Oxidation of alcohols to aldehydes or ketones with 1-acetoxy-1,2- benziodoxole-3(1H)-one derivatives

Article abstract of DOI:10.1002/ejoc.201301466

Various benzylic and aliphatic alcohols were smoothly oxidized to the corresponding aromatic aldehydes and ketones as well as aliphatic ketones by treatment with 1-acetoxy-5-nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-chloro-1,2- benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new tri-valent iodine compounds were prepared from 5-substituted 2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-CPBA). ANBX and ABBX were the most effective reagents for this oxidation of alcohols, and this present reaction is very attractive because of the ease of product isolation and the reusability of the reagents.

Full text of DOI:10.1002/ejoc.201301466

Job/Unit: O31466
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FULL PAPER
DOI: 10.1002/ejoc.201301466
Oxidation of Alcohols to Aldehydes or Ketones with 1-Acetoxy-1,2-
benziodoxole-3(1H)-one Derivatives
Masataka Iinuma,[a] Katsuhiko Moriyama,[a] and Hideo Togo*[a]
Keywords: Oxidation / Hypervalent compounds / Iodine / Alcohols / Aldehydes / Ketones
Various benzylic and aliphatic alcohols were smoothly oxid- valent iodine compounds were prepared from 5-substituted
ized to the corresponding aromatic aldehydes and ketones as
well as aliphatic ketones by treatment with 1-acetoxy-5-
nitro-1,2-benziodoxole-3(1H)-one (ANBX), 1-acetoxy-5-
bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-
chloro-1,2-benziodoxole-3(1H)-one (ACBX), and 1-acetoxy-
5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX). These new tri-
2-iodobenzoic acids and meta-chloroperoxybenzoic acid (m-
CPBA). ANBX and ABBX were the most effective reagents
for this oxidation of alcohols, and this present reaction is very
attractive because of the ease of product isolation and the
reusability of the reagents.
report the preparation of the new compounds 1-acetoxy-5-
nitro-1,2-benziodoxole-3(1H)-one (ANBX),[6] 1-acetoxy-5-
bromo-1,2-benziodoxole-3(1H)-one (ABBX), 1-acetoxy-5-
chloro-1,2-benziodoxole-3(1H)-one (ACBX), and 1-acet-
oxy-5-fluoro-1,2-benziodoxole-3(1H)-one (AFBX, see Fig-
ure 1) as well as the employment of these trivalent iodine
compounds under mild conditions for the oxidation of vari-
ous alcohols.
Introduction
Because of their environmentally benign character and
highly selective oxidizing ability, hypervalent iodine com-
pounds have recently become more and more popular.[1]
The Dess–Martin periodinane [1,1,1-triacetoxy-1,1-di-
hydro-1,2-benziodoxol-3(1H)-one][2] and 1-hydroxy-1,2-
benziodoxol-3(1H)-one (2-iodoxybenzoic acid, IBX)[3] are
examples of pentavalent iodine compounds (IV) that are
used for the efficient oxidation of alcohols. The Dess–Mar-
tin periodinane, in particular, is the most popular and best
reagent for the selective oxidation of alcohols that contain
a variety of functional groups to give the corresponding
aldehydes or ketones, as these reactions can be carried out
in dichloromethane or chloroform at room temperature.
However, the Dess–Martin periodinane and IBX are heat-
and shock-sensitive reagents, and, therefore, all experimen-
tal operations must be carried out behind a safety shield to
protect from explosions.[2c] In this regard, it is difficult to
use these compounds for the large-scale oxidation of
alcohols. Recently, the 2,2,6,6-tetramethylpiperidine-1-oxyl-
catalyzed (TEMPO-catalyzed) oxidation of alcohols by
treatment with (diacetoxyiodo)benzene (DIB) at room tem-
perature to give aldehydes or ketones has become very pop-
ular in organic synthesis.[4] However, in this case, the reac-
tion mixture must be purified by column chromatography
to remove the coproduct iodobenzene and an oxoammon-
ium salt of TEMPO, which is the actual active species for
the oxidation. Herein, as part of our study of new trivalent
iodine compounds for organic synthesis,[5] we would like to
Figure 1. Trivalent iodine compounds.
Results and Discussion
(Diacetoxyiodo)benzene, which is the most typical and
popular trivalent iodine compound, is often used in organic
synthesis because of its wide synthetic utility and nonex-
plosive character. However, DIB does not oxidize alcohols
smoothly. For example, when p-methylbenzyl alcohol was
[a] Graduate School of Science, Chiba University,
Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
E-mail: togo@faculty.chiba-u.jp
http://reaction-2.chem.chiba-u.jp/index.html
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201301466.
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Table 1. Optimization for oxidation of p-methylbenzyl alcohol with treated with DIB in N,N-dimethylformamide (DMF),
DIB, ANBX, and ABBX.
CHCl3, CH3CN, or tetrahydrofuran (THF) at 60 °C for
24 h or in CH2Cl2 at 40 °C for 24 h, p-methylbenzaldehyde
was obtained in yields of 19–31%, and mostly the starting
material was recovered as shown in Table 1 (see Entries 1–
5). The poor oxidizing ability of DIB with alcohols is be-
cause the electron density at the iodine atom is not suffi-
ciently low. To enhance the oxidizing ability of trivalent
iodine compounds, the new substances ANBX, ABBX,
ACBX, and AFBX that have two electron-withdrawing
groups on the benzene ring, that is, a carboxy group along
with a nitro, bromo, chloro, or fluoro group, were proposed
(see Figure 1). ANBX, ABBX, ACBX, and AFBX were
easily prepared in high yields by using our previous method
that employs the oxidation of 2-iodo-5-nitrobenzoic acid,
5-bromo-2-iodobenzoic acid, 5-chloro-2-iodobenzoic acid,
and 5-fluoro-2-iodobenzoic acid, respectively, with m-
chloroperoxybenzoic acid (m-CPBA) in acetic acid (see
Scheme 1).[7] First, the reactivity of ANBX and ABBX was
examined with regard to the oxidation of p-methylbenzyl
alcohol. ANBX showed a high reactivity when the reaction
was performed in either DMF or dimethyl sulfoxide
(DMSO) at 60 °C for 24 h to give p-methylbenzaldehyde in
good yields (see Table 1, Entries 10 and 15). ABBX also
showed a high reactivity not only in DMF and DMSO but
also in CHCl3 at 60 °C for 24 h to give p-methylbenzalde-
hyde in good yields (see Table 1, Entries 19, 22, and 24).
