Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic aldehydes and ketones

Article abstract of DOI:10.1016/j.tet.2016.09.019

Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with iodic acid in DMF at 60?°C for 2?h and with iodic acid in the presence of TEMPO (5?mol?%) in DMF at room temperature, respectively. The former method was effective for the oxidation of sterically hindered alcohols at 60?°C and the latter method was effective for the oxidation of less sterically hindered alcohols at room temperature.

Full text of DOI:10.1016/j.tet.2016.09.019

Accepted Manuscript
Synthetic utility of iodic acid in the oxidation of benzylic alcohols to aromatic
aldehydes and ketones
Sho Imai, Hideo Togo
PII:
S0040-4020(16)30926-7
10.1016/j.tet.2016.09.019
TET 28090
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 16 July 2016
Revised Date: 5 September 2016
Accepted Date: 11 September 2016
Please cite this article as: Imai S, Togo H, Synthetic utility of iodic acid in the oxidation of benzylic
alcohols to aromatic aldehydes and ketones, Tetrahedron (2016), doi: 10.1016/j.tet.2016.09.019.
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Synthetic Utility of Iodic Acid in the Oxidation of
Benzylic Alcohols to Aromatic Aldehydes and
Ketones
Sho Imai and Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 Japan
Method A :
HIO3 (1.1 equiv.), DMF, 60 °C, 2 h
O
OH
Method B :
HIO3 (1.1 equiv.), TEMPO (5 mol%),
DMF, r.t., 2 h
Ar
Ar
R
R
36 substrates for
each Method
Ar = aryl; R = H, alkyl

ACCEPTED MANUSCRIPT
Tetrahedron
1
TETRAHEDRON
Pergamon
Synthetic Utility of Iodic Acid in the Oxidation of Benzylic
Alcohols to Aromatic Aldehydes and Ketones
Sho Imai and Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 Japan
Abstract—Various primary and secondary benzylic alcohols were efficiently oxidized to aromatic aldehydes and aromatic ketones with
iodic acid in DMF at 60 °C for 2 h and with iodic acid in the presence of TEMPO (5 mol%) in DMF at room temperature, respectively. The
former method was effective for the oxidation of sterically hindered alcohols at 60 °C and the latter method was effective for the oxidation
of less sterically hindered alcohols at room temperature.
© 2016 Elsevier Science. All rights reserved
DIB-AZADO oxidation, etc. Among the many oxidants
for the oxidation of alcohols, the use of iodic acid (HIO3) as
a less toxic reagent has been little studied, although iodic
acid is less expensive than (diacetoxy)iodobenzene (DIB),
and is an inorganic reagent and not a transition-metal
reagent. As synthetic uses of iodic acid, the oxidative
dehydrogenation of ketones to α,β-unsaturated ketones
with HIO3 in DMSO at 50 °C,8a the oxidation of alcohols to
carbonyl compounds with iodic acid in the presence of KBr
and wet SiO2 in CHCl3 at room temperature,8b and the
oxidation of alcohols to aldehydes and ketones with iodic
acid in the presence of NaHSO4 in wet acetonitrile at
refluxing temperature7c were reported. However, we
would like to question the veracity of the third report.8c
Although we performed the oxidation of p-bromobenzyl
alcohol, 1-phenylethanol, and (-)-menthol carefully on the
basis of the reported reaction conditions, we obtained only
a yield of 24% for p-bromobenzaldehyde, 5% for
acetophenone, and 0% for (-)-menthone, together with the
starting alcohols. Thus, we found that the reaction is not
reproducible. Here, we would like to report a practical
oxidation of primary and secondary benzylic alcohols to
aromatic aldehydes and aromatic ketones, respectively,
with iodic acid alone in DMF at 60 °C and with iodic acid
in the presence of TEMPO in DMF at room temperature.
1. Introduction
The oxidation of alcohols is one of the most important
organic transformation reactions, and therefore, studies for
the mild oxidation methods of alcohols with less toxic
reagents have been carried out extensively.1) Among those
methods, the oxidation of alcohols to aldehydes or ketones
with trifluoroacetic anhydride or oxalyl chloride with
dimethyl sulfoxide (DMSO) in the presence of Et3N in
CH2Cl2
(Swern
oxidation),2)
with
1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3(1H)-2-one
(Dess-Martin periodinane oxidation) in CH2Cl2,3) with
2-iodoxybenzoic acid (IBX) in DMSO,4) with
(diacetoxy)iodobenzene (DIB) in the presence of
2,2,6,6-tetramethylpiperidine 1-oxyl radical (TEMPO) in
CH2Cl2,5) with DIB in the presence of 2-azaadamantane
N-oxyl radical (AZADO) in CH2Cl2,6) and with NaClO in
the presence of TEMPO and KBr in CH2Cl2-H2O7) are the
most popular and useful, because the reactions can be
carried out under mild and transition-metal-free conditions.
However, those methods have drawbacks, such as the
formation of highly malodorous volatile dimethyl sulfide in
the Swern oxidation, the use of explosive and expensive
pentavalent iodine in the Dess-Martin periodinane and IBX
oxidation, and the need to remove of iodobenzene, a
co-product, from the reaction mixture by column
chromatography in the DIB-TEMPO oxidation and the
2. Results and Discussion

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2
Tetrahedron
Table 2. Oxidation of Alcohols with HIO3 and HIO3-TEMPO systems
Method A : HIO3 (1.1 equiv.),
First, the oxidation of p-bromobenzyl alcohol I-1 (1.0
mmol) with iodic acid (1.1 equiv.) was carried out in
acetonitrile (2.0 mL), t-butyl alcohol (2.0 mL),
N,N-dimethylformamide (DMF, 2.0 mL), and dimethyl
sulfoxide (DMSO, 2.0 mL) at 60 °C for 2 h to provide
p-bromobenzaldehyde II-1 in 22%, 36%, 95%, and 95%
yields, respectively, as shown in Table 1. When the
oxidation was carried out in DMF and DMSO at room
temperature for 2 h, p-bromobenzaldehyde II-1 was
obtained in 12% and 25% yields, together with the starting
material I-1 in 81% and 72% yields, respectively. Thus,
warming treatment at 60 °C is effective, and other less
polar solvents, such as dichloromethane and chloroform,
were not effective due to the insolubility of iodic acid in
them. For example, the DMF solution of alcohol with
iodic acid became a homogeneous solution at 60 °C,
although the same reaction at room temperature did not
produce a homogeneous solution.
