramethylpiperidinyl-1-oxy and potassium peroxodisulfate

Article abstract of DOI:10.1007/s00706-010-0260-1

An efficient, facile, and mild oxidation of alcohols to the corresponding aldehydes or ketones with potassium peroxodisulfate and 2,2,6,6- tetramethylpiperidinyl-1-oxy in the presence of a catalytic amount of iodobenzene is reported. The oxidation proceeded in a mixed solvent to afford carbonyl compounds in moderate to excellent yields. A possible mechanism for the oxidation is proposed.

Full text of DOI:10.1007/s00706-010-0260-1

Monatsh Chem (2010) 141:327–331
DOI 10.1007/s00706-010-0260-1
ORIGINAL PAPER
Catalytic hypervalent iodine oxidation of alcohols
to corresponding aldehydes or ketones using 2,2,6,6-
tetramethylpiperidinyl-1-oxy and potassium peroxodisulfate
Chenjie Zhu
•
Lei Ji Yunyang Wei
•
Received: 21 December 2009 / Accepted: 21 January 2010 / Published online: 12 February 2010
Ó Springer-Verlag 2010
Abstract Anefficient, facile,andmildoxidationofalcohols
to the corresponding aldehydes or ketones with potassium
peroxodisulfate and 2,2,6,6-tetramethylpiperidinyl-1-oxy in
the presence of a catalytic amount of iodobenzene is reported.
The oxidation proceeded in a mixed solvent to afford carbonyl
compounds in moderate to excellent yields. A possible
mechanism for the oxidation is proposed.
co-oxidants such as m-chloroperbenzoic acid (mCPBA)
[16–28], oxone (2KHSO ÁKHSO ÁK SO ) [29–36], H O
5
4
2
4
2 2
[37, 38], tetraphenylphosphonium monoperoxysulfate
(TPPP) [39], NaBO ÁH O [40], O [41], Ru [42], peracetic
3
2
2
acid [43], or combinations with the nitroxy radical 2,2,6,6-
tetramethylpiperidinyl-1-oxy (TEMPO) [44]. To the best of
our knowledge, there is no report on the use of K S O as
2
2 8
co-oxidant for catalytic hypervalent iodine oxidation. The
advantages of using K S O are due in part to its stability,
Keywords Alcohols Á Catalysis Á Hypervalent iodine Á
Oxidations Á TEMPO
2
2 8
nontoxic nature, low cost, and easy and safe handling.
On the other hand, it is well known that nitroxyl radicals
such as TEMPO and N-hydroxyphthalimide (NHPI) pro-
mote oxidation of various alcohols to the corresponding
carbonyl compounds effectively under mild reaction
conditions (for reviews see [45–48]). Piancatelli and
co-workers have reported a mild and selective method for the
oxidation of primary and secondary alcohols using TEMPO
Introduction
The selective oxidation of alcohols to the corresponding
carbonyl compounds is a fundamental transformation in
both laboratory synthesis and industrial production [1–3].
Numerous hypervalent iodine compounds, e.g., 1,1,1-triace-
toxy-1,1-dihydro-1,2-benzodoxol-3H-one (DMP), 1-hydroxy-
and stoichiometric bis(acetoxy)iodobenzene [PhI(OAc) ] as
2
a reoxidant [49].
1
,2-benzodoxol-3H-one 1-oxide (IBX), PhI(OAc) , and
2
In continuation of our interest in exploring systems for
the oxidation of organic compounds [50–53], we report
herein a facile procedure for the oxidation of alcohols to
the corresponding carbonyl compounds with K S O in the
PhIO, in stoichiometric amounts have been traditionally
employed to accomplish this transformation [4, for reviews
see 5–10]. However, some of these reagents are potentially
explosive, and use of stoichiometric amounts of iodine
reagents leads to the production of equimolar amounts of
organic iodine waste. From economic and environmental
perspectives, the development of catalytic systems based on
hypervalent iodine has received great attention (for reviews
see [11–15]). Many highly efficient systems have been
developed for catalytic hypervalent iodine oxidation using
2
2 8
presence of CF COOH, catalytic amounts of PhI, and
3
TEMPO (Scheme 1).
Results and discussion
Initial experiments were carried out using 4-nitrobenzyl
alcohol as the model substrate. When 4-nitrobenzyl alcohol
was oxidized with K S O /PhI/CF COOH/TEMPO in
C. Zhu Á L. Ji Á Y. Wei (&)
2
2
8
3
School of Chemical Engineering,
Nanjing University of Science and Technology,
Nanjing 210094, China
MeCN/H O at 40 °C for 4 h, 92% conversion of the
2
alcohol and 98% selectivity to the corresponding aldehyde
e-mail: ywei@mail.njust.edu.cn
were observed (Table 1, entry 1). However, in the absence
123