However, both cases required 2 equiv. of ANBX or ABBX
for the effective oxidation of the alcohol. Overall, ANBX
showed the best reactivity in DMF and DMSO among the
examined solvents CHCl3, CH3CN, CH2Cl2, tetra-
hydrofuran (THF), DMF, and DMSO (see Table 1, En-
tries 6–15), and DMF was a slightly better solvent than
DMSO (see Table 1, Entries 10 and 15). This is a conse-
quence of the moderate solubility of ANBX in DMF and
DMSO under warm conditions, as ANBX is scarcely solu-
ble in THF, CH3CN, CH2Cl2, or CHCl3. On the other
hand, ABBX is a slightly soluble in CHCl3 in addition to
DMF and DMSO. Therefore, the oxidation of the alcohol
by treatment with ABBX proceeded smoothly not only in
DMF and DMSO but also in CHCl3 (see Table 1, En-
tries 19, 22, and 24).
Scheme 1. Preparation of ANBX, ABBX, ACBX, AFBX, and ABX.
On the basis of the optimum reaction conditions, the re-
[a] Purified yield. [b] Purity after extraction of the reaction mixture
activities of the known compound 1-acetoxy-1,2-benz-
iodoxole-3(1H)-one (ABX) and ANBX in DMF along with
with Et2O/hexane and removal of the solvent. [c] NMP = N-
methyl-2-pyrrolidone.
2
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Oxidation of Alcohols to Aldehydes or Ketones
Table 2. Oxidation of alcohols with ABX, ANBX, ABBX, ACBX, and AFBX.
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Table 2. (Continued)
[a] Purified yield. [b] Purity after extraction of the reaction mixture with Et2O/hexane and removal of the solvent. [c] Recovered and
regenerated ANBX was used. [d] Recovered and regenerated ABBX was used. [e] ANBX (1.6 equiv.) was used. [f] ABX, ANBX, ABBX,
ACBX, or AFBX (3.0 equiv.) was used.
those of ABBX, ACBX, and AFBX in CHCl3 were com- ylbenzaldehyde in good yields. ANBX in DMF showed the
pared with regard to the oxidation of p-methylbenzyl best reactivity to furnish p-methylbenzaldehyde in higher
alcohol (see Table 2, Entries 1, 2, 4, 6, and 7). ABX, ABBX, yields than those obtained with ABX, ABBX, ACBX, or
ACBX, and AFBX showed high reactivities to form p-meth- AFBX. Here, ABX is slightly soluble in DMF, as is ANBX,
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Oxidation of Alcohols to Aldehydes or Ketones
but it is scarcely soluble in CHCl3. On the other hand, sim- dodecanol, and β-cholestanol were treated with ANBX in
ilar to ABBX, ACBX and AFBX are slightly soluble in DMF and ABBX in CHCl3 at 60 °C for 24 h to form the
CHCl3. The present oxidation reactions offer two tremen- corresponding aliphatic aldehydes and ketones in good
dous advantages. The first is that the aldehyde could be yields (see Table 2, Entries 69–85). When the reactivities of
obtained in high yield with high purity by a simple extrac- ABX, ANBX, ABBX, ACBX, and AFBX were again com-
tion of the reaction mixture with diethyl ether/hexane after pared with respect to the oxidation of cyclododecanol, we
quenching with aqueous NaHCO3. The second is that acidi- found that ABX showed poor reactivity, whereas ACBX and
fication of the aqueous solution induces the precipitation AFBX showed moderate reactivities, and ANBX and ABBX
of 2-iodo-5-nitrobenzoic acid and 5-bromo-2-iodobenzoic showed high reactivities to provide cyclododecanone in
acid in high yields, and upon treatment mCPBA, ANBX good yields (see Table 2, Entries 78–82). In this case, ANBX
and ABBX could be regenerated in high yields and reused showed the best reactivity. Thus, ABX is not an efficient
in the same oxidation reaction to give p-methylbenzalde- oxidant for the oxidation reaction of aliphatic secondary
hyde in 95 and 87% yields, respectively, with high purity alcohols (see Table 2, Entries 71, 78, 83). Finally, 2,3,4,6-
(see Table 2, Entries 3 and 5). Thus, after recovery and re- tetra-O-benzyl-d-glucose and 1-[2Ј-(4ЈЈ-methoxycarbonyl)-
generation, ANBX and ABBX could be repeatedly used in ethylphenoxy]-2-propanol, which contain ether and ester
the same reaction. In addition, ABX, ACBX, and AFBX groups, underwent oxidation by treatment with ANBX and
were recovered in moderate yields (60–75%). p-Chloro- ABBX to give the corresponding lactone and ketone,
benzyl alcohol was also treated with ABX and ANBX in respectively, in good yields (see Table 2, Entries 87–90).
DMF as well as with ABBX in CHCl3 to provide p-chloro- Again, ABX showed poor reactivity (see Table 2, Entry 86).
benzaldehyde in good yields with high purity (see Table 2, Overall, ANBX in DMF gave slightly higher yields than
Entries 8, 9, and 11). The regenerated ANBX and ABBX ABBX in CHCl3. However, ABBX can be used when the
also gave the aldehyde in good yields with high purity (see oxidation is carried out in CHCl3.
Table 2, Entries 10 and 12). Other benzylic alcohols that
Neither of the trivalent iodine compounds ANBX or
contain acetal, phenyl, allyl, nitro, methoxy, trimethyl, and ABBX could oxidize primary alcohols such as 1-octanol
methylthio groups on the aromatic ring as well as hetero- and 1-decanol, and the starting alcohols were recovered
aromatic benzylic alcohols, such as 2-thiophenemethanol, quantitatively. However, adamantanemethanol,
a neo-
3-pyridinemethanol, 2-benzothiophenemethanol, 2-benzo- pentyl-type aliphatic alcohol, could be oxidized. This is
furanmethanol, and N-tosyl-3-indolemethanol, were treated probably a consequence of the higher electron density of
with ABX and ANBX in DMF and ABBX in CHCl3 at the oxygen atom of an aliphatic secondary alcohol in com-
60 °C for 24 h to give the corresponding aromatic aldehydes parison to that of an aliphatic primary alcohol. Therefore,
in good yields. ANBX in DMF and ABBX in CHCl3, in ANBX and ABBX could selectively oxidize benzylic
particular, gave the corresponding aldehydes in high yields alcohols and aliphatic secondary alcohols to give the corre-
with high purity (see Table 2, Entries 13–48) by simple ex- sponding aromatic aldehydes and ketones as well as ali-
traction of the reaction mixture followed by removal of the phatic ketones, respectively. When a mixture of 1-phenyl-1-
solvent.
propanol and 1-octanol was treated with ANBX (2 equiv.)