O
OH
DMF, 60 °C, 2 h
R
R'
R
R'
Method B : HIO3 (1.1 equiv.),
TEMPO (5 mol%),
DMF, r.t., 2 h
II
I
product, yielda (%)
O
O
O
Cl
Br
Me
II-3
A : 91%
B : 86%
II-1 A : 95%
II-2
II-5
A : 93%
B : 94%
B : 94%, 99%i
Cl
O
O
O
O2N
II-6
Cl
A : 89%
B : 89%
A : 92%
B : 91%
II-4
A : 84%
B : 93%
Table 1. Oxidation of 4-Bromobenzyl Alcohol I-1 with HIO3 (Method A)
O
O
O
Me
F3C
II-7
MeO2C
II-8
OH
S
O
HIO3 (1.1 equiv.)
A : 75%
B : 60%
A : 0% (96%)b
B : 86%g
O
A : 98%
B : 92%
II-9
Solvent (2.0 mL)
Temp., 2 h
Br
Br
I-1
II-1
(1.0 mmol)
O
O
Entry
Solvent
CH3CN
t-BuOH
DMF
Temp. (°C)
Yield (%)
22 (70)a
36 (64)a
95
MeO
II-10
Ph
1
2
3
4
5
6
60
60
60
60
r.t.
r.t.
A : 71% (11%)c
B : 88%
A : 94%
B : 99%
II-11
II-12 A : 85%
B : >99%
O
O
O
O
DMSO
DMF
95
O
O
II-14
12 (81)a
25 (72)a
A : 45%d
B : 91%
A : 53%
B : 71%
A : 55%
B : 82%
II-15
II-13
DMSO
a Yield of recovered I-1.
S
O
O
O
N
II-17
A : 42%(41%)e
B : 67%
A : 82% f
B : 64%
Based on those results, various benzylic alcohols, such as
p-methylbenzyl alcohol I-2, p-chlorobenzyl alcohol I-3,
m-chlorobenzyl alcohol I-4, o-chlorobenzyl alcohol I-5,
p-nitrobenzyl alcohol I-6, p-(trifluoromethyl)benzyl
alcohol I-7, p-(methoxycarbonyl)benzyl alcohol I-8,
p-(methylthio)benzyl alcohol I-9, p-methoxybenzyl alcohol
II-18 A: 52%f
B: >99%
II-16
O
O
O
I-10,
p-(phenyl)benzyl
alcohol
I-11,
and
A : 65%, 71%g
B : >99%
A : 72%g
B : 90%
1-naphthalenemethanol I-12, were treated with iodic acid
(1.1 equiv.) in DMF at 60 °C for 2 h to give the
corresponding aromatic aldehydes II-2~II-12 in good
yields, as shown in Table 2 (Method A), although the
treatment of p-(methylthio)benzyl alcohol I-9 generated
p-(methanesulfinyl)benzaldehyde II-9’ in good yield.
Thus, iodic acid oxidizes a sulfenyl group to a sulfinyl
group. The same oxidation of p-(allyloxy)benzyl alcohol
I-13, p-(1,3-dioxolan-2-yl)benzyl alcohol I-14, and
cinnamyl alcohol I-15 with iodic acid gave the
corresponding aldehydes II-13~II-15 in moderate yields.
These results come from the partial oxidation of the
carbon-carbon double bond and the partial hydrolysis of
acetal by iodic acid under the present warming conditions.
The same oxidation of benzylic alcohols bearing
II-21
II-20
II-19 A : 32% f
B : 64%
O
O
O
(CH2)6CH3
Br
II-23
A : 71%, 76%g
B : >99%, 99%j
A : 83%g
B : 92%
II-22 A : 86%g
B : 99%
II-24
O
O
O
A: 68%g
B : 98%
II-25 A: 98%g
II-26 A: 99%g
II-27
B : 86%
B : 98%

ACCEPTED MANUSCRIPT
Tetrahedron
3
heteroaromatics, such as 2-thiophenemethanol I-16 and
product, yielda (%)
α-(cyclohexyl)benzyl alcohol I-29, α-(t-butyl)benzyl
alcohol
I-30,
α-mesityl-α-ethylmethanol
I-31,
α-mesityl-α-cyclohexylmethanol
I-32,
and
O
O
O
α-mesityl-α-t-butylmethanol I-33, which are sterically
hindered benzylic alcohols, in DMF at 60 °C for 2 h to
generate the corresponding aromatic ketones II-28~II-33 in
good yields, respectively. Thus, iodic acid is effective for
the oxidation of sterically hindered secondary benzylic
alcohols. However, the oxidation of aliphatic primary and
secondary alcohols, such as cyclohexanemethanol I-34,
1-adamantanemethanol I-35, cyclooctanol I-36, and
borneol I-37, with iodic acid in DMF at 60 °C for 2 h is not
effective, giving the corresponding aliphatic aldehydes
II-34 and II-35, and ketones II-36 and II-37 in 17%, 28%,
45%, and 60% yields, respectively. The low yields for
cyclohexanemethanol I-34 and cyclooctanol I-36 are due to
the partial α−iodination of the formed aldehyde and ketone
A : 62% f,g
B : 0%
II-28 A : 71%g
A : 95% f,g
II-30
II-29
B : 25%
71%k
O
B : 40%
89%k
31%k
O
O
A : 71%g
A : 78%g
B : 25%
29%k
A : 71%g
B : 14%
57%k
II-33
II-31
II-32
II-35
B : 63%
92%k
O
O
to α
aldehyde and α
ketone, and the
O
oxidative dehydrogenation to α,β-unsaturated aldehyde and
ketone, respectively. The oxidative dehydrogenation of
aliphatic ketones to α,β-unsaturated ketones with iodic acid
in DMSO at 50 °C is known.8a) Consequently, HIO3
oxidation (Method A) partly induces electrophilic
iodination of aromatic ring (i.e., II-10’ and II-16’), when
electron-rich benzylic alcohols, such as p-methoxybenzyl
alcohol (I-10) and 2-thiophenemethanol (I-16), were used.
Additionally, α-iodonation of the formed ketone, such as
cyclooctanone, partly occurs (i.e., II-36’). Those reasons
probably come from that co-product HIO2, formed in the
present oxidation of alcohols with HIO3, is not stable at
warming conditions and disproportionates to HOI and HIO3,
and HOI works as iodination species of electron-rich
aromatic ring of alcohols or α-iodonation of aldehyde and
ketone.
