Development of a general and practical iron nitrate/TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes/ketones: Catalysis with table salt

Article abstract of DOI:10.1002/adsc.201100033

Oxidation of alcohols is a fundamental transformation related to our daily life. Traditional approaches with at least one stoichiometric amount of oxidants are expensive and cause serious environmental burdens. There are many reports on the aerobic oxidation of simple alcohols such as alkyl or phenyl carbinols and allylic alcohols, which used oxygen or air as the environmentally benign oxidant forming water as the only by-product. However, no such protocol has been reported for allenols and propargylic alcohols. Thus, it still highly desirable to develop efficient room temperature oxidations of alcohols with a wide scope including allenols and propargylic alcohols. In this paper, an efficient and clean aerobic oxidation of so far the widest spectrum of alcohols using 1 atm of oxygen or air, producing aldehydes/ketones at room temperature in fairly high isolated yields mostly within a couple of hours is described. It is interesting to observe that the reaction has been efficiently expedited by a catalytic amount of sodium chloride in easily recoverable 1,2-dichloroethane. A mechanism involving NO and NO₂ has been proposed based on the results of the control experiments and GC-MS studies of the in-situ formed gas phase of the reaction mixture.

Full text of DOI:10.1002/adsc.201100033

FULL PAPERS
DOI: 10.1002/adsc.201100033
Development of a General and Practical Iron Nitrate/TEMPO-
Catalyzed Aerobic Oxidation of Alcohols to Aldehydes/Ketones:
Catalysis with Table Salt
Shengming Ma,a,b,* Jinxian Liu,a Suhua Li,b Bo Chen,b Jiajia Cheng,b
Jinqiang Kuang,a Yu Liu,a Baoqiang Wan,b Yuli Wang,a Juntao Ye,b Qiong Yu,a
Weiming Yuan,a and Shichao Yub
a
Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal
University, 3663 North Zhongshan Lu, Shanghai 200062, Peopleꢀs Republic of China
Fax : (+86)-21-6260-9305; e-mail: masm@sioc.ac.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
b
Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China
Received: January 14, 2011; Published online: April 13, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.201100033.
Abstract: Oxidation of alcohols is a fundamental aerobic oxidation of so far the widest spectrum of al-
transformation related to our daily life. Traditional cohols using 1 atm of oxygen or air, producing alde-
approaches with at least one stoichiometric amount hydes/ketones at room temperature in fairly high iso-
of oxidants are expensive and cause serious environ- lated yields mostly within a couple of hours is de-
mental burdens. There are many reports on the aero- scribed. It is interesting to observe that the reaction
bic oxidation of simple alcohols such as alkyl or has been efficiently expedited by a catalytic amount
phenyl carbinols and allylic alcohols, which used of sodium chloride in easily recoverable 1,2-dichloro-
oxygen or air as the environmentally benign oxidant ethane. A mechanism involving NO and NO2 has
forming water as the only by-product. However, no been proposed based on the results of the control ex-
such protocol has been reported for allenols and periments and GC-MS studies of the in-situ formed
propargylic alcohols. Thus, it still highly desirable to gas phase of the reaction mixture.
develop efficient room temperature oxidations of al-
cohols with a wide scope including allenols and prop- Keywords: aerobic oxidation; alcohols; catalysis;
argylic alcohols. In this paper, an efficient and clean iron nitrate; TEMPO
Introduction
the only by-product with transition metal catalysts of
Pd,[3–6] Ru,[7–9] Mo-Co,[10] Co,[11] Pt,[12] Os-Cu,[13] Os,[14]
Oxidation of alcohols to aldehydes/ketones is a funda- Ni,[15] Cu,[16–19] Fe,[20–25] etc.[26] or even without a metal-
mental transformation in many organic chemistry-re- lic catalyst.[27,28] Obviously, a room temperature proto-
lated disciplines since aldehydes/ketones are common col would be most energy-effective for all the alcohols
precursors for the synthesis of compounds ranging and advantageous for those thermo-sensitive com-
from fragrances to drugs to materials used for many pounds. However, the reported room temperature
purposes.[1,2] Traditionally, at least a stoichiometric protocols suffer from being limited to aldehyde for-
amount of certain expensive oxidants is applied with mation,[19] the application of expensive or non-con-
possible uncontrollable explosive danger yielding venient catalysts[24]/solvents,[16,25] acidic conditions,[28]
almost the same amount of oxidant-derived waste, or in slow rates (8~72 h),[21,24,25,28] except for those
which causes a heavy burden to the environment with a high additive loading;[22] more critically, among
during continuous mass manufacturing.[1] For this the known aerobic oxidations, in addition to the
reason, over the last three decades, much attention simple non-functionalized alkylic or phenyl carbinols,
has been paid to eco-friendly aerobic oxidations of al- the only functionalized alcohols studied are simple
cohols using oxygen as the oxidant forming water as and non-sterically hindered allylic alcohols.[16] In reali-
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1005

Shengming Ma et al.
FULL PAPERS
ty, we are facing the oxidation of alcohols bearing
very diversified funtionalities which may be elaborat-
ed afterwards. Furthermore, there are usually issues
of over-oxidation to carboxylic acids for primary alco-
hols and very different reactivities for primary and
secondary alcohols.[25,29,30] These have severely limited
the daily practice of the known alcohol aerobic oxida-
tions. We have been studying the aerobic oxidation of
2,3-allenols by applying the known aerobic oxidation
protocols,[3–25,28] however, it turned out to be very
challenging since all these aerobic procedures did not
work very well here. The main problem is a very slow
reaction and the required high temperature implicat-
ing the issue of instability of the forming 1,2-allenyl
ketones. Thus, we conceived that if we could develop
Scheme 1. FeCl3/NaNO2-4-acetamido-TEMPO-catalyzed
aerobic oxidation of 3-(n-hexyl)-1,2-octadien-4-ol.
an efficient room temperature aerobic oxidation for creasing the loadings to 10 mol% each led to 25%
the most challenging 2,3-allenols, it would be easily yield of the ketone with 50% of the allenol being re-
applicable to various types of other different alcohols covered after 24 h (Scheme 1). In this paper, we wish
commonly encountered in industry and academic or- to disclose an iron nitrate/TEMPO-catalyzed aerobic
ganic chemistry-related laboratories with highly oxidation by applying an unusual inorganic ligand
loaded functionalities for further elaboration.