Under these conditions, the thiomethyl moiety of the in DMF at 60 °C for 24 h, propiophenone was obtained in
aromatic aldehyde did not oxidize (see Table 2, Entries 33– 86% yield along with 1-octanol in 99% yield [see Scheme 2,
35). Next, the oxidation of benzylic secondary alcohols by Equation (1)], and when a mixture of cyclododecanol and
treatment with ANBX in DMF and ABBX in CHCl3 was 1-octanol was treated with ANBX (3 equiv.) in DMF at
carried out at 60 °C for 24 h to give the corresponding aro- 60 °C for 24 h, cyclododecanone was obtained in 80% yield
matic ketones in good yields with high purities, and, again, along with 1-octanol in 99% yield [see Scheme 2, Equa-
this occurred by simple extraction of the reaction mixture tion (2)]. Moreover, when 1,10-dihydroxydodecane was
followed by removal of the solvent (see Table 2, Entries 49– treated with ANBX (3 equiv.) in DMF at 60 °C for 24 h,
60). In these cases as well, the thiomethyl and olefinic 1-hydroxydodecan-10-one was obtained in 81% yield [see
groups were not affected during the oxidation (see Table 2, Scheme 2, Equation (3)]. Similarly, when a mixture of 1-
Entries 57 and 58). ABX in DMF gave the corresponding phenyl-1-propanol and 1-octanol was treated with ABBX
aromatic ketones in moderate to good yields (see Table 2, (2 equiv.) in CHCl3 at 60 °C for 24 h, propiophenone was
Entries 49 and 54). The treatment of cinnamyl alcohol, p- obtained in 82% yield together with 1-octanol in 99% yield
chlorocinnamyl alcohol, and p-methoxycinnamyl alcohol [see Scheme 3, Equation (4)], and when a mixture of cyclo-
with ABX and ANBX in DMF as well as ABBX in CHCl3 dodecanol and 1-octanol was treated with ABBX (3 equiv.)
also gave the corresponding cinnamaldehydes in good in CHCl3 at 60 °C for 24 h, cyclododecanone was obtained
yields, and ANBX and ABBX showed high reactivities to in 75% yield together with 1-octanol in 99% yield [see
provide the corresponding α,β-unsaturated aldehydes in Scheme 3, Equation (5)]. Moreover, when 1,10-dihydroxy-
good yields with high purity (see Table 2, Entries 61–68). dodecane was treated with ABBX (3 equiv.) in CHCl3 at
Then, aliphatic alcohols such as geraniol, which is an allylic 60 °C for 24 h, 1-hydroxydodecan-10-one was obtained in
alcohol that contains another olefinic group, 1-adamant- 72% yield [see Scheme 3, Equation (6)]. Therefore, ANBX
anemethanol, borneol, cyclohexanol that contains an O- and ABBX can be used for the selective oxidation of sec-
tert-butyldiphenylsilyl (TBDPS) group at 4-position, cyclo- ondary alcohols.
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the coproducts 5-nitro-2-iodobenzoic acid and 5-bromo-2-
iodobenzoic acid could be recovered by acidification of the
aqueous reaction solution, and ANBX and ABBX could be
regenerated and reused for the same oxidation reaction to
give once again the aldehyde or ketone in good yields with
high purity. Thus, ANBX and ABBX can be used as ef-
ficient oxidants of benzylic primary alcohols, benzylic sec-
ondary alcohols, and aliphatic secondary alcohols that con-
tain various functional groups.
Experimental Section
1
General Methods: The H and 13C NMR spectroscopic data were
recorded with JEOL-JNM-ECX400, JEOL-JNM-ECS400, and
JEOL-JNM-ECA500 spectrometers. Chemical shifts are expressed
in δ (ppm) downfield from TMS. Mass spectra were recorded with
JMS-T100GCV, JMS-HX110, and Thermo LTQ Orbitrap XL
spectrometers. IR spectra were measured with a JASCO FT/IR-
4100 spectrometer. Melting points were recorded with a Yamato
Melting Point Apparatus Model MP-21. Silica gel 60F254 (Merck)
was used for TLC, and silica gel 60 (Kanto Kagaku Co.) was used
for short column chromatography.
Scheme 2. Selective oxidation of secondary alcohols with ANBX.
General Procedure for the Preparation of New Trivalent Iodine Com-
pounds: To
a solution of 2-iodo-5-nitrobenzoic acid (1.46 g,
5.0 mmol) in a mixture of AcOH (20 mL) and Ac2O (20 mL) was
added m-CPBA (1.46 g, 5.5 mmol). The mixture was stirred at
60 °C for 48 h. Upon completion, Et2O (40 mL) was added to the
reaction mixture at 0 °C, and the resulting mixture was filtered to
afford 1-acetoxy-5-nitro-1,2-benziodoxol-3(1H)-one (1.67 g, 95%
yield).
Large-Scale Preparation of ANBX: To a solution of 2-iodo-5-nitro-
benzoic acid (5.85 g, 20.0 mmol) in a mixture of AcOH (80 mL)
and Ac2O (80 mL) was added m-CPBA (5.84 g, 22.0 mmol). The
mixture was stirred at 60 °C for 48 h. Upon completion, Et2O
(160 mL) was added to the reaction mixture at 0 °C, and the re-
sulting mixture was filtered to afford 1-acetoxy-5-nitro-1,2-benzi-
odoxol-3(1H)-one (6.12 g, 87% yield).
1-Acetoxy-5-nitro-1,2-benziodoxol-3(1H)-one (ANBX): (1.67 g, 95%
yield); m.p. 175–179 °C. IR (neat): ν = 1697, 1665, 1525, 1346 cm–1.
˜
1H NMR (500 MHz, [D7]DMF): δ = 1.96 (s, 3 H), 8.26 (d, J =
8.9 Hz, 1 H), 8.67 (d, J = 2.3 Hz, 1 H), 8.78 (dd, J = 2.3 Hz, J =
8.9 Hz, 1 H) ppm. 13C NMR (125 MHz, [D7]DMF): δ = 20.84,
125.52, 128.20, 128.81, 128.85, 134.31, 150.81, 166.82, 172.53 ppm.