A : 28%g
B : 76%
76%k
A : 17%
B : 23%
41%k
II-34
II-37
II-36
A : 45%(42%)h
B : 86%g
96%k
O
A : 60%g
B : 99%
99%k
b Yield of II-9'. c Yield of II-10'.
a Isolated yield.
d Reaction was carried out for 1 h. e Yield of II-16'.
f Reaction was carried out for 8 h.
g HIO3 (2.0 equiv.) was added.
h Yield of II-36'.
i Reaction was carried out in CH2Cl2 instead of DMF for 7 h.
jReaction was carried out in CH2Cl2 instead of DMF for 22 h.
k AZADO (5 mol%) was used instead of TEMPO.
I
O
O
I
S
I
O
Me
O
S
MeO
O
II-36'
II-9'
II-10'
II-16'
The TEMPO-catalyzed oxidation of alcohols with DIB,5)
and the related AZADO-catalyzed oxidation of alcohols
with DIB6) have become very popular because the reaction
can be carried out without any practical problems,
including bad smell, explosion, toxicity, and high cost of
3-pyridinemethanol I-17, with iodic acid provided the
corresponding aromatic aldehydes II in good yields,
although the former compound gave a mixture of
2-thiophenecarboxaldehyde
II-16
(42%)
and
5-iodo-2-thiophenecarboxaldehyde II-16’ (41%). On the
other hand, the oxidation of 2,4,6-trimethylbenzyl alcohol
I-18 and 2,4,6-triisopropylbenzyl alcohol I-19 with iodic
acid in DMF at 60 °C gave the corresponding aromatic
aldehydes II-18 and II-19 in moderate yields, respectively.
The oxidation of secondary benzylic alcohols, such as
reagents.
Thus, the present iodic acid (1.1 equiv.)
oxidation of alcohols was carried out in the presence of
TEMPO (5 mol%) in DMF at room temperature for 2 h.
Various primary benzylic alcohols, such as p-bromobenzyl
alcohol I-1, p-methylbenzyl alcohol I-2, p-chlorobenzyl
alcohol I-3, m-chlorobenzyl alcohol I-4, o-chlorobenzyl
1-phenylethanol
I-20,
1-phenyl-1-propanol
I-21,
alcohol
p-(trifluoromethyl)benzyl
p-(methoxycarbonyl)benzyl
I-5,
p-nitrobenzyl
alcohol
alcohol
alcohol
I-6,
I-7,
I-8,
1-phenyl-1-octanol I-22, 1-(4’-bromophenyl)ethanol I-23,
1-(4’-methylphenyl)ethanol I-24, diphenylmethanol I-25,
phenyl-p-tolylmethanol I-26, and 1,2-diphenylethanol I-27,
with iodic acid (2.0 equiv.) in DMF at 60 °C for 2 h gave
the corresponding aromatic ketones II-20~II-27 in good
yields, respectively. The yield of aromatic ketones with
2.0 equivalents of iodic acid was better than that with 1.1
equivalent of iodic acid for the oxidation of secondary
benzylic alcohols, as shown in the oxidation of
1-phenylethanol I-20 and 1-(4’-bromophenyl)ethanol I-23.
Moreover, iodic acid (2.0 equiv.) was used for the
p-(methylthio)benzyl alcohol I-9, p-methoxybenzyl alcohol
I-10, p-phenylbenzyl alcohol I-11, 1-naphthalenemethanol
I-12,
p-(allyloxy)benzyl
alcohol
I-13,
and
p-(1,3-dioxolan-2-yl)benzyl alcohol I-14, were smoothly
oxidized at room temperature to give the corresponding
aromatic aldehydes II-1~II-14 in good yields, respectively,
as shown in Table 2 (Method B). Here, the carbon-carbon
double bond was not oxidized and the sulfenyl group was
not oxidized to the sulfinyl group as well. In the
TEMPO-catalyzed oxidation of alcohols with iodic acid in
oxidation
of
α-(isopropyl)benzyl
alcohol
I-28,

ACCEPTED MANUSCRIPT
4
Tetrahedron
DMF at room temperature, the solution gradually became
homogeneous as the reaction proceeded. The same
TEMPO-catalyzed oxidation of cinnamyl alcohol I-15 also
proceeded smoothly to provide trans-cinnamaldehyde II-15
yield of ketones II-30 and II-33 was low. Therefore,
AZADO-catalyzed oxidation with iodic acid can be used
for oxidation of sterically hindered benzylic alcohols in
DMF at room temperature. AZADO-catalyzed oxidation
of aliphatic primary and secondary alcohols with DIB was
also effective. Thus, Thus, AZADO (5 mol%)-catalyzed
oxidation of 1-adamantanemethanol I-35, cyclooctanol I-36,
and borneol I-37 with DIB (1.1 equiv.) in DMF at room
temperature for 2 h was carried out to give the
corresponding aldehyde II-35, and ketones II-36 and II-37
in good yields, respectively, although the yield of aldehyde
II-34 was low.
in good yield.
2-thiophenemethanol I-16, 3-pyridinemethanol I-17,
2,4,6-trimethylbenzyl alcohol I-18, and
2,4,6-triisopropylbenzyl alcohol I-19, with iodic acid also
provided the corresponding aromatic aldehydes
The TEMPO-catalyzed oxidation of
II-16~II-19 in good yields, respectively. In addition, the
same TEMPO-catalyzed oxidation of various secondary
benzylic alcohols, such as 1-phenylethanol I-20,
1-phenyl-1-propanol I-21, 1-phenyl-1-octanol I-22,
1-(4’-bromophenyl)ethanol
I-23,
1-(4’-methylphenyl)ethanol I-24, diphenylmethanol I-25,
phenyl-p-tolylmethanol I-26, and 1,2-diphenylethanol I-27,
with iodic acid in DMF at room temperature for 2 h gave
the corresponding aromatic ketones II-20~II-27 in good
As gram-scale experiments, treatment of p-bromobenzyl
alcohol I-1 (10 mmol) with iodic acid (1.1 equiv.) in DMF
at 60 °C for 2 h (Method A) and treatment of
p-bromobenzyl alcohol I-1 (10 mmol) with iodic acid (1.1
equiv.) in the presence of TEMPO (5 mol%) in DMF at
yields,
respectively.
In
contrast,
the
same
TEMPO-catalyzed oxidation of α-(isopropyl)benzyl
alcohol I-28, α-(cyclohexyl)benzyl alcohol I-29,
α-(t-butyl)benzyl alcohol I-30, α-mesityl-α-ethylmethanol
room temperature for
2
h
(Method B) gave
(Method A)
I-31,
α-mesityl-α-cyclohexylmethanol
I-32,
and
HIO3 (2.0 equiv.)