(NaCl) approach, which is very efficient at room tem-
It should be noted that TEMPO has been utilized perature, and is complete within a couple of hours for
as the catalyst together with at least one molar equiv- essentially all types of alcohols bearing different unsa-
alent of NaOCl to oxidize the alcohols in industry.[1] turated carbon-carbon bonds with high efficiency, not
In addition, it may convert simple non-functionalized mentioning the simple alkyl or phenyl carbinols.
alkyl/phenyl carbinols and allylic alcohols to the cor-
responding aldehydes or ketones with oxygen as the
oxidant in the presence of organic or inorganic addi- Results and Discussion
tives.[9,16,25,27,28]
As we know, living organisms utilize copper and Optimization of Reaction Conditions
iron for their oxidation reactions and iron-containing
hemoglobin carries oxygen for our breathing. In addi- Based on our previous control experiment
tion, the following values were reported by: Martin (Scheme 1), we used the highly sterically hindered 3-
(10 mol% of iron nitrate and 5 mol% of FeBr3 for (n-hexyl)-1,2-octadien-4-ol as the model alcohol with
24 h, no reaction for 18 alkyl carbinols),[21] Firouzaba- TEMPO as the catalyst and set the following criteria
di (50~62.5 mol% of iron nitrate together with 5~ for the to-be-established new aerobic oxidation proto-
10 mol% of H3PW),[22] and Varma (66~100 mol% of col to have a practical procedure for aerobic oxida-
iron nitrate at 60~808C).[23] In all these studies the tion of alcohols to aldehydes: (i) cheap routine chemi-
catalyst loading is too high, thus, not practical for cals (the catalysts and solvent); (ii) a room tempera-
large-scale preparations. Recently, Liang et al. ob- ture reaction for energy efficiency and thermodynam-
served that 5~8 mol% of iron nitrate and 3~8 mol% ically sensitive substrates; (iii) an atmospheric pres-
of the modified TEMPO (4-OH-TEMPO) (for 10~ sure of oxygen for an autoclave-free easy and
24 h) may catalyze the aerobic oxidation of alco- controllable operation; (iv) a spot-to-spot fast reac-
hols.[24] Based on that Liang-Liu reported a better tion.
protocol using FeCl3-NaNO2-unmodified TEMPO as
Thus, our first attempt is to identify the best solvent
the catalyst,[25a] which works for primary or secondary for the reaction with 10 mol% each of iron nitrate
benzylic alcohols and secondary alkanols in an expen- and TEMPO as the catalysts and the results are
sive solvent (PhCF3) at room temperature. Much re- shown in Table 1. It turned out that the reaction in
cently, Liang and Liu et al. further reported a modi- 1,2-dichloroethane gave the highest conversion
fied procedure by using FeCl3/4-acetamido-TEMPO/ (entry 5, Table 1). In addition, it should be noted that
NaNO2 as the catalyst to partially solve the problems under the Martinꢀs[21] or Liangꢀs earlier protocols,[24]
of the limitation to primary alkanols and the solvent; the corresponding reaction in MeCN is extremely
the reaction was conducted at 508C with 0.4 MPa of low-yielding although the conversion reached 55%
oxygen.[25b] We noticed that even under their most re- (entry 6, Table 1).
cently modified procedure,[25b] the NMR yield of the
Based on this observation, we used 1,2-dichloro-
ketone after 24 h was only 11% with the starting 3-(n- ethane as the solvent to see whether there is any
hexyl)-1,2-octadien-4-ol being recovered in 62%; in- better inorganic catalyst for this purpose with the re-
1006
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
Table 1. Fe
(NO3)3·9H2O/TEMPO-catalyzed room tempera-
Table 3. FeACTHNGUTERN(NUG NO3)3·9H2O/TEMPO-catalyzed room tempera-
ture aerobic oxidation of 3-(n-hexyl)-1,2-octadien-4-ol in dif-
ture aerobic oxidation of 3-(n-hexyl)-1,2-octadien-4-ol in
1,2-dichloroethane-screening for a cheap additive as the co-
catalyst for a fast reaction.[a]
ferent solvents.[a]
Entry
Solvent
Time
[h]
Conv.
[%, NMR]
Yield
ACHTUNGTRNE[NUNG %, NMR]
Entry
Additive
Time
[h]
Conv.
[%, NMR]
Yield
ACHTUNGTRNE[NUNG %, NMR]
G
G
1
2
3
4
5
6
7
8
9
10
DCM
toluene
THF
DME
DCE
CH3CN
CH3CN/H2O[b]
benzene
DMF
48
48
48
48
48
39
39
39
39
39
44
52
50
54
75
55
28
59
23
57
25
21
19
22
43
13
9
20
4
21
1
2
3
4
5
6
7
8
NaNO2
KNO2
TBN
LiCl·H2O
NaCl
KCl
RbCl
CsCl
KF·2H2O
KBr
36
36
36
10
4
4.5
3
3
25
25
25
5
55
48
58
95
100
100
100
100
49
35
24
24
74
72
81
74
73
13
50
20
72
9
ethyl acetate
10
11
12
75
45
100
[a]
Reaction conditions: alcohol (0.2 mmol), TEMPO
KI
.