HRMS (ESI): calcd. for C9H7O6NI [M + H]+ 351.9313; found
351.9320.
Scheme 3. Selective oxidation of secondary alcohols with ABBX.
1-Acetoxy-5-bromo-1,2-benziodoxol-3(1H)-one (ABBX): (1.80 g,
94% yield); m.p. 176–179 °C. IR (neat): ν = 1682, 1668 cm–1. 1H
˜
Conclusions
NMR (400 MHz, CDCl3): δ = 2.26 (s, 3 H), 7.85 (d, J = 8.7 Hz, 1
H), 8.01 (dd, J = 2.3 Hz, J = 8.6 Hz, 1 H), 8.38 (d, J = 2.3 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.21, 116.41, 126.57,
130.63, 130.92, 136.04, 138.86, 166.63, 176.40 ppm. HRMS (ESI):
calcd. for C9H7O4BrI [M + H]+ 384.8567; found 384.8560.
The new trivalent iodine compounds ANBX, ABBX,
ACBX, and AFBX were prepared, and their reactivities
were compared when employed in the oxidation of alcohols.
As a result, ANBX in DMF and ABBX in either CHCl3 or
DMF showed high reactivities when used in the oxidation
of benzylic primary alcohols, benzylic secondary alcohols,
and aliphatic secondary alcohols to give the corresponding
aldehydes and ketones in good yields with high purity by
employing a simple ether/hexane extraction of the reaction
1-Acetoxy-5-chloro-1,2-benziodoxol-3(1H)-one (ACBX): (1.56 g,
92% yield); m.p. 193–195 °C. IR (neat): ν = 1703, 1659, 1259 cm–1.
˜
1H NMR (500 MHz, CDCl3): δ = 2.28 (s, 3 H), 7.69 (dd, J =
1.8 Hz, J = 8.0 Hz, 1 H), 7.99 (d, J = 1.7 Hz, 1 H), 8.15 (d, J =
8.2 Hz, 1 H) ppm. 13C NMR (125 MHz, CDCl3): δ = 20.30, 119.00,
127.68, 129.33, 132.06, 133.59, 142.76, 167.09, 176.58 ppm. HRMS
mixture and subsequent removal of the solvent. Moreover, (ESI): calcd. for C9H7O4ClI [M + H]+ 340.9072; found 340.9071.
6
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Oxidation of Alcohols to Aldehydes or Ketones
1
1-Acetoxy-5-fluoro-1,2-benziodoxol-3(1H)-one (AFBX): (1.20 g,
833 cm–1. H NMR (400 MHz, CDCl3): δ = 7.40 (t, J = 7.2 Hz, 1
74% yield); m.p. 139–142 °C. IR (neat): ν = 1696, 1632 cm–1. 1H H), 7.47 (t, J = 7.2 Hz, 2 H), 7.62 (d, J = 7.2 Hz, 2 H), 7.73 (d, J
˜
NMR (400 MHz, CDCl3): δ = 2.27 (s, 3 H), 7.43 (ddd, JH,H
=
= 8.2 Hz, 2 H), 7.93 (d, J = 8.2 Hz, 2 H), 10.04 (s, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 126.94, 127.26, 128.06, 128.60,
129.85, 134.77, 139.26, 146.74, 191.49 ppm.
7.7 Hz, JH,H = 7.7 Hz, JH,F = 2.3 Hz, 1 H), 7.76 (dd, JH,H = 7.5 Hz,
JH,F = 1.6 Hz, 1 H), 8.22 (dd, JH,F = 5.2 Hz, JH,H = 8.6 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.26, 117.32 (d, JC,F
= 28.7 Hz), 119.36 (d, JC,F = 22.9 Hz), 119.69 (d, JC,F = 10.5 Hz),
4-(Allyloxy)benzaldehyde:[8a] Oil (147.4 mg, 91% yield). IR (neat):
ν = 2787, 1686, 1596, 1251, 1157, 829 cm–1. H NMR (400 MHz,
1
˜
125.41, 134.53 (d, JC,F = 9.5 Hz), 167.11, 167.47 (d, JC,F
=
CDCl3): δ = 4.62 (d, J = 5.2 Hz, 2 H), 5.33 (d, J = 10.6 Hz, 1 H),
5.44 (d, J = 17.4 Hz, 1 H), 6.00–6.10 (m, 1 H), 7.01 (d, J = 8.8 Hz,
2 H), 7.83 (d, J = 8.6 Hz, 2 H), 9.88 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 68.90, 114.89, 118.27, 129.91, 131.87,
132.18, 163.49, 190.71 ppm.
261.3 Hz), 176.55 ppm. HRMS (ESI): calcd. for C9H7O4FI [M +
H]+ 324.9368; found 324.9364.
Typical Procedure for the Oxidation of Alcohols to Aldehydes or
Ketones in DMF: To
a solution of 4-methylbenzyl alcohol
(122.1 mg, 1.0 mmol) in DMF (4 mL) was added 1-acetoxy-5-nitro-
1,2-benziodoxol-3-(1H)-one (703.8 mg, 2.0 mmol). The mixture
was stirred at 60 °C for 24 h. Upon completion, the reaction mix-
ture was added to aqueous NaHCO3 (10 mL). The aqueous layer
was extracted with a mixture of Et2O/hexane (1:1; 3ϫ 10 mL). The
combined organic layers were dried with Na2SO4 and filtered. Re-
moval of the solvent under reduced pressure gave 4-methylbenzal-
dehyde (116.4 mg, 97% yield, 98% purity). The purity was esti-
4-Nitrobenzaldehyde: (141.9 mg, 94% yield); m.p. 101–103 °C (com-
mercially available, m.p. 102–107 °C). IR (neat): ν = 2827, 1702,
˜
1536, 1343, 1194, 813, 737 cm–1. 1H NMR (500 MHz, CDCl3): δ =
8.10 (d, J = 8.9 Hz, 2 H), 8.40 (d, J = 8.6 Hz, 2 H), 10.19 (s, 1
H) ppm. 13C NMR (125 MHz, CDCl3): δ = 124.20, 130.40, 139.99,
151.02, 190.26 ppm.