OH
OH
α-mesityl-α-t-butylmethanol I-33 with iodic acid in DMF
at room temperature gave the corresponding aromatic
ketones II-28~II-33 in low to moderate yields, respectively.
Thus, the TEMPO-catalyzed oxidation with iodic acid in
DMF is effective for primary and secondary benzylic
alcohols. However, it is not effective for the oxidation of
sterically hindered alcohols. This is because the reactive
1)
O
HO
HO
DMF, 60 °C, 2 h
II-38
84%
I-38
(Method B)
HIO3 (2.0 equiv.)
TEMPO (5 mol%)
OH
O
2)
O
DMF, MS, r.t., 4 h
I-38
II-38' 72%
species
for
the
oxidation
of alcohols
with
Scheme 1. Oxidation of I-38 with Method A and Method B
TEMPO-catalyzed iodic acid is oxoammonium derived
from the oxidation of TEMPO by iodic acid. Generally,
the TEMPO-catalyzed oxidation of alcohols with DIB is
conducted in dichloromethane as a solvent. However,
DMF is better solvent than dichloromethane in the present
TEMPO-catalyzed oxidation of alcohols with iodic acid,
because the reaction proceeds smoothly at room
temperature (for 2 h) due to the moderate solubility of iodic
acid in DMF as compared with dichloromethane, as shown
in Table 2, i.e. the oxidation of p-bromobenzyl alcohol I-1
(for 7 h) and 1-(4’-bromophenyl)ethanol I-23 (for 22 h).
The utility of the TEMPO-catalyzed oxidation of aliphatic
primary and secondary alcohols with DIB is dependent on
HIO3 Oxidation (Method A)
R
R
C
O
O
O
R
H
HO
I
CH OH
O
I
OH
R
OH
R
C
O
-HIO2
-H2O
R
HIO3 - TEMPO Oxidation (Method B)
the
1-adamantanemethanol I-35, cyclooctanol I-36, and
borneol I-37 effectively proceeded to give
1-adamantanecarboxaldehyde II-35, cyclooctanone II-36,
and camphor II-37 in 76%, 86%, and 99% yields,
substrates.
Thus,
the
oxidation
of
O•
N
TEMPO
R
HIO3
O
H
R
respectively.
cyclohexanemethanol
However, the same oxidation of
C
I-34 gave
O
O
R
cyclohexanecarboxaldehyde II-34 in only 23% yield.
AZADO-catalyzed oxidation of benzylic alcohols with DIB
is more effective than that with TEMPO-catalyzed
oxidation of benzylic alcohols with DIB, especially for
sterically hindered alcohols.6) Thus, AZADO (5
mol%)-catalyzed oxidation of sterically hindered alcohols
I-28~I-33 with DIB (1.1 equiv.) in DMF at room
temperature for 2 h was carried out to give the
corresponding ketones II-28, II-29, II-31, and II-32 in
71%, 89%, 92%, and 57% yields, respectively, although the
N
N
CH OH
R
HIO3
OH
N
R
C
O
R
Scheme 2. Plausible Reaction Mechanism

ACCEPTED MANUSCRIPT
Tetrahedron
5
p-bromobenzaldehyde II-1 in 94% and 84% yields,
respectively. Finally, as a demonstration of Method A
and Method B, 3-(4’-hydroxymethyl)phenyl-1-propanol
I-38 was treated with Method A and Method B to give
4.2.2 Typical Experimental Procedure with HIO3 in the
Presence of TEMPO (Method B): To a solution of
1-(p-bromophenyl)ethanol I-23 (201 mg, 1.0 mmol) in
DMF (2.0 mL) was added HIO3 (194 mg, 1.1 mmol) and
TEMPO (7.8 mg, 0.05 mmol). The mixture was stirred
for 2 h at room temperature under an Ar atmosphere.
After the reaction, the reaction mixture was poured into aq.
Na2S2O3, and extracted with a mixture of Et2O : hexane =
1:1 (3×10 mL). Then, the organic layer was poured into
sat. NaCl (10 mL) and extracted with Et2O (10 mL). The
3-(4’-formylphenyl)-1-propanol
II-38
and
3-(4’-formylphenyl)propanal II-38’ in 84% and 72% yields,
respectively, as shown in eqs. 1 and 2 (Scheme 1).
The plausible reaction mechanisms for Method A and
Method B are shown in Scheme 2. The reactive species
for the oxidation of alcohols in Method A is iodic acid, and
that in Method B is oxoammonium species. Therefore,
Method B is not effective for the oxidation of sterically
hindered secondary benzylic alcohols.
organic layer was dried over Na2SO4.
After being
filtration and removal of the solvent under reduced pressure,
the residue was purified by flash short column
chromatography on silica gel (EtOAc–hexane, 1:4) to give
p-bromoacetophenone II-23 in 99% yield.
3. Conclusion
4.3.1 4-Bromobenzaldehyde (II-1)
:
Mp: 59 °C
(commercially available, Mp: 57~61 °C). IR (neat): 2857,
A variety of primary and secondary benzylic alcohols could
be smoothly oxidized to aromatic aldehydes and aromatic
ketones in good yields by treatment with iodic acid in DMF
at 60 °C (Method A) or by treatment with iodic acid in the
presence of TEMPO in DMF at room temperature (Method
B). Overall, method A is effective for the oxidation of
sterically hindered benzylic alcohols, and iodic acid can be
used for the TEMPO-catalyzed or AZADO-catalyzed
oxidation of alcohols (Method B), instead of DIB. The
two methods A and B, which employ inexpensive,
non-explosive, and odorless iodic acid, would be useful for
the formation of aromatic aldehydes and aromatic ketones
from primary and secondary benzylic alcohols under mild
and transition-metal-free conditions.
1
1686 cm-1. H NMR (400 MHz, CDCl3): δ =7.65~7.78 (m,
4 H), 9.98 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ =
129.78, 130.97, 132.43, 135.05, 191.06.
4.3.2 4-Methylbenzaldehyde (II-2) : Oil (commercially
1
available, Oil). IR (neat): 2823, 2733, 1686 cm-1. H NMR
(400 MHz, CDCl3): δ = 7.33 (d, J = 7.8 Hz, 2 H), 7.77 (d, J
= 7.8 Hz, 2 H), 9.96 (s, 1 H). 13C NMR (100 MHz, CDCl3):
δ = 21.81, 129.64, 129.79, 134.12, 145.49, 191.95.