NaCl[b]
(0.02 mmol), and FeACTHNUTRGNEUN(G NO3)3 9H2O (0.02 mmol) in solvent
(2 mL) at room temperature.
CH3CN/H2O=9/1
[a]
[b]
Reaction conditions: alcohol (0.5 mmol), TEMPO
(0.05 mmol), nitrate (0.05 mmol), additive (0.05 mmol),
DCE (3 mL), 258C.
[b]
NaCl (20 mol%) was used.
sults being summarized in Table 2. Based on the re-
sults presented in Table 2, it turned out that
FeACHTUNGTRENNUNG(NO3)3·9H2O and 1,2-dichloroethane is the best Traditionally, organic ligands are frequently used,
combination, however, the reaction is still very slow however, in order to have a cheap, readily available,
(75% of conversion after 2 days!). Thus, we started to easy to use ligand, we took a different approach by
test the effect of additives (Table 3): The addition of screening inorganic halide ligands since halide anions
NaNO2, KNO2, or TBN[25,28,30] did not help much (en- have been reported to act as ligands for transition
tries 1–3); then we proceeded to consider of adding metals.[21,28,31] Thus, the cheap and readily available in-
suitable ligands to in-situ form a highly active catalyst. organic halides were screened in the first place for
such a purpose. With this approach we were excited
to observe that 10 mol% of LiCl improved the con-
Table 2. TEMPO-catalyzed room temperature aerobic oxi-
dation of 3-(n-hexyl)-1,2-octadien-4-ol in 1,2-dichloro-
ethane-screening for a better cocatalyst.[a]
version to 95% within 10 h (entry 4)! Furthermore,
10 mol% of NaCl, KCl, RbCl, or CsCl all converted
the slow reaction into a very efficient one, which goes
to completion within a couple of hours! In terms of
efficiency the order is CsCl>RbCl>KCl>NaCl>
LiCl (entries 4–9). For the obvious reason of cost and
availability, we chose the kitchen chemical sodium
chloride as the additive: the reaction was completed
within 4 h to afford 3-(n-hexyl)-1,2-octadien-4-one in
72% isolated (entry 5); the results of KF, KBr, and KI
are poor (entries 9–11).
Entry Salts
Time Conv.
Yield
ACHTUNGTRNE[NUNG %, NMR]
[h]
N
1[b]
2
3
Fe
FeCl3 6H2O
Cu
Zn(NO3)2 6H2O
G
48
24
75
19
44
10
43
12
33
2
4
24
The Scope of the Reaction
[a]
Reaction conditions: alcohol (0.5 mmol), TEMPO
(0.05 mmol), salt (0.05 mmol), solvent (3 mL), room tem-
perature.
After further optimization, we defined 5 mol% of Fe-
AHCTNURTGEG(NNNU NO3)3·9H2O, 3 or 5 mol% of TEMPO, and 5 mol%
[b]
of NaCl as the standard catalytic formula. We were
pleased to observe that this protocol easily converts
1 mmol of differently substituted primary as well as
Reaction conditions: alcohol (0.2 mmol), TEMPO
(0.02 mmol), Fe
(2 mL), rt.
ACHTUGNTRENUN(GN NO3)3·9H2O (0.02 mmol), solvent
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1007

Shengming Ma et al.
FULL PAPERS
secondary allenols into allenyl aldehydes or ketones
all within 10 h although with the sterically bulky alle-
nols (the examples with footnote[c]) require 10 mol%
each of iron nitrate, TEMPO and NaCl (Scheme 2).
Over-oxidation to acids from primary allenols was not
observed.
In addition, quitely surprisingly we also noticed
that there is essentially no report on the aerobic oxi-
dation of readily available propargylic alcohols to the
synthetically very useful 2-alkynones. Control experi-
ments show that the aerobic oxidation of 1-(p-me-
thoxyphenyl)-2-heptynol with FeCl3-NaNO2-4-acet-
amido-TEMPO[25] is very slow and the purity of the
isolated product is very low (Scheme 3). Happily, we
found that this recipe may be applied smoothly to the
aerobic oxidation of a series of different primary or
secondary propargylic alcohols, a class of very readily
available functionalized alcohols (Scheme 3 and
Scheme 4). As we know 2-alkynones are very useful
in organic synthesis, showing the potential of this
methodology.
Last but not the least, we are very pleased to see
that this protocol is also applicable to the aerobic oxi-
dation of the most commonly sudied allylic alcohols
(Scheme 5, Part 1), phenyl carbinols (Scheme 5, Part
1), and normal alkyl carbinols (Scheme 5, Part 3).
Again, it works for both primary and secondary alco-
hols. In order to compare the efficiency of the current
protocol with the known room temperature
Scheme 2. Room temperature aerobic oxidation of allenols
to aldehydes or ketones [reaction time, NMR yield (%), and
isolated yield (%)].
Scheme 3. Control experiment of aerobic oxidation of 1-(p-methoxy)-phenyl-2-heptynol.
1008
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
Scheme 4. Room temperature aerobic oxidation of propargylic alcohols to aldehydes or ketones [reaction time, NMR yield
(%), and isolated yield (%)].
Scheme 5. Room temperature aerobic oxidation of most commonly stuided alcohols to aldehydes or ketones [reaction time,
NMR yield (%), and isolated yield (%)].
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1009

Shengming Ma et al.
FULL PAPERS
ones,[16,19,21,22,24,25,28] some 10 mmol scale reactions of employed to produce a 91% isolated yield of pure
comparable or same substrates were conducted with phenyl methyl ketone [Eq. (2)]. It should be noted
the results shown in Scheme 5 (examples with footno- that commercially available chemicals were used di-
te[i]): the reactions of benzylic alcohols and allylic al- rectly without further treatment.
cohols are much faster and those of alkyl carbinols
are at the same level, if not better.