4-Methoxybenzaldehyde: (130.6 mg, 96% yield); oil (commercially
1
mated by H NMR spectroscopic analysis. To recover the ANBX,
available, oil). IR (neat): ν = 2840, 1698, 1602, 1511, 1263,
˜
the aqueous layer was acidified (pH ≈ 2) by using aqueous HCl (1 m
solution, 15 mL), and the resulting mixture was filtered to afford 2-
iodo-5-nitrobenzoic acid (538.9 mg, Ͼ92% yield). Oxidation of 2-
iodo-5-nitrobenzoic acid with mCPBA again afforded ANBX
(Ͼ92% yield).
1162 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.89 (s, 3 H), 7.01 (d,
J = 8.7 Hz, 2 H), 7.84 (d, J = 8.8 Hz, 2 H), 9.89 (s, 1 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 55.54, 114.26, 129.91, 131.94,
164.56, 190.76 ppm.
2,4,6-Trimethylbenzaldehyde: (139.2 mg, 94% yield); oil (commer-
1
cially available, oil). IR (neat): ν = 2921, 1681, 1607, 780 cm–1. H
Typical Procedure for the Oxidation of Alcohols to Aldehydes or
Ketones in CHCl3: To a solution of 4-methylbenzyl alcohol
(122.1 mg, 1.0 mmol) in CHCl3 (4 mL) was added 1-acetoxy-5-
bromo-1,2-benziodoxol-3-(1H)-one (767.7 mg, 2.0 mmol). The
mixture was stirred at 60 °C for 24 h. Upon completion, the reac-
tion mixture was added to aqueous NaHCO3 (10 mL). The aque-
ous layer was extracted with CHCl3 (3ϫ 10 mL). The combined
organic layers were dried with Na2SO4 and filtered. Removal of the
solvent under reduced pressure gave 4-methylbenzaldehyde
(108.0 mg, 90% yield, 90% purity). The purity was estimated by
1H NMR spectroscopic analysis. To recover the ABBX, the aque-
ous layer was acidified (pH ≈ 2) by using aqueous HCl (1 m solu-
tion, 15 mL), and the resulting mixture was filtered to afford 2-
iodo-5-bromobenzoic acid (593.0 mg, Ͼ91% yield). Oxidation of
2-iodo-5-bromobenzoic acid with mCPBA again afforded ABBX
(Ͼ93% yield).
˜
NMR (500 MHz, CDCl3): δ = 2.30 (s, 3 H), 2.56 (s, 6 H), 6.87 (s,
2 H), 10.54 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 20.10,
21.05, 129.51, 130.10, 141.03, 143.37, 192.49 ppm.
4-(Methylthio)benzaldehyde: (130.7 mg, 86% yield); oil (commer-
cially available, oil), IR (neat): ν = 2829, 1691, 1588, 1090,
˜
1
808 cm–1. H NMR (400 MHz, CDCl3): δ = 2.53 (s, 3 H), 7.31 (d,
J = 8.4 Hz, 2 H), 7.77 (d, J = 8.4 Hz, 2 H), 9.91 (s, 1 H) ppm. 13C
NMR (100 MHz, CDCl3); δ = 14.51, 125.04, 129.89, 132.80,
147.81, 191.15 ppm.
2-Thiophenecarboxaldehyde: (104.1 mg, 93% yield); oil (commer-
cially available, oil). IR (neat): ν = 2820, 2761, 1671 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 7.22 (dd, J = 4.8, 3.8 Hz, 1 H), 7.75–7.82
(m, 2 H), 9.95 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
128.22, 135.03, 136.21, 143.94, 182.89 ppm.
Aldehydes and Ketones Resulting from the Oxidation of Alcohols
with ABBX
Nicotinaldehyde: (87.7 mg, 82% yield); oil (commercially available,
oil). IR (neat): ν = 2839, 1699, 1588, 700 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 7.50–7.54 (m, 1 H), 8.20 (d, J = 8.8 Hz, 1
4-Methylbenzaldehyde: (108.0 mg, 90% yield); oil (commercially
H), 8.87 (d, J = 8.6 Hz, 1 H), 9.10 (s, 1 H), 10.14 (s, 1 H) ppm. 13
C
available, oil). IR (neat): ν = 2827, 2734, 1702, 809 cm–1. 1H NMR
˜
NMR (100 MHz, CDCl3): δ = 123.45, 131.02, 135.49, 151.55,
154.27, 190.49 ppm.
(400 MHz, CDCl3): δ = 2.44 (s, 3 H), 7.33 (d, J = 7.9 Hz, 2 H),
7.78 (d, J = 7.9 Hz, 2 H), 9.97 (s, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 21.50, 129.33, 129.46, 133.81, 145.15, 191.62 ppm.
Benzo[b]thiophen-2-carbaldehyde: (150.7 mg, 93% yield); m.p. 34–
4-Chlorobenzaldehyde: (128.8 mg, 92% yield); m.p. 48–49 °C (com-
35 °C (commercially available, m.p. 35–36 °C). IR (neat): ν = 2823,
˜
1665, 1515, 1133, 747, 725 cm–1. 1H NMR (400 MHz, CDCl3): δ =
7.38 (t, J = 7.6 Hz, 1 H), 7.44 (t, J = 7.6 Hz, 1 H), 7.81 (d, J =
7.6 Hz, 1 H), 7.86 (d, J = 7.7 Hz, 1 H), 7.92 (s, 1 H), 10.03 (s, 1
H) ppm. 13C NMR (100 MHz, CDCl3:): δ = 122.92, 124.96, 126.01,
127.89, 134.36, 138.21, 142.23, 142.93, 184.44 ppm.
mercially available, m.p. 47–50 °C). IR (Nujol):
ν = 2727,
˜
1
1710 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), 9.98 (s, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 128.93, 130.36, 134.16, 140.39, 190.31 ppm.
Piperoylaldehyde: (141.0 mg, 94% yield); m.p. 37–39 °C (commer-
cially available, m.p. 36–38 °C). IR (Nujol): ν = 2725, 1685 cm–1.
Benzofuran-2-carbaldehyde:[8b] Oil (137.2 mg, 93% yield). IR (neat):
˜
1H NMR (400 MHz, CDCl3): δ = 6.07 (s, 2 H), 6.93 (d, J = 7.9 Hz,
1 H), 7.32 (d, J = 1.6 Hz, 1 H), 7.41 (dd, J = 7.9 Hz, 1.6 Hz, 1 H),
9.80 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 102.02,
106.77, 108.24, 128.55, 131.77, 148.60, 153.00, 190.17 ppm.