4.3.3 4-Chlorobenzaldehyde (II-3) : Mp: 47~49 °C
(commercially available, Mp: 47~50 °C). IR (neat): 2858,
1
1691 cm-1. H NMR (400 MHz, CDCl3): δ = 7.52 (d, J =
8.4 Hz, 2 H), 7.83 (d, J = 8.4 Hz, 2 H), 9.99 (s, 1 H). 13C
NMR (100 MHz, CDCl3): δ = 129.41, 130.87, 134.64,
140.90, 190.85.
4. Experimental
4.3.4 3-Chlorobenzaldehyde (II-4) : Oil (commercially
available, Oil). IR (neat): 2823, 2728, 1697 cm-1. H NMR
4.1 General: Melting points were determined with a
Yamato MP-21 melting point apparatus. IR spectra were
measured with a JASCO FT/IR-4100 spectrophotometer.
1H and 13C NMR spectra were obtained with JEOL
JNM-ECS400 and JEOL JNM-ECA500 spectrometers.
Chemical shifts (δ) are expressed in ppm downfield from
TMS. Mass spectra were recorded on JMS T100GCV and
Thermo LTQ Orbitrap XL spectrometers. Merck silica gel
60F254 was used for TLC, and column chromatography for
the purification of products was carried out with silica gel
60 from Kanto Kagaku Co.
Most aromatic aldehydes and ketones are commercially
available and were identified with the authentic samples.
4.2.1 Typical Experimental Procedure with HIO3
(Method A): To a solution of p-bromobenzyl alcohol I-1
(187 mg, 1.0 mmol) in DMF (2.0 mL) was added HIO3
(194 mg, 1.1 mmol). The mixture was stirred at 60 °C for
2 h under an Ar atmosphere. After the reaction, the
reaction mixture was poured into aq. Na2S2O3, and
extracted with a mixture of Et2O : hexane = 1:1 (3×10 mL).
The organic layer was dried over Na2SO4. After being
filtration and removal of the solvent under reduced pressure,
the residue was purified by flash short column
chromatography on silica gel (EtOAc–hexane, 1:4) to give
p-bromobenzaldehyde II-1 in 95% yield.
1
(400 MHz, CDCl3): δ = 7.49 (t , J = 7.9 Hz, 1 H), 7.61 (ddd,
J = 7.9, 2.0, 1.3 Hz, 1 H), 7.77 (dt, J = 7.9 , 1.3 Hz, 1 H),
7.86 (t, J = 2.0 Hz, 1 H), 9.98 (s, 1 H). 13C NMR (100
MHz, CDCl3): δ = 127.94, 129.26, 130.34, 134.36, 135.41,
137.76, 190.81.
4.3.5 2-Chlorobenzaldehyde (II-5): Oil (commercially
1
available, Oil). IR (neat): 2852, 1695 cm-1. H NMR (400
MHz, CDCl3): δ = 7.40 (t, J = 7.9 Hz, 1 H), 7.46 (d, J = 7.9
Hz, 1 H), 7.54 (td, J = 7.9, 1.8 Hz 1 H), 7.93 (dd, J = 7.7,
1.8 Hz, 1 H), 10.49 (s, 1 H). 13C NMR (100 MHz, CDCl3):
δ = 127.24, 129.33, 130.57, 132.41, 135.10, 137.91,
189.78.
4.3.6 4-Nitrobenzaldehyde (II-6): Mp: 104 °C
(commercially available, Mp: 102~107 °C). IR (neat): 2850,
1
1702, 1539, 1342 cm-1. H NMR (400 MHz, CDCl3): δ =
8.11 (d, J = 8.8 Hz, 2 H), 8.42 (d, J = 8.8 Hz, 2 H), 10.19
(s,1 H). 13C NMR (100 MHz, CDCl3): δ = 124.22, 130.43,
139.96, 151.00, 190.31.
4.3.7 4-(Trifluoromethyl)benzaldehyde (II-7)
: Oil
(commercially available, Oil). IR (neat): 2836, 1708 cm-1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.1 Hz, 2 H),
8.02 (d, J = 8.1 Hz, 2 H), 10.11 (s, 1 H). 13C NMR (100
MHz, CDCl3): δ = 123.40 (q, JC-F = 273.4 Hz), 126.06 (q,
JC-F = 3.8 Hz), 129.88, 135.53 (q, JC-F = 32.0 Hz), 138.60,
191.08

ACCEPTED MANUSCRIPT
6
Tetrahedron
4.3.8 Methyl 4-formylbenzoate (II-8) : Mp: 61~63 °C
(100 MHz, CDCl3): δ = 128.44, 128.50, 129.04, 131.23,
(commercially available, Mp: 58~63 °C). IR (neat): 2961,
133.92, 152.77, 193.69.
1
1721, 1682 cm-1. H NMR (400 MHz, CDCl3): δ = 3.97 (s,
4.3.17
Thiophene-2-carbaldehyde
(II-16):
Oil
3 H), 7.96 (d, J = 8.3 Hz, 2 H), 8.20 (d, J = 8.3 Hz, 2 H),
10.11 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ = 52.55,
129.48, 130.13, 135.02, 139.07, 166.00, 191.61.
(commercially available, Oil). IR (neat): 2820, 2789, 1655
1
cm-1. H NMR (400 MHz, CDCl3): δ = 7.23 (dd, J = 4.8,
3.9 Hz, 1 H), 7.76~7.81 (m, 2 H), 9.95 (s, 1 H). 13C NMR
(100 MHz, CDCl3): δ = 128.27, 135.10, 136.31, 143.97,
182.98.
4.3.9
4-(Methylthio)benzaldehyde
(II-9)
:
Oil
(commercially available, Oil). IR (neat): 2829, 2736, 1692
1
cm-1. H NMR (400 MHz, CDCl3): δ = 2.52 (s, 3 H), 7.31
4.3.18 Nicotinaldehyde (II-17): Oil (commercially
1
(d, J = 8.4 Hz, 2 H), 7.76 (d, J = 8.4 Hz, 2 H), 9.91 (s, 1 H).
13C NMR (100 MHz, CDCl3): δ = 14.48, 124.96, 129.81,
132.72, 147.76, 191.09.