The results shown in Scheme 2, Scheme 4, and
Scheme 5 nicely demonstrate the beauty of this new
methodology: (i) functional groups such as OMe, CF3,
NO2, Cl, TMS, OTBS, terminal alkyne, etc. have been
smoothly tolerated; (ii) the reaction is very clean and
fast: spot to spot transformation mostly within a
couple of hours; (iii) high-yielding; (iv) general for
both primary and secondary alcohols; for primary al- Mechanistic Studies
cohols, over-oxidation to carboxylic acids was not ob-
served; (v) a room temperature reaction with the In order to understand the role of each catalyst, a few
lowest energy consumption; (vi) an efficient transfor- control experiments have been conducted: No reac-
mation mostly with 5 mol% of FeACTHNUTRGNE(UNG NO3)3·9H2O, tion occurred in the absence of TEMPO (entry 1,
3 mol% of TEMPO, and 5 mol% of NaCl; (vii) the Table 4); the reaction did not take place in the pres-
widest scope so far covering alcohols with nearly all ence of 2.5 equiv. of TEMPO, 2.5 equiv. of TEMPO
the types of unsaturated functionalities for further together with 1 equiv. of NaCl, or 2.5 equiv. of
elaboration in a synthetic chemistry-related laborato- TEMPO together with 1 equiv. each of NaCl and
ry.
NaNO3 indicating the importance of the Fe3+ in the
current oxidation reaction of alcohols and catalyst re-
generation.
Large-Scale Reactions for Practical Use
In addition, we noticed in the very beginning that
[32]
NaNO3 and HNO3
failed to replace FeACTHNGUTERNNU(G NO3)3 in
The reaction may be conducted by just using the the recation of 3-(n-hexyl)-1,2-octadien-4-ol, indicat-
oxygen in the air with the same result [Eq. (1)].
ing the importance of Fe3+ in the reaction (Scheme 6).
In the large-scale reaction shown in Eq. (2), NO
has been detected by GC-MS analysis and the pres-
ence of NO2 was confirmed by its characteristic red-
dish-brown color in the gas phase of the reaction mix-
ture. Thus, a rationale was proposed for this recation
(Scheme 7): TEMPO should couple with Fe3+ to
afford intermediate 1, which would react with the al-
cohol to form intermediate 2 by releasing H+. This in-
To further show the practicality and efficiency of termediate would undergo b-H elimination and re-
this catalytic system, a 1.0-mol reaction of 1-phenyl- ductive elimination to produce the aldehyde or
ACHTUNGTRENNUNG
ethanol was conducted by using 2 mol% each of ketone, Fe2+, and TEMPOH. TEMPOH may be con-
FeACHTUNGTRENNUNG(NO3)3·9H2O, TEMPO, and NaCl to give phenyl
methyl ketone in 91% isolated yield within 4 h (Part
3, Scheme 5). Its industrial potential has further been
demonstrated by running the oxidation of 488.64 g
(4 mol) of 1-phenylethanol to phenyl methyl ketone
Table 4. Control experiments for the aerobic oxidation of 1-
phenylethanol.
with just 1 mol% each of FeACTHNUTRGNE(UNG NO3)3·9H2O, TEMPO,
and NaCl using a line to provide 1 atm of oxygen gas
within ~9 h after addition without external heating.
Due to the highly exothermic nature here, the addi-
tion rate for the alcohol had to be manipulated to
ensure a mild, controllable and safe reaction, which is
vital for industrial application. After the reaction was
complete as monitored by TLC, no work-up is
needed: the resulting mixture was directly distilled
under the atmospheric pressure to recover 88% of
1,2-dichloroethane and collect 59 mL of the by-prod-
uct water. After this, distillation under vacuum was
Etry TEMPO
(equiv.)
NaCl
(equiv.)
Time
[h]
Conv. (yield)
[%]
1[a]
2
0
2.5
2.5
0.1
0
1
26
10
10
10
2 (1)
1 (0)
0 (0)
1 (0)
3
4[b] 2.5
1
[a]
0.05 equiv. of FeCAHTUNGTRENNUNG
[b]
AHCTUNGTRENNUNG
1010
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
most commonly used alcohols in academic and indus-
trial laboratories such as primary as well as secondary
normal alkanols, benzylic, allylic, propargylic acco-
hols, and allenols expedited by a catalytic amount of
sodium chloride efficiently. Of particular interest, it
should be noted that for 2,3-allenols and propargylic
alcohols, this is the only reported aerobic oxidation
protocol producing the synthetically attractive 1,2-al-
lenyl ketones and 2-alkynones. Based on a compari-
son with the known protocols for the commonly stud-
ied alcohols, this is the most efficient room tempera-
ture aerobic reaction with just ꢀ5 mol% of the cata-
lyst loadings so far. In a large scale experiment
(4 mol), a loading of 1 mol% for each catalyst is
enough with direct distillation to yield the product.
This spot-to-spot protocol with 1 atm oxygen is
energy-effective, going to completion at room temper-
ature within just a couple of hours, which may be of
high interest both to the academic laboratories and
industry in terms the scale of the reaction, cost, effi-
ciency, and energy consumption. Further studies are
needed to unveil the mechanism and the exact role of
sodium chloride. Further studies including the role of
NaCl and better solvents for industrial use and appli-
cation of this reaction in organic synthesis is in prog-
ress in this group.
Scheme 6. The importance of Fe3+ in the current reaction.
Experimental Section
Typical Procedure for the Synthesis of Aldehydes or
Ketones
To
a
10-mL, dried three-necked flask were added
Fe(NO3)3·9H2O (0.05 mmol), DCE (4 mL), TEMPO
AHCTUNGTRENNUNG
Scheme 7. A proposed mechanism.