3
28
C. Zhu et al.
Scheme 1
OH
K2S2O8/CF3COOH
cat. PhI, TEMPO
O
1
R = aryls, alkyls
+
H2O
2
R1
R2
R1
R2
R = aryls, alkyls, H
o
MeCN/H2O(4:1 v/v) 40 C
Table 1 Oxidation of 4-nitrobenzyl alcohol
4, 8, 11, and 13) and ketones from secondary alcohols
Table 2, entries 5, 6, 9, and 12). For the oxidation of
(
Entry PhI
2
K S
O
2 8
Acid
Additive
Conv./sel.
a
(%)
primary alcohols, no noticeable overoxidation of aldehyde
to carboxylic acids was detected. Benzylic alcohols
underwent smooth oxidation (Table 2, entries 1–6). An
allylic alcohol, cinnamyl alcohol (Table 1, entry 7), was
also oxidized efficiently without any observable reaction at
the double-bond functionality. Even for the oxidation of
furan-2-ylmethanol an excellent yield was also obtained
(equiv) (equiv)
1
2
3
4
5
6
7
8
9
1
1
1
1
0.1
0.1
0.1
0.1
0.1
None
0.05
0.1
0.1
0.1
0.1
0.1
0.1
3
CF
CF
CF
3
3
3
COOH
COOH
COOH
TEMPO
TEMPO
None
92/98
71/99
21/63
36/96
\10/–
33/90
90/99
\10/–
\10/–
54/93
88/59
\10/–
\10/–
b
3
3
3
None
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
TEMPO
NHPI
None
CF
CF
CF
3
COOH
3
COOH
3
COOH
3
3
3
3
3
3
3
3
(Table 1, entry 10). The electronic properties of the sub-
stituents in the aromatic ring had remarkable influence on
the rate of the oxidation of alcohols. Strong electron-
withdrawing groups, e.g., a nitro group, lowered the reac-
tion rate (Table 2, entry 2). Strong electron-donating
AcOH
HCl
0
1
2
3
3 2
(CF CO) O
CF
CF
CF
3
COOH
3
COOH
3
COOH
groups, such as a –OCH group, accelerated the oxidation
3
BF
3
ÁEt
2
O
(Table 2, entry 3). Use of the present procedure for the
oxidation of aliphatic alcohols under the same conditions
gave moderate yields (61–77%) in prolonged reaction
times (Table 2, entries 8, 11, 12, and 13). In view of the
fact that the oxidation of aliphatic alcohols is much more
difficult than the oxidation of benzylic alcohols, results
obtained with the present procedure were also satisfactory.
Table 3 shows the results of the competitive oxidation
of primary and secondary alcohols. The competing oxida-
tion of an equimolar mixture of benzyl alcohol and
1-phenylethanol resulted in a 93% yield of benzaldehyde
and less than 5% yield of acetophenone (Table 3, entry 1).
Oxidation of an equimolar mixture of octan-1-ol and octan-
2-ol gave 67% caprylic aldehyde, whereas no ketone could
be detected (Table 3, entry 2). These results suggest that
chemoselective oxidation of primary alcoholic functional-
ity in the presence of secondary alcoholic functionality is
possible with the present oxidation system.
c
˚
3 A MS
Reactions were performed by using 1 mmol 4-nitrobenzyl alcohol,
3
3
mmol K
MeCN/H
O (4 cm /1 cm ) at 40 °C for 4 h unless otherwise noted
GC conversion and selectivity
2 2 8
S O , 1 cm acid, 0.2 mmol additive, and 0.1 mmol PhI in
3
3
2
a
b
Without H
˚
2
O
c
0
.1 g 3 A molecular sieve was added
of H O the conversion of the alcohol was decreased to 71%
2
(
Table 1, entry 2). This result suggests that the presence of
H O as a co-solvent is beneficial for the dissolution of
2
K S O . As control experiments, the same reaction was
2 2 8
carried out in the absence of TEMPO, CF COOH, K S O ,
3 2 2 8
or PhI. In all cases, the conversion of the alcohol was much
lower (Table 1, entries 3–6). It was possible to decrease
the amount of PhI to as low as 0.05 equivalent without
significant loss in catalytic efficiency (Table 1, entry 7).
Use of other acids or anhydrides instead of CF COOH in
3
Recently, Kitamura and co-workers reported a facile
experimental procedure for the direct preparation of
this reaction was not successful (Table 1, entries 8–10).
Moreover, a range of additives were tested for this reaction.
However, all of them were unsatisfactory except for
TEMPO (Table 1, entries 10–13). Besides, we also tested
other co-oxidants such as NaBO ÁH O, NaIO , urea
ArI(OCOCF ) from the respective iodoarenes in CF COOH,
3 2 3
using potassium peroxodisulfate (K S O ) as the oxidant
2 2 8
(Scheme 2) [56]. Inspired by the preliminary research, in
our present procedure, PhI and CF COOH may be initially
oxidized by K S O to form the highly reactive hyperva-
3
2
4
3
hydrogen peroxide adduct (UHP), and Na CO Á3H O in
2
3
2
2
2 2 8
this experiment, all of which were not successful.
lent iodine(III) compound PhI(OCOCF
) . The role of
3 2
In order to evaluate the versatility of this novel catalytic
system, we applied the procedure to the oxidation of a wide
range of alcohols, including benzylic, allylic, heterocyclic,
and aliphatic alcohols. As shown in Table 2, most alcohols
underwent oxidation to afford the corresponding aldehydes
or ketones in excellent yield. The present protocol afforded
aldehydes from primary alcohols (Table 2, entries 1, 2, 3,
PhI(OCOCF ) is to regenerate TEMPO from TEMPOH,
3 2
then TEMPO is responsible for the actual oxidation in this
reaction to oxidize alcohols to the corresponding aldehydes
or ketones. A plausible mechanism for this reaction is
depicted in Scheme 3.
In conclusion, a novel and mild catalytic system for the
oxidation of alcohols to the corresponding aldehydes or
1
23