4.3.10 4-(Methanesulfinyl)benzaldehyde (II-9’) : Mp:
81~82 °C. IR (neat): 2847, 1695, 1040 cm-1. 1H NMR (400
MHz, CDCl3): δ = 2.79 (s, 3 H), 7.83 (d, J = 8.3 Hz, 2 H),
8.06 (d, J = 8.0 Hz, 2 H), 10.10 (s, 1 H). 13C NMR (100
MHz, CDCl3): δ = 43.75, 124.12, 130.37, 138.07, 152.41,
191.10. HRMS (ESI) [M + H]+ Calcd for C8H9O2S =
169.0318, Found = 169.0314.
available, Oil). IR (neat): 2839, 2742, 1698 cm-1. H NMR
(400 MHz, CDCl3): δ = 7.51 (dd, J = 7.8, 4.9 Hz, 1 H),
8.20 (dt, J = 7.8, 1.8 Hz, 1 H), 8.86 (dd, J = 4.9, 1.8 Hz, 1
H), 9.10 (d, J = 1.8 Hz, 1 H), 10.14 (s, 1 H). 13C NMR (100
MHz, CDCl3): δ = 124.04, 131.35, 135.76, 152.02, 154.68,
190.71.
4.3.19
2,4,6-Trimethylbenzaldehyde
(II-18):
Oil
(commercially available, Oil). IR (neat): 2765, 1682 cm-1.
1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 3 H), 2.58 (s, 6
H), 6.89 (s, 2 H), 10.56 (s, 1 H). 13C NMR (100 MHz,
CDCl3): δ = 20.46, 21.42, 129.89, 130.47, 141.43, 143.78,
192.92.
4.3.11
4-Methoxybenzaldehyde
(II-10)
:
Oil
(commercially available, Oil). IR (neat): 2840, 2738, 1680
1
cm-1. H NMR (400 MHz, CDCl3): δ = 3.89 (s, 3 H), 7.01
4.3.20 2,4,6-Triisopropylbenzaldehyde (II-19): Oil. IR
1
(d, J = 8.7 Hz, 2 H), 7.84 (d, J = 8.7 Hz, 2 H), 9.89 (s, 1 H).
13C NMR (100 MHz, CDCl3): δ = 55.54, 114.26, 129.89,
131.94, 164.56, 190.80.
(neat): 2868, 1687 cm-1. H NMR (400 MHz, CDCl3): δ =
1.25~1.30 (m, 18 H), 2.92 (sept, J = 7.0 Hz, 1 H), 3.60
(sept, J = 6.8 Hz, 2 H), 7.11 (s, 2 H), 10.66 (s, 1 H). 13C
NMR (100 MHz, CDCl3): δ = 23.71, 24.17, 28.73, 34.67,
121.56, 130.18, 150.41, 153.57, 195.00. HRMS (APCI) [M
+ H]+ Calcd for C16H25O = 233.1900, Found = 233.1897.
HRMS (APCI) [M + H]+ Calcd for C16H25O = 233.1900,
Found = 233.1897.
4.3.21 Acetophenone (II-20): Oil (commercially available,
Oil). IR (neat): 1681 cm-1. 1H NMR (400 MHz, CDCl3): δ =
2.61 (s, 3 H), 7.46 (t, J = 7.3 Hz, 2 H), 7.57 (t, J = 7.3 Hz, 1
H), 7.96 (d, J = 7.3 Hz, 2 H). 13C NMR (100 MHz, CDCl3):
δ = 26.56, 128.25, 128.50, 133.05, 137.03, 198.13.
4.3.12 4-Phenylbenzaldehyde (II-11) : Mp: 44~45 °C
(commercially available, Mp: 57~60 °C). IR (neat): 2845,
2728, 1698 cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.41 (tt,
J = 7.2, 1.4 Hz, 1 H), 7.47 (tt, J = 7.6, 1.6 Hz, 2 H), 7.63 (dt,
J = 7.0, 1.5 Hz, 2 H), 7.74 (dt, J = 8.1, 1.6 Hz, 2 H), 7.94
(dt, J = 8.5, 1.8 Hz, 2 H), 10.04 (s, 1 H). 13C NMR (100
MHz, CDCl3): δ = 127.30, 127.62, 128.43, 128.96, 130.22,
135.10, 139.62, 147.12, 191.90.
4.3.13 1-Naphthaldehyde (II-12): Oil (commercially
1
available, Oil). IR (neat): 2725, 1683 cm-1. H NMR (400
MHz, CDCl3): δ = 7.55~7.64 (m, 2H), 7.68 (t, J = 7.3 Hz, 1
H), 7.90 (d, J = 8.2 Hz, 1 H), 7.96 (d, J = 7.0 Hz, 1 H), 8.07
(d, J = 8.2 Hz, 1 H), 9.25 (d, J = 8.6 Hz, 1 H), 10.38 (s, 1
H). 13C NMR (100 MHz, CDCl3): δ = 124.82 (2C), 126.90,
128.42, 129.01, 130.46, 131.32, 133.65, 135.24, 136.65,
193.51.
4.3.22 Propiophenone (II-21): Oil (commercially
1
available, Oil). IR (neat): 1684 cm-1. H NMR (400 MHz,
CDCl3): δ = 1.23 (t, J = 7.3 Hz, 3 H), 3.02 (q, J = 7.3 Hz, 2
H), 7.46 (t, J = 7.5 Hz, 2 H), 7.56 (t, J = 7.5 Hz, 1 H), 7.97
(d, J = 7.5 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 8.19,
31.73, 127.92, 128.50, 132.83, 136.85, 200.82.
4.3.14 4-(Allyloxy)benzaldehyde (II-13)9a : Oil. IR (neat):
4.3.23 Octanophenone (II-22): Oil (commercially
1
1
2829, 2738, 1686 cm-1. H NMR (400 MHz, CDCl3): δ =
available, Oil). IR (neat): 1685 cm-1. H NMR (400 MHz,
4.63 (dt, J = 5.2, 1.6 Hz, 2 H), 5.34 (dq, J = 10.7, 1.4 Hz, 1
H), 5.44 (dq, J = 17.2, 1.4 Hz, 1 H), 6.00~6.12 (m, 1 H),
7.02 (d, J = 8.7 Hz, 2 H), 7.84 (d, J = 8.7 Hz, 2 H), 9.89 (s,
1 H). 13C NMR (100 MHz, CDCl3): δ = 68.89, 114.89,
118.25, 129.89, 131.86, 132.15, 163.47, 190.70.