(0.10 mmol) and NaCl (0.10 mmol) under an atmosphere of
oxygen. The resulting suspension was stirred at room tem-
perature for 5 min under oxygen. A solution of alcohol
(1.0 mmol) in DCE (1,2-dichloroethane, 1 mL) was then
added to the suspension and the resulting mixture was
stirred at room temperature with oxygen from a balloon
until the reaction was complete as monitored by TLC
(eluent: petroleum ether/ethyl acetate=10:1). The resulting
mixture was diluted with diethyl ether (30 mL), dried over
anhydrous MgSO4, and filtered through a short column of
silica gel to remove the inorganic salts. After evaporation,
the NMR yield was determined by 1H NMR analysis and
the residue was purified by column chromatography on
silica gel (petroleum ether/diethyl ether=20/1) to afford the
corresponding the aldehyde or ketone.
verted to TEMPO by its reaction with Fe3+.[33] Fe2+
would be reoxidized to Fe3+ by the reaction with NO2
in the presence of a proton, forming NO and water aÀt
the same time. NO2 was first generated from NO3
and would be regenerated by the reaction of NO with
O2. Although the role of NaCl is not quite clear yet,
we believe that ClÀ is most likely behaving as a
unique electron-donating ligand31 to pump electrons
to the d orbitals of Fe3+ to facilitate the semi-oxida-
tive addition-type coupling with TEMPO. Due to the
+3 oxidation state, this coupling reaction of TEMPO
with Fe3+ would be very slow in the absence of
sodium chloride. Of course, further study is obviously
needed to unveil the actual mechanism.
Synthesis of 2-Benzylbuta-2,3-dienal
The reaction of 2-benzylbuta-2,3-dien-1-ol (160.6 mg,
1.0 mmol), FeACTHNUTRGNE(UNG NO3)3·9H2O (20.3 mg, 0.05 mmol), TEMPO
(15.6 mg, 0.10 mmol) and NaCl (5.8 mg, 0.10 mmol) in DCE
(5 mL) afforded 2-benzylbuta-2,3-dienal as an oil; yield:
114.5 mg (72%); 1H NMR (300 MHz, CDCl3): d=9.61 (s,
1H), 7.31–7.15 (m, 5H), 5.28 (t, J=2.4 Hz, 2H), 3.52 (t, J=
Conclusions
In conclusion, we have developed a mild and practical
FeACHTUNGTRENNUNG
(NO3)3/TEMPO-catalyzed aerobic oxidation of the 2.6 Hz, 2H); 13C NMR (75.4 MHz, CDCl3): d=222.50,
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1011

Shengming Ma et al.
FULL PAPERS
191.41, 138.52, 128.84, 128.35, 126.41, 110.62, 80.83, 30.84;
IR (neat): n=2827, 2728, 1955, 1928, 1677, 1602, 1495, 1454,
1426, 1227, 1144, 1071, 1030 cmÀ1; MS (EI): m/z=158 (M+,
5.25), 129 (100); HR-MS: m/z=158.0733, calcd. for C11H10O
(M+): 158.0732.
1.58–1.25 (m, 8H), 0.90 (t, J=6.5 Hz, 3H); 13C NMR
(75.4 MHz, CDCl3): d=216.95, 194.78, 138.34, 131.85,
128.97, 127.73, 106.88, 79.26, 31.56, 28.85, 27.83, 27.80, 22.53,
13.98; IR (neat): n=3059, 2955, 2856, 1932, 1650, 1598,
1579, 1447, 1315, 1269, 1177, 1072 cmÀ1; MS (EI): m/z=228
(M+, 1.69), 105 (100); HR-MS: m/z=228.1512, calcd. for
C16H20O (M+): 228.1514.
The reaction of 2-benzylbuta-2,3-dien-1-ol (160.2 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (20.3 mg, 0.05 mmol), TEMPO
(7.8 mg, 0.05 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE
(5 mL) afforded 2-benzylbuta-2,3-dienal as an oil; yield:
112.5 mg (71%).
Synthesis of 1-(4-Chlorophenyl)buta-2,3-dien-1-one
The reaction of 1-(4-chlorophenyl)-buta-2,3-dien-1-ol
(178.4 mg, 1.0 mmol), FeACTHNUTRGNE(NUG NO3)3·9H2O (19.8 mg, 0.05 mmol),
Synthesis of 2,3-Tridecadienal
TEMPO (8.1 mg, 0.05 mmol) and NaCl (5.6 mg, 0.10 mmol)
in DCE (5 mL) afforded 1-(4-chlorophenyl)buta-2,3-dien-1-
The reaction of 2,3-tridecadien-1-ol (196.4 mg, 1.0 mmol),
1
Fe
N
one[34] as an oil; yield: 136.9 mg (78%); H NMR (300 MHz,
0.10 mmol) and NaCl (5.8 mg, 0.10 mmol) in DCE (5 mL)
afforded 2,3-tridecadienal as an oil; yield: 156.2 mg (80%)
(petroleum ether/ethyl acetate=40/1); H NMR (300 MHz,
CDCl3): d=7.84 (d, J=8.7 Hz, 2H), 7.42 (d, J=8.7 Hz, 2H),
6.39 (t, J=6.5 Hz, 1H), 5.27 (d, J=6.6 Hz, 2H); 13C NMR
(75.4 MHz, CDCl3): d=217.1, 189.9, 139.1, 135.7, 130.1,
128.6, 93.2, 79.4; IR (neat): n=3065, 2987, 1960, 1930, 1653,
1586, 1487, 1400, 1276, 1211, 1174, 1090, 841 cmÀ1; MS (EI):
1
CDCl3): d=9.44 (d, J=7.2 Hz, 1H), 5.84–5.71 (m, 2H),
2.25–2.10 (m, 2H), 1.55–1.42 (m, 2H), 1.42–1.20 (m, 12H),
0.84 (t, J=6.6 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d=
218.94, 192.00, 98.47, 96.19, 31.73, 29.38, 29.17, 29.15, 28.82,
28.71, 27.36, 22.53, 13.94; MS(EI): m/z=194 (M+, 0.79), 81
(100); IR (neat): n=2924, 2854, 1943, 1690, 1465, 1107,
m/z=180 [M
The reaction of 1-(4-chlorophenyl)-buta-2,3-dien-1-ol
(180.1 mg, 1.0 mmol), Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol),
(37Cl)+, 1.61], 178 [M(35Cl)+, 5.71], 139 (100).