ν = 2827, 1677, 1555, 1118, 831, 750, 732 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 7.34 (t, J = 7.8 Hz, 1 H), 7.52 (t, J =
7.8 Hz, 1 H), 7.57 (s, 1 H), 7.60 (d, J = 7.8 Hz, 1 H), 7.75 (d, J =
7.8 Hz, 1 H), 9.87 (s, 1 H) ppm. 13C NMR(100 MHz, CDCl3): δ
= 112.62, 117.84, 123.60, 124.13, 126.56, 129.16, 152. 58, 156.16,
4-Phenylbenzaldehyde: (163.8 mg, 90% yield); m.p. 57–58 °C (com-
mercially available, m.p. 58 °C). IR (Nujol): ν = 2726, 1708, 179.7 ppm.
˜
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7

Job/Unit: O31466
/KAP1
Date: 25-11-13 15:48:15
Pages: 10
M. Iinuma, K. Moriyama, H. Togo
FULL PAPER
1-Tosyl-1H-indole-3-carbaldehyde:[8c] (254.2 mg, 85% yield); m.p.
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 128.79, 129.28, 129.51,
144–146 °C. IR (neat): ν = 2824, 1678, 1376, 1098, 1080, 969, 743,
132.36, 137.09, 150.96, 193.28 ppm.
˜
1
658 cm–1. H NMR (500 MHz, CDCl3): δ = 2.36 (s, 3 H), 7.29 (d,
trans-p-Methoxycinnamaldehyde: (131.2 mg, 81% yield); oil (com-
J = 8.1 Hz, 2 H), 7.32–7.42 (m, 2 H), 7.85 (d, J = 8.1 Hz, 2 H),
7.95 (d, J = 8.3 Hz, 1 H), 8.24 (s, 1 H), 8.25 (d, J = 7.4 Hz, 1 H),
10.09 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.62,
113.20, 122.27, 122.55, 125.01, 126.22, 126.26, 127.19, 130.29,
134.23, 135.15, 136.29, 146.15, 185.42 ppm.
mercially available, oil). IR (neat): ν = 2827, 1665, 1596, 1246, 1122,
˜
813 cm–1. 1H NMR (400 MHz, CDCl3): δ = 3.85 (s, 3 H), 6.60 (dd,
J = 7.8, 15.9 Hz, 1 H), 6.94 (d, J = 8.9 Hz, 2 H), 7.42 (d, J =
15.8 Hz, 1 H), 7.52 (d, J = 8.9 Hz, 2 H), 9.65 (d, J = 7.8 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.34, 114.44, 126.36,
126.63, 130.25, 152.66, 162.08, 193.62 ppm.
4-(1,3-Dioxolan-2-yl)benzaldehyde:[8d] (151.3 mg, 85% yield); m.p.
1
108–109 °C. IR (neat): ν = 2827, 1698, 1204, 1078 cm–1. H NMR
˜
Geranial: (142.9 mg, 94% yield); oil (commercially available, oil).
1
IR (neat): ν = 2768, 1673 cm–1. H NMR (400 MHz, CDCl ): δ =
(400 MHz, CDCl3): δ = 4.05–4.15 (m, 4 H), 5.88 (s, 1 H), 7.65 (d,
J = 8.1 Hz, 2 H), 7.90 (d, J = 8.2 Hz, 2 H), 10.03 (s, 1 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 65.38, 102.77, 127.04, 129.76,
136.82, 144.33, 191.96 ppm.
˜
3
1.61 (s, 3 H), 1.69 (s, 3 H), 2.17 (s, 3 H) 2.17–2.27 (m, 4 H), 5.03–
5.14 (m, 1 H), 5.88 (d, J = 7.9 Hz, 1 H), 9.99 (d, J = 7.9 Hz, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 16.87, 16.99, 24.92,
25.02, 39.89, 121.86, 126.68, 132.14, 163.07, 190.54 ppm.
Propiophenone: (112.6 mg, 84% yield); oil (commercially available,
oil). IR (neat): ν = 1686 cm–1. 1H NMR (400 MHz, CDCl3): δ =
1-Adamantanecarboxaldehyde:[8e] (134.5 mg, 82% yield); m.p. 140–
˜
142 °C. IR (Nujol):
ν =
˜
2815, 2698, 1722 cm–1. 1H NMR
1.23 (t, J = 7.3 Hz, 3 H), 3.00 (q, J = 7.3 Hz, 2 H), 7.45 (t, J =
7.7 Hz, 2 H), 7.55 (t, J = 7.7 Hz, 1 H), 7.96 (d, J = 7.7 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.72, 31.25, 127.44,
128.02, 132.35, 136.39, 200.28 ppm.
(400 MHz, CDCl3): δ = 1.68–1.80 (m, 12 H), 2.03–2.09 (m, 3 H),
9.32 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 27.31, 35.80,
36.52, 44.82, 206.09 ppm.
1-Phenylnonan-1-one: (176.7 mg, 81% yield); oil (commercially Camphor: (109.5 mg, 72% yield); m.p. 170–173 °C (commercially
available, m.p. 172–180 °C). IR (Nujol): ν˜ = 1749 cm–1. H NMR
CDCl3): δ = 0.88 (t, J = 6.0 Hz, 3 H), 1.20–1.40 (m, 10 H), 1.67– (400 MHz, CDCl3): δ = 0.84 (s, 3 H), 0.91 (s, 3 H), 0.96 (s, 3 H),
1
1
available, oil). IR (neat): ν = 1685, 689 cm–1. H NMR (400 MHz
˜
1.77 (m, 2 H), 2.92 (t, J = 7.3 Hz, 2 H), 7.41 (t, J = 7.2 Hz, 2 H),
1.30–1.45 (m, 2 H), 1.68 (td, J = 12.5, 4.0 Hz, 1 H), 1.84 (d, J =
18.4 Hz, 1 H), 1.90–2.00 (m, 1 H), 2.09 (t, J = 4.0 Hz, 1 H), 2.35
7.50 (t, J = 7.2 Hz, 1 H), 7.94 (d, J = 7.2 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 13.86, 22.44, 24.24, 28.97, 29.15, 29.26, (dt, J = 18.4, 4.0 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ
31.62, 38.28, 127.75, 128.24, 132.53, 136.80, 199.92 ppm.
= 9.08, 18.98, 19.61, 26.89, 29.75, 42.89, 43.14, 46.62, 57.53,
219.53 ppm.