CDCl3): δ = 0.88 (t, J = 7.0 Hz, 3 H), 1.23~1.42 (m, 8 H),
1.74 (quint, J = 7.4 Hz, 2 H), 2.96 (t, J = 7.4 Hz, 2 H), 7.46
(t, J = 7.2 Hz, 2 H), 7.55 (t, J = 7.2 Hz, 1 H), 7.96 (d, J =
7.2 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 14.06,
22.60, 24.34, 29.12, 29.30, 31.69, 38.60, 128.02, 128.50,
132.82, 137.04, 200.61.
4.3.15 4-(1’,3’-Dioxolan-2’-yl)benzaldehyde (II-14)9b
:
1
Oil. IR (neat): 2887, 1698 cm-1. H NMR (400 MHz,
CDCl3): δ = 4.03~4.16 (m, 4H), 5.88 (s, 1 H), 7.65 (d, J =
7.9 Hz, 2 H), 7.90 (d, J = 7.9 Hz, 2 H), 10.03 (s, 1 H). 13C
NMR (100 MHz, CDCl3): δ = 65.38, 102.77, 127.04,
129.75, 136.83, 144.33, 191.94.
4.3.24 4-Bromoacetophenone (II-23): Mp: 50~52 °C
(commercially available, Mp: 50~54 °C). IR (neat): 1670
1
cm-1. H NMR (400 MHz, CDCl3): δ = 2.59 (s, 3 H), 7.61
(d, J = 8.6 Hz, 2 H), 7.82 (d, J = 8.6 Hz, 2 H). 13C NMR
(100 MHz, CDCl3): δ = 26.55, 128.30, 129.83, 131.88,
135.78, 197.04.
4.3.16 Cinnamaldehyde (II-15) : Oil (commercially
1
available, Oil). IR (neat): 2813, 2742, 1669 cm-1. H NMR
4.3.25 4-Methylacetophenone (II-24): Oil (commercially
1
(400 MHz, CDCl3): δ = 6.72 (dd, J = 15.9, 7.7 Hz, 1 H),
available, Oil). IR (neat): 1677 cm-1. H NMR (400 MHz,
7.41~7.59 (m 6 H), 9.71 (d, J = 7.7 Hz, 1 H). 13C NMR
CDCl3): δ = 2.42 (s, 3 H), 2.58 (s, 3 H), 7.26 (d, J = 8.1 Hz,

ACCEPTED MANUSCRIPT
Tetrahedron
7
2 H), 7.86 (d, J = 8.1 Hz, 2 H). 13C NMR (100 MHz,
CDCl3): δ = 21.56, 26.46, 128.35, 129.15, 134.60, 143.79,
197.80.
4.3.34 t-Butyl mesityl ketone (II-33): Oil. IR (neat): 1686
1
cm-1. H NMR (400 MHz, CDCl3): δ = 1.23 (s, 9 H), 2.17
(s, 6 H), 2.27 (s, 3 H), 6.82 (s, 2 H). 13C NMR (100 MHz,
CDCl3): δ = 20.28 (2C), 20.92, 28.05 (3C), 44.75, 128.35,
132.02, 137.32, 139.61, 219.78. HRMS (ESI) [M + H]+
Calcd for C14H21O = 205.1587, Found = 205.1584.
4.3.26 Benzophenone (II-25): Oil (commercially available,
Oil). IR (neat): 1655 cm-1. 1H NMR (400 MHz, CDCl3): δ =
7.49 (t, J = 7.2 Hz, 4 H), 7.59 (t, J = 7.2 Hz, 2 H), 7.81 (d, J
= 7.2 Hz, 4 H). 13C NMR (100 MHz, CDCl3): δ = 128.25
(2C), 130.04 (2C), 132.39 (2C), 137.55 (2C), 196.75.
4.3.27 4-Methylbenzophenone (II-26): Mp: 55~56 °C
(commercially available, Mp: 54~58 °C). IR (neat): 1651
4.3.35 1-Adamantanecarboxaldehyde (II-35)9c : Mp:
1
139 °C. IR (neat): 2849, 1720 cm-1. H NMR (400 MHz,
CDCl3): δ = 1.65~1.83 (m, 12 H), 2.08 (brs, 3H), 9.32 (s, 1
H). 13C NMR (100 MHz, CDCl3): δ = 27.26, 35.75, 36.47,
44.74, 205.88.
1
cm-1. H NMR (400 MHz, CDCl3): δ = 2.44 (s, 3 H), 7.28
(d, J = 7.9 Hz, 2 H), 7.47 (t, J = 7.9 Hz, 2 H), 7.58 (t, J =
7.4 Hz, 1 H), 7.73 (d, J = 8.3 Hz, 2 H), 7.78 (d, J = 7.0 Hz,
2 H). 13C NMR (100 MHz, CDCl3): δ = 21.61, 128.16,
128.93, 129.87, 130.26, 132.12, 134.81, 137.88, 143.19,
196.46.
4.3.36 Cyclooctanone (II-36) : Mp: 37 °C (commercially
1
available, Mp: 37~45 °C). IR (neat): 1696 cm-1. H NMR
(400 MHz, CDCl3): δ = 1.34~1.42 (m, 2 H), 1.51~1.59 (m,
4 H), 1.84~1.92 (m, 4 H), 2.38~2.44 (m, 4 H). 13C NMR
(100 MHz, CDCl3): δ = 24.46, 25.42 (2C), 26.92 (2C),
41.69 (2C), 218.05.
4.3.37 Camphor (II-37): Mp: 172~174 °C (commercially
available, Mp: 172=180 °C). IR (neat): 1739 cm-1. 1H NMR
(400 MHz, CDCl3): δ = 0.84 (s, 3 H), 0.92 (s, 3 H), 0.96 (s,
3 H), 1.30~1.45 (m, 2 H), 1.68 (td, J = 13.2, 3.8 Hz, 1 H),
1.85 (d, J = 18.3 Hz, 1 H), 1.90~2.00 (m, 1 H), 2.09 (t, J =
4.7 Hz, 1 H), 2.36 (td, J = 18.3, 3.8 Hz, 1 H). 13C NMR
(100 MHz, CDCl3): δ = 9.19, 19.09, 19.72, 26.98, 29.85,
42.97, 43.24, 46.74, 57.65, 219.72.
4.3.28 Benzyl phenyl ketone (II-27): Mp: 56 °C
(commercially available, Mp: 55~59 °C). IR (neat): 1682
1
cm-1. H NMR (400 MHz, CDCl3): δ = 4.29 (s, 2 H),
7.22~7.36 (m, 5 H), 7.46 (t, J = 7.4 Hz, 2 H), 7.56 (t, J =
7.4 Hz, 1 H), 8.02 (d, J = 7.4 Hz, 2 H). 13C NMR (100
MHz, CDCl3): δ = 45.45, 126.84, 128.56, 128.60, 128.63,
129.43, 133.13, 134.48, 136.52, 197.58.