ACHUTGTNRENNUG CAHTUNGTRENNUGN
AHCTUNGTRENNUNG
TEMPO (15.7 mg, 0.10 mmol) and NaCl (5.9 mg,
0.10 mmol) in DCE (5 mL) afforded 1-(4-chlorophenyl)bu-
ta-2,3-dien-1-one;[34] NMR yield: 84%.
1081 cmÀ1
; HR-MS: m/z=194.1671, calcd. for C13H22O
(M+): 194.1671.
The reaction of 2,3-tridecadien-1-ol (196.5 mg, 1.0 mmol),
The reaction of 1-(4-chlorophenyl)-buta-2,3-dien-1-ol
Fe
G
(180.6 mg, 1.0 mmol), FeACHTNGUTER(NNUG NO3)3·9H2O (20.3 mg, 0.05 mmol),
0.05 mmol) and NaCl (3.1 mg, 0.05 mmol) in DCE (5 mL)
afforded 2,3-tridecadienal as an oil; yield: 159.6 mg (82%)
(petroleum ether/ethyl acetate=40/1).
TEMPO (8.0 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-(4-chlorophenyl)buta-2,3-dien-1-
one;[34] NMR yield: 83%.
Synthesis of Trideca-1,2-dien-4-one
Synthesis of 3-Hexylocta-1,2-dien-4-one
The reaction of trideca-1,2-dien-4-ol (197.0 mg, 1.0 mmol),
The reaction of 3-hexylocta-1,2-dien-4-ol (211.3 mg,
Fe
G
1.0 mmol), FeACHTNGUTERNNU(G NO3)3·9H2O (41.0 mg, 0.10 mmol), TEMPO
0.10 mmol) and NaCl (6.2 mg, 0.10 mmol) in DCE (5 mL)
afforded trideca-1,2-dien-4-one as an oil; yield: 169.0 mg
(87%); H NMR (300 MHz, CDCl3): d=5.74 (t, J=6.5 Hz,
(16.1 mg, 0.10 mmol) and NaCl (5.4 mg, 0.10 mmol) in DCE
(5 mL) afforded 3-hexylocta-1,2-dien-4-one as an oil; yield:
156.1 mg (75%); 1H NMR (300 MHz, CDCl3): d=5.16 (t,
J=2.9 Hz, 2H), 2.64 (t, J=7.7 Hz, 2H), 2.20–2.10 (m, 2H),
1.61–1.49 (m, 2H), 1.42–1.21 (m, 10H), 0.93–0.82 (m, 6H);
13C NMR (75.4 MHz, CDCl3): d=216.25, 201.38, 108.62,
79.35, 38.94, 31.61, 28.88, 27.82, 27.21, 26.27, 22.58, 22.37,
14.02, 13.82; IR (neat): n=2957, 2928, 2858, 1934, 1677,
1464, 1410, 1379, 1349, 1259, 1175, 1086, 1020 cmÀ1; MS
(EI): m/z=208 (M+, 0.48), 85 (100); HR-MS: m/z=
208.1826, calcd. for C14H24O (M+): 208.1827.
1
1H), 5.20 (d, J=6.3 Hz, 2H), 2.57 (t, J=7.4 Hz, 2H), 1.63–
1.50 (m, 2H), 1.35–1.17 (m, 12H), 0.85(t, J=6.3 Hz, 3H);
13C NMR (75.4 MHz, CDCl3): d=216.57, 200.88, 96.62,
79.16, 39.19, 31.81, 29.37, 29.33, 29.19, 29.14, 24.53, 22.59,
14.00; IR (neat): n=2955, 2854, 1961, 1934, 1681, 1465,
1410, 1365, 1157, 1105, 1068 cmÀ1; MS (EI): m/z=194 (M+,
1.37), 41 (100); HR-MS: m/z=194.1673, calcd. for C13H22O
(M+): 194.1671.
The reaction of trideca-1,2-dien-4-ol (196.3 mg, 1.0 mmol),
The reaction of 3-hexylocta-1,2-dien-4-ol (2.1031 g,
Fe
G
10.0 mmol), FeACHTNGUTERNNU(G NO3)3·9H2O (208.2 mg, 0.5 mmol), TEMPO
0.05 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE (5 mL)
afforded trideca-1,2-dien-4-one as an oil; yield: 171.5 mg
(88%).
(77.7 mg, 0.50 mmol) and NaCl (59.7 mg, 1.0 mmol) in DCE
(4 mL) afforded 3-hexylocta-1,2-dien-4-one as an oil: yield:
1.3472 g (65%).