Benzophenone: (152.9 mg, 84% yield); m.p. 49–52 °C (commercially
available, m.p. 49 °C). IR (Nujol): ν = 1657 cm–1. 1H NMR
4-(tert-Butyldiphenylsilyloxy)cyclohexanone: (260.6 mg, 74% yield);
˜
m.p. 100–102 °C. IR (neat): ν = 1703, 1037, 1002, 701 cm–1. 1H
˜
(400 MHz CDCl3): δ = 7.48 (t, J = 7.5 Hz, 4 H), 7.58 (t, J = 7.5 Hz,
2 H), 7.80 (d, J = 7.5 Hz, 4 H) ppm. 13C NMR(100 MHz, CDCl3):
δ = 128.20, 129.98, 132.35, 137.51, 196.70 ppm.
NMR (500 MHz, CDCl3): δ = 1.10 (s, 9 H), 1.74–1.80 (m, 2 H),
1.92–1.98 (m, 2 H), 2.18–2.25 (m, 2 H), 2.70–2.80 (m, 2 H), 4.14–
4.17 (m, 1 H), 7.39 (t, J = 7.5 Hz, 4 H), 7.45 (t, J = 7.5 Hz, 2 H),
7.68 (d, J = 7.5 Hz, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
19.09, 26.79, 33.56, 36.77, 66.71, 127.52, 129.63, 133.71, 135.49,
211.54 ppm. HRMS (ESI): calcd. for C22H28O2NaSi [M + Na]+
375.1751; found 375.1749.
1-[4Ј-(Methylthio)phenyl]pent-4-en-1-one: (185.4 mg, 90% yield);
m.p. 56–58 °C. IR (neat): ν = 1677, 1404, 1065 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 2.46–2.53 (m, 4 H), 3.03 (t, J = 7.4 Hz, 2
H), 5.01 (d, J = 10.2 Hz, 1 H), 5.08 (d, J = 17.3 Hz, 1 H), 5.84–
5.96 (m, 1 H), 7.26 (d, J = 8.0 Hz, 2 H), 7.88 (d, J = 8.0 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.46, 27.98, 37.22,
115.01, 124.66, 128.17, 132.89, 137.11, 145.49, 198.00 ppm. HRMS
(ESI): calcd. for C12H15OS [M + H]+ 207.0838; found 207.0836.
Cyclododecanone: (142.0 mg, 78% yield); m.p. 60–62 °C (commer-
cially available, m.p. 61 °C). IR (neat): ν = 1702, 1470 cm–1. 1H
˜
NMR (500 MHz, CDCl3): δ = 1.20–1.36 (m, 14 H), 1.66–1.76 (m,
4 H), 2.46 (t, J = 6.2 Hz, 4 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 21.99, 22.21, 23.87, 24.25, 24.40, 40.01, 212.46 ppm.
1-[4Ј-(Methylthio)phenyl]tridecan-1-one: (284.9 mg, 89% yield);
m.p. 78–80 °C. IR (neat): ν = 1680, 1394, 1232 cm–1. 1H NMR
˜
5α-Cholestan-3-one: (293.6 mg, 76% yield); m.p. 123–125 °C (com-
(400 MHz, CDCl3): δ = 0.88 (t, J = 6.8 Hz, 3 H), 1.20–1.40 (m, 18
H), 1.68–1.75 (m, 2 H), 2.52 (s, 3 H), 2.91 (t, J = 7.5 Hz, 2 H), 7.27
(d, J = 8.8 Hz, 2 H), 7.87 (d, J = 8.8 Hz, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.07, 14.69, 22.64, 24.45, 29.29, 29.34,
29.44, 29.46, 29.57 (2 C), 29.61, 31.86, 38.36, 124.89, 128.42,
133.31, 145.42, 199.53 ppm. HRMS (ESI): calcd. for C20H33OS [M
+ H]+ 321.2247; found 321.2242.
mercially available, m.p. 128–129 °C). IR (Nujol): ν = 1719 cm–1.
˜
1H NMR (400 MHz, CDCl3,): δ = 0.68 (s, 3 H), 0.69–0.76 (m, 1
H), 0.84–0.92 (m, 9 H), 1.01 (s, 3 H), 0.94–1.18 (m, 9 H), 1.23–1.44
(m, 9 H), 1.46–1.60 (m, 4 H), 1.66–1.74 (m, 1 H), 1.78–1.89 (m, 1
H), 1.96–2.12 (m, 3 H), 2.21–2.44 (m, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 11.43, 12.04, 18.64, 21.42, 22.53, 22.79,
23.79, 24.19, 27.98, 28.21, 28.95, 31.69, 35.36, 35.61, 35.76, 36.11,
38.17, 38.54, 39.47, 39.88, 42.56, 44.70, 46.68, 53.78, 56.23,
212.12 ppm.
trans-Cinnamaldehyde: (116.2 mg, 88% yield); oil (commercially
available, oil). IR (neat): ν = 2816, 2743, 1676 cm–1. 1H NMR
˜
(400 MHz, CDCl3): δ = 6.72 (dd, J = 7.7, 16.1 Hz, 1 H), 7.41–7.46
(m, 3 H), 7.48 (d, J = 16.1 Hz, 1 H), 7.54–7.60 (m, 2 H), 9.71 (d,
J = 7.7 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 128.31,
128.42, 128.93, 131.09, 133.81, 152.60, 193.52 ppm.
2,3,4,6-Tetra-O-benzyl-D-glucono-1,5-lactone: Oil (425.2 mg, 79%
yield). IR (neat): ν = 1755, 1454, 1165, 1094, 738, 698 cm–1. 1H
˜
NMR (400 MHz, CDCl3): δ = 3.64–3.75 (m, 2 H), 3.88–3.98 (m, 2
H), 4.12 (d, J = 6.1 Hz, 1 H), 4.43–4.76 (m, 8 H), 4.98 (d, J =
trans-p-Chlorocinnamaldehyde: (144.4 mg, 87% yield); m.p. 61– 11.3 Hz, 1 H), 7.15–7.41 (m, 20 H) ppm. 13C NMR (100 MHz,
63 °C (commercially available, m.p. 60–63 °C). IR (neat): ν = 2826,
CDCl3): δ = 68.21, 73.52, 73.69 (2 C), 73.91, 76.01, 77.30, 78.12,
˜
1
1693, 1078, 805 cm–1. H NMR (400 MHz, CDCl3): δ = 6.68 (dd, 80.92, 127.79 (3 C), 127.91, 127.96 (3 C), 128.08, 128.37, 128.41 (2
J = 7.7, 16.8 Hz, 1 H), 7.40 (d, J = 8.8 Hz, 2 H), 7.43 (d, J =
16.8 Hz, 1 H), 7.50 (d, J = 8.6 Hz, 2 H), 9.70 (d, J = 7.8 Hz, 1
C), 128.45, 136.90, 137.46 (2 C), 137.55, 169.31 ppm. HRMS (ESI):
calcd. for C34H35O6 [M + H]+ 539.2428; found 539.2423.