Catalytic hypervalent iodine oxidation of alcohols to corresponding aldehydes or ketones
329
Table 2 K
catalyzed oxidation of alcohols
2 2 8
S O /PhI/TEMPO
a
Yield
%)
c
Entry
Alcohols
Products
Time (h)
Ref.
(
OH
O
1
2
1
4
95
90
[54a, 55a]
[54b, 55b]
OH
OH
O
O
O2N
2
O N
3
4
2
4
97
91
[54c, 55c]
[54d, 55d]
MeO
Cl
MeO
Cl
OH
O
5
OH
O
2.5
93
96
[54e, 55e]
OH
O
6
7
5
5
[54f, 55f]
[54g, 55g]
OH
O
92
77
O
OH
8
9
8
8
[54h, 55h]
[54i, 55i]
Reaction conditions: 1 mmol
alcohol, 3 mmol K
2
S
2 8
O ,
b
OH
O
71
3
0
.1 mmol PhI, 1 cm
3
CF COOH, 0.2 mmol TEMPO,
O
O
3
3
O (4 cm /1 cm ),
b
MeCN/H
0 °C
2
10
11
12
13
OH
5
88
75
70
61
[54j, 55j]
[54k, 54k]
[54l, 55l]
O
4
a
b
Yields of isolated products
unless otherwise noted
CH
3
(CH
2
)
7
OH
CH
3
(CH
2
)
6
CHO
12
12
12
OH
)4
O
b
b
b
Yields were determined by
(
( )4
GC
c
References for isolated
products
n-C H -CH OH
n-C H -CHO
11 23
[54m, 55m]
11
23
2
Table 3 Competitive oxidation
of primary and secondary
alcohols
a
Entry
Substrate
Product
Time (h)
1
Yield (%)
a
OH
O
9
3
1
2
OH
O
<5
67
CH
3
(CH
2
)
7
OH
CH
3
(CH
2
)
6
CHO
Reactions were carried out on a
1:1 mixture of primary and
secondary alcohols, on a
8
OH
O
1
a
mmol scale
GC yield
not detectable
()4
()4
123

3
30
C. Zhu et al.
Scheme 2
K S O , CH Cl
2
2
2
8
2
ArI
+
CF COOH
ArI(OCOCF3)2
3
o
3
6-38 C
Scheme 3
OCOCF3
PhI
OH
2
2
KHSO4
N
O
R1
R2
OCOCF3
O
cat. PhI
+
K S O
8
2
2
R1
R2
2
CF COOH
3
2
N
OH
ketones with K S O /PhI/TEMPO was developed. PhI was
2 2 8
organic layer was separated, and the aqueous layer was
extracted with ether. The combined ether phase was con-
centrated under vacuum. The crude product was purified
by column chromatography (petroleum ether/ethyl ace-
tate = 10/1) to provide the analytically pure product. The
identity of products was determined either by comparison
with authentic samples using gas chromatography or by GC/
MS analysis.
oxidized by K S O in situ to highly active hypervalent
2 2 8
iodine(III) species, a reoxidant of TEMPO, which allowed
the oxidation of various kinds of alcohols, including ben-
zylic, alicyclic, heterocyclic, and aliphatic alcohols to
afford carbonyl compounds in moderate to excellent yields.
The procedure can be used for the synthesis of aldehydes
from primary alcohols or ketones from secondary alcohols.
Selective oxidation of primary alcohols in the presence of
secondary alcohols was also achieved.
Acknowledgments We are grateful to Nanjing University of
Science and Technology for financial support.
Experimental
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