Synthesis of 2-Hexyl-1-phenylbuta-2,3-dien-1-one
Synthesis of Non-2-ynal
The
reaction
of
2-hexyl-1-phenylbuta-2,3-dien-1-ol
(NO3)3·9H2O (40.6 mg, 0.10 mmol),
The reaction of non-2-yn-1-ol (140.3 mg, 1.0 mmol), Fe-
ACHTNUGERTN(NUGN NO3)3·9H2O (20.5 mg, 0.05 mmol), TEMPO (7.7 mg,
(229.4 mg, 1.0 mmol), Fe
N
TEMPO (15.7 mg, 0.10 mmol) and NaCl (5.7 mg,
0.10 mmol) in DCE (5 mL) afforded 2-hexyl-1-phenylbuta-
2,3-dien-1-one as an oil: yield: 123.1 mg (54%) (petroleum
ether/ethyl acetate=30/1): H NMR (300 MHz, CDCl3): d=
7.76 (d, J=7.8 Hz, 2H), 7.49 (t, J=7.1 Hz, 1H), 7.38 (t, J=
7.7 Hz, 2H), 5.04 (t, J=2.7 Hz, 2H), 2.45–2.35 (m, 2H),
0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE (5 mL)
afforded non-2-ynal[35] as an oil; yield: 121.6 mg (88%) (pe-
troleum ether/ethyl acetate=15/1); 1H NMR (300 MHz,
CDCl3): d=9.18 (s, 1H), 2.41 (t, J=7.1 Hz, 2H), 1.66–1.50
(m, 2H), 1.48–1.24 (m, 6H), 0.90 (t, J=6.6 Hz, 3H);
13C NMR (75.4 MHz, CDCl3): d=176.86, 99.20, 81.61, 31.07,
1
1012
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
28.39, 27.41, 22.34, 19.00, 13.86; IR (neat): n=2930, 2859,
TEMPO (8.1 mg, 0.05 mmol) and NaCl (6.0 mg, 0.10 mmol)
2237, 2200, 1716, 1670, 1458, 1380, 1278, 1225, 1137 cmÀ1
;
in DCE (5 mL) afforded (4-methoxyphenyl)propynal[38] as a
solid; yield: 124.2 mg (78%) (petroleum ether/diethyl
ether=20/1).
MS (EI): m/z=138 (M+, 0.40), 137 (M+ÀH, 1.57), 41 (100).
The reaction of non-2-yn-1-ol (139.2 mg, 1.0 mmol), Fe-
ACHTUNGTRENNUNG(NO3)3·9H2O (20.7 mg, 0.05 mmol), TEMPO (4.7 mg,
0.03 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE (5 mL)
afforded non-2-ynal[35] as an oil; yield: 117.6 mg (86%) (pe-
troleum ether/ethyl acetate=20/1).
Synthesis of 1-(4-Trifluoromethylphenyl)hept-2-yn-1-
one
The reaction of 1-(4-trifluoromethylphenyl)hept-2-yn-1-ol
(256.1 mg, 1.0 mmol), FeACTHNUTRGNE(NUG NO3)3·9H2O (20.2 mg, 0.05 mmol),
Synthesis of 3-Phenylpropynal
TEMPO (7.8 mg, 0.05 mmol) and NaCl (2.9 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-(4-trifluoromethyl-phenyl)hept-2-
yn-1-one as an ouil; yield: 227.2 mg (89%) (petroleum
The reaction of 3-phenylprop-2-yn-1-ol (132.3 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (19.8 mg, 0.05 mmol), TEMPO
1
(7.8 mg, 0.05 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE
(5 mL) afforded 3-phenylpropynal[36] as an oil: yield:
112.1 mg (86%) (petroleum ether/diethyl ether=20/1);
1H NMR (300 MHz, CDCl3): d=9.41 (s, 1H), 7.59 (d, J=
7.8 Hz, 2H), 7.48 (t, J=6.9 Hz, 1H), 7.39 (t, J=6.9 Hz, 2H);
13C NMR (75.4 MHz, CDCl3): d=176.61, 133.16, 131.19,
128.65, 119.34, 94.96, 88.35; IR (neat): n=2854, 2738, 2240,
2185, 1654, 1489, 1443, 1387, 1260, 1070 cmÀ1; MS (EI):
m/z=130 (M+, 64.02), 102 (100).
ether/diethyl ether=20/1); H NMR (300 MHz, CDCl3): d=
8.24 (d, J=8.1 Hz, 2H), 7.74 (d, J=8.1 Hz, 2H), 2.54 (t, J=
6.9 Hz, 2H), 1.75–1.61 (m, 2H), 1.58–1.44 (m, 2H), 0.98 (t,
J=7.4 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d=176.78,
139.45, 134.91 (q, J=32.3 Hz), 129.70, 125.60–125.40 (m),
123.54 (q, J=272.6 Hz), 98.27, 79.38, 29.70, 22.02, 18.85,
13.37; IR (neat): n=2962, 2936, 2875, 2239, 2201, 1650,
1583, 1509, 1466, 1411, 1322, 1261, 1170, 1128, 1108, 1064,
1016 cmÀ1; MS (EI): m/z=254 (M+, 3.14), 173 (100); HR-
MS: m/z=254.0919, calcd. for C14H13OF3 (M+): 254.0918.
The reaction of 1-(4-trifluoromethylphenyl)hept-2-yn-1-ol
The reaction of 3-phenylprop-2-yn-1-ol (1.3092 mg,
10.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (205.0 mg, 0.5 mmol), TEMPO
(45.4 mg, 0.3 mmol) and NaCl (30.5 mg, 0.5 mmol) in DCE
(4 mL) afforded 3-phenylpropynal[36] as an oil: yield: 1.024 g
(79%) (petroleum ether/diethyl ether=20/1).
(256.0 mg, 1.0 mmol), FeACTHNUTRGNE(NUG NO3)3·9H2O (20.5 mg, 0.05 mmol),
TEMPO (4.7 mg, 0.03 mmol) and NaCl (2.9 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-(4-trifluoromethyl-phenyl)hept-2-
yn-1-one as an oil: yield: 197.8 mg (78%) (petroleum ether/
diethyl ether=20/1).