4.3.29 Isobutyrophenone (II-28) : Oil (commercially
1
available, Oil). IR (neat): 1681 cm-1. H NMR (400 MHz,
CDCl3): δ = 1.22 (d, J = 6.7 Hz, 6 H), 3.57 (sept, J = 6.7 Hz,
1 H), 7.47 (t, J = 7.4 Hz, 2 H), 7.56 (t, J = 7.4 Hz, 1 H),
7.96 (d, J = 7.4 Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ =
19.13 (2C), 35.32, 128.28, 128.57, 132.76, 136.17, 204.49.
4.3.30 Cyclohexyl phenyl ketone (II-29): Oil. IR (neat):
1679 cm-1. 1H NMR (400 MHz, CDCl3): δ = 1.21~ 1.95 (m,
10 H), 3.27 (tt, J = 11.3, 3.2 Hz, 1 H), 7.46 (t, J = 7.2 Hz, 2
4.3.38 3-(4’-Formylphenyl)-1-propanol (II-38): Oil. IR
(neat): 3434, 2866, 1693 cm-1. 1H NMR (400 MHz,
CDCl3): δ = 1.88~1.97 (m, 2 H), 2.81 (t, J = 7.5 Hz, 2 H),
3.69 (t, J = 6.3 Hz, 2 H), 7.37 (d, J = 7.9 Hz, 2 H), 7.81 (d,
J = 7.9 Hz, 2 H), 9.97 (s, 1 H). 13C NMR (100 MHz,
CDCl3): δ = 32.27, 33.70, 61.88, 129.10, 129.98, 134.50,
149.40, 192.02. HRMS (ESI) [M + H]+ Calcd for C10H13O2
= 165.0910, Found = 165.0909.
H), 7.55 (t, J = 7.2 Hz, 1 H), 7.95 (d, J = 7.2 Hz, 2 H). 13
C
NMR (100 MHz, CDCl3): δ = 25.83 (2C), 25.94, 29.40
(2C), 45.60, 128.23, 128.55, 132.69, 136.31, 203.87.
HRMS (ESI) [M + H]+ Calcd for C13H17O = 189.1274 ,
Found = 189.1270.
4.3.31 t-Butyl phenyl ketone (II-30) : Oil. IR (neat): 1672
cm-1. 1H NMR (400 MHz, CDCl3): δ = 1.35 (s, 9 H), 7.40 (t,
J = 7.4 Hz, 2 H), 7.46 (t, J = 7.4 Hz, 1 H), 7.69 (d, J = 7.4
Hz, 2 H). 13C NMR (100 MHz, CDCl3): δ = 27.99 (3C),
44.18, 127.80, 128.03, 130.78, 138.57, 209.30. HRMS
(ESI) [M + H]+ Calcd for C11H15O = 163.1117, Found =
163.1115.
4.3.39 3-(4’-Formylphenyl)propanal (II-38’): Oil. IR
(neat): 2735, 1712, 1694 cm-1. 1H NMR (400 MHz,
CDCl3): δ = 2.85 (t, J = 7.4 Hz, 2 H), 3.05 (t, J = 7.4 Hz, 2
H), 7.37 (d, J = 8.2 Hz, 2 H), 7.82 (d, J = 8.2 Hz, 2 H), 9.84
(s, 1 H), 9.98 (s, 1 H). 13C NMR (100 MHz, CDCl3): δ =
28.13, 44.67, 129.04, 130.11, 134.82, 147.73, 191.88,
200.59. HRMS (ESI) [M + H]+ Calcd for C10H11O2 =
163.0754, Found = 163.0753.
Supporting Information (see footnote on the first page of
1
this article): … Copies of H NMR and 13C NMR spectra
4.3.32 Ethyl mesityl ketone (II-31): Oil. IR (neat): 1697
for all aromatic aldehydes and ketones.
1
cm-1. H NMR (400 MHz, CDCl3): δ = 1.19 (t, J = 7.3 Hz,
3 H), 2.18 (s, 6 H), 2.27 (s, 3 H), 2.70 (q, J = 7.3 Hz, 2 H),
6.83 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 7.62, 19.03
(2C), 20.99, 37.92, 128.36, 132.38, 138.13, 139.82, 211.55.
HRMS (ESI) [M + H]+ Calcd for C12H17O = 177.1274,
Found = 177.1272.
4.3.33 Cyclohexyl mesityl ketone (II-32): Oil. IR (neat):
1689 cm-1. 1H NMR (400 MHz, CDCl3): δ = 1.18~1.97 (m,
10 H), 2.19 (s, 6 H), 2.27 (s, 3 H), 2.68 (tt, J = 11.7, 3.4 Hz,
1 H), 6.83 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 19.62
(2C), 20.99, 25.84 (3C), 28.16 (2C), 52.22, 128.51, 133.23,
138.19, 139.11, 213.66. HRMS (APCI) [M + H]+ Calcd for
C16H23O = 231.1743, Found = 231.1742.
Acknowledgement
Financial support in the form of a Grant-in–Aid for
Scientific Research (No. 15K05418) from the Ministry of
Education, Culture, Sports, Science, and Technology in
Japan is acknowledged.
References
(1) (a) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995,
34, 259. (b) Sheldon, R. A. Chem. Ind. 1997, 12. (c)

ACCEPTED MANUSCRIPT
8
Tetrahedron
Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew.
(6) Shibuya, M.; Tomizawa, M.; Suzuki, I.; Iwabuchi, Y.
Chem. Int. Ed. 2001, 40, 2004. Recent reports: d)
NaBr-H2O2 at 60°C Komagawa, H.; Maejima, Y.;
Nagano, T. Synlett 2016, 27, 789. e) FeCl3,
TEMPO,O2-toluene reflux Zhang, G.; Li, S.; Lei, J.;
Zhang, G.; Xie, X.; Ding, C.; Liu, R. Synlett 2016, 27,
956.
J. Am. Chem. Soc. 2006, 128, 8412.
(7) (a) Anelli, P. L.; Biffi, C.; Montanari, F.; Quici, S. J.
Org. Chem. 1987, 52, 2559. (b) Siedlecka, R.;
Skarzewski, J.; Miochowski, J. Tetrahedron Lett.
1990, 31, 2177. (c) Leanna, M. R.; Sowin, T. J.;
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