8
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O31466
/KAP1
Date: 25-11-13 15:48:15
Pages: 10
Oxidation of Alcohols to Aldehydes or Ketones
son, Synthesis 2011, 517–538; q) T. Wirth (Ed.), Hypervalent
Methyl 3-[4Ј-(2ЈЈ-Oxopropoxy)phenyl]propanoate: Oil (184.1 mg,
1
78% yield). IR (neat): ν = 1730, 1509, 1169, 1065 cm–1. H NMR
Iodine Chemistry: Modern Developments in Organic Synthesis,
in: Topics in Current Chemistry, Springer, Berlin, 2003, vol. 224.
[2] a) D. S. Dess, J. C. Martin, J. Org. Chem. 1983, 48, 4155–4156;
b) D. S. Dess, J. C. Martin, J. Am. Chem. Soc. 1991, 113, 7277–
7287; c) R. K. Boeckman Jr., P. Shao, J. J. Mullins, Org. Synth.,
Coll. Vol. 10 2004, 696–701; d) D. D. Holsworth, in: Name Re-
actions for Functional Group Transformations (Eds.: J. J. Li, E. J.
Corey.), John Wiley & Sons, Inc., Hoboken, 2007, p. 218.
[3] a) E. J. Corey, A. Palani, Tetrahedron Lett. 1995, 36, 3485–
3488; b) M. Frigerio, M. Santagostino, S. Sputore, J. Org.
Chem. 1999, 64, 4537–4538; c) K. C. Nicolaou, P. S. Baran, Y.
Zhong, J. Am. Chem. Soc. 2001, 123, 3183–3185.
˜
(500 MHz, CDCl3): δ = 2.26 (s, 3 H), 2.60 (t, J = 7.7 Hz, 2 H),
2.90 (t, J = 7.7 Hz, 2 H), 3.65 (s, 3 H), 4.51 (s, 2 H), 6.81 (d, J =
8.7 Hz, 2 H), 7.11 (d, J = 8.7 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 26.51, 29.92, 35.74, 51.52, 73.01, 114.44, 129.37,
133.64, 156.13, 173.21, 205.81 ppm. HRMS (ESI): calcd. for
C13H16O4Na [M + Na]+ 259.0941; found 259.0936.
1-Hydroxydodecan-10-one: (142.1 mg, 71% yield); m.p. 48–51 °C.
1
IR (neat): ν = 3333, 2916, 1699, 1059 cm–1. H NMR (400 MHz,
˜
CDCl3): δ = 1.05 (t, J = 7.4 Hz, 3 H), 1.25–1.42 (m, 10 H), 1.55–
1.65 (m, 4 H), 2.38–2.50 (m, 4 H), 3.64 (t, J = 6.6 Hz, 2 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 7.79, 23.85, 25.64, 29.17, 29.28
(2 C), 29.32, 32.70, 35.80, 42.35, 62.93, 212.06 ppm. HRMS (ESI):
calcd. for C12H25O2 [M + H]+ 201.1849; found 201.1850.
[4] a) A. De Mico, R. Margarita, L. Parlanti, A. Vescovi, G. Pian-
catelli, J. Org. Chem. 1997, 62, 6974–6977; b) K. Sakuratani,
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Togo, P. H. Toy, Org. Biomol. Chem. 2005, 3, 970–971; d) G.
Piancatelli, F. Leonelli, Org. Synth. 2006, 83, 18–23; e) J. Vatele,
Tetrahedron Lett. 2006, 47, 715–718; f) D. J. Vugts, L. Veum,
K. al-Mafraji, R. Lemmens, R. F. Schmitz, F. J. J. de Kanter,
M. B. Groen, U. Hanefeld, R. V. A. Orru, Eur. J. Org. Chem.
2006, 7, 1672–1677; g) H. Fuwa, M. Yamaguchi, M. Sasaki,
Org. Lett. 2010, 12, 1848–1851; h) H. Uchiro, R. Kato, Y. Arai,
M. Hasegawa, Y. Kobayakawa, Org. Lett. 2011, 13, 6268–6271;
i) J. Shimokawa, T. Harada, S. Yokoshima, T. Fukuyama, J.
Am. Chem. Soc. 2011, 133, 17634–17637; j) C. R. Reddy, N. N.
Rao, P. Sujitha, C. G. Kumar, Eur. J. Org. Chem. 2012, 1819–
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Supporting Information (see footnote on the first page of this arti-
cle): Copies of 1H and 13C NMR spectra for ANBX, ABBX, ACBX,
AFBX, and all aldehydes and ketones.
Acknowledgments
Financial support in the form of a Grant-in-Aid for Scientific Re-
search from the Ministry of Education, Culture, Sports, Science,
and Technology in Japan (grant number 25105710) and the Iodine
Research Project in Chiba University is gratefully acknowledged.
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Received: September 27, 2013
Published Online: ᭿
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9

Job/Unit: O31466
/KAP1
Date: 25-11-13 15:48:15
Pages: 10
M. Iinuma, K. Moriyama, H. Togo
FULL PAPER
Oxidation of Alcohols
The trivalent iodine compounds 1-acetoxy-5-
nitro-1,2-benziodoxole-3(1H)-one (ANBX),
1-acetoxy-5-bromo-1,2-benziodoxole-3(1H)-
one (ABBX), 1-acetoxy-5-chloro-1,2-benz-
iodoxole-3(1H)-one (ACBX), and 1-acetoxy-
5-fluoro-1,2-benziodoxole-3(1H)-one
(AFBX) were used for the oxidation of
benzylic alcohols and aliphatic secondary
alcohols to give the corresponding alde-
hydes and ketones.
M. Iinuma, K. Moriyama,
H. Togo* ......................................... 1–10
Oxidation of Alcohols to Aldehydes or
Ketones with 1-Acetoxy-1,2-benziodoxole-
3(1H)-one Derivatives
Keywords: Oxidation / Hypervalent com-
pounds / Iodine / Alcohols / Aldehydes /
Ketones
10
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Eur. J. Org. Chem. 0000, 0–0