Synthesis of 3-(4-Nitrophenyl)propynal
The reaction of 3-(4-nitrophenyl)prop-2-yn-1-ol (178.3 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (20.5 mg, 0.05 mmol), TEMPO
Synthesis of 1-Phenylhept-1-yn-3-one
The
1.0 mmol), FeACHTUNGTRENNUNG
reaction
of
1-phenylhept-1-yn-3-ol
(187.8 mg,
(8.0 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE
(5 mL) afforded 3-(4-nitrophenyl)-propynal[37] as a yellow
solid; yield: 151.9 mg (86%) (petroleum ether/diethyl
(NO3)3·9H2O (20.5 mg, 0.05 mmol), TEMPO
(16.0 mg, 0.10 mmol) and NaCl (6.0 mg, 0.10 mmol) in DCE
(5 mL) afforded 1-phenylhept-1-yn-3-one[39] as an oil: yield:
161.3 mg (87%) (petroleum ether/diethyl ether=20/1);
1H NMR (300 MHz, CDCl3): d=7.56 (d, J=7.5 Hz, 2H),
7.47–7.30 (m, 3H), 2.66 (t, J=7.4 Hz, 2H), 1.78–1.64 (m,
2H), 1.46–1.31 (m, 2H), 0.95 (t, J=7.4 Hz, 3H); 13C NMR
(75.4 MHz, CDCl3): d=188.01, 132.87, 130.50, 128.50,
119.97, 90.37, 87.77, 45.14, 26.14, 22.05, 13.70; IR (neat): n=
3063, 2958, 2872, 2201, 1666, 1489, 1443, 1272, 1158, 1125,
1067 cmÀ1; MS (EI): m/z=186 (M+, 1.67), 129 (100).
The reaction of 1-phenylhept-1-yn-3-ol (187.9 mg,
1.0 mmol), FeACTHNUTRGNE(UNG NO3)3·9H2O (20.1 mg, 0.05 mmol), TEMPO
(7.9 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE
(5 mL) afforded 1-phenylhept-1-yn-3-one[39] as an oil; yield:
169.3 mg (91%) (petroleum ether/diethyl ether=20/1).
The reaction of 1-phenylhept-1-yn-3-ol (1.8686 g,
1
ether=20/1); H NMR (300 MHz, CDCl3): d=9.43 (s, 1H),
8.24 (d, J=8.4 Hz, 2H), 7.75 (d, J=8.7 Hz, 2H); 13C NMR
(75.4 MHz, CDCl3): d=176.03, 148.70, 133.78, 125.87,
123.71, 90.67, 90.49; IR (neat): n=2924, 2854, 2195, 1655,
1592, 1511, 1342, 1103 cmÀ1; MS (EI): m/z=175 (M+, 54.92),
75 (100).
The reaction of 3-(4-nitrophenyl)prop-2-yn-1-ol (177.6 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (20.3 mg, 0.05 mmol), TEMPO
(4.9 mg, 0.03 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE
(5 mL) afforded 3-(4-nitrophenyl)-propynal[37] as a yellow
solid; yield: 133.7 mg (76%) (petroleum ether/ethyl ace-
tate=10/1).
Synthesis of 3-(4-Methoxyphenyl)propynal
The 3-(4-methoxyphenyl)prop-2-yn-1-ol
reaction
of
10.0 mmol), FeACTHNUTRGNEUNG(NO3)3·9H2O (205.9 mg, 0.5 mmol), TEMPO
(161.9 mg, 1.0 mmol), FeACHTUTGNREN(NUGN NO3)3·9H2O (20.2 mg, 0.05 mmol),
(47.7 mg, 0.3 mmol) and NaCl (28.6 mg, 0.5 mmol) in DCE
(4 mL) afforded 1-phenylhept-1-yn-3-one[39] as an oil; yield:
1.7103 g (93%) (petroleum ether/diethyl ether=20/1).
TEMPO (15.6 mg, 0.10 mmol) and NaCl (6.0 mg,
0.10 mmol) in DCE (5 mL) afforded (4-methoxyphenyl)pro-
pynal[38] as a solid; yield: 110.8 mg (69%) (petroleum ether/
diethyl ether=20/1); 1H NMR (300 MHz, CDCl3): d=9.38
(s, 1H), 7.54 (d, J=8.7 Hz, 2H), 6.90 (d, J=8.7 Hz, 2H),
3.83 (s, 3H); 13C NMR (75.4 MHz, CDCl3): d=176.32,
161.78, 135.03, 114.14, 110.67, 96.15, 88.37, 55.07; IR (neat):
n=2178, 1643, 1598, 1507, 1303, 1254, 1175, 1022 cmÀ1; MS
(EI): m/z (%)=160 (M+, 100).
Synthesis of 1-(tert-Butyldimethylsilyloxy)undec-2-yn-
4-one
The reaction of 1-(tert-butyldimethylsilanyloxy)undec-2-yn-
4-ol (298.8 mg, 1.0 mmol), FeACTHNUTRGNE(UNG NO3)3·9H2O (21.2 mg,
0.05 mmol), TEMPO (7.9 mg, 0.05 mmol) and NaCl (3.1 mg,
0.05 mmol) in DCE (5 mL) afforded 1-(tert-butyldimethylsi-
lanyloxy)undec-2-yn-4-one as an oil; yield: 271.3 mg (92%)
The reaction of 3-(4-methoxyphenyl)prop-2-yn-1-ol
(162.2 mg, 1.0 mmol), FeACTHNUTRGNE(NUG NO3)3·9H2O (20.6 mg, 0.05 mmol),
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1013

Shengming Ma et al.
FULL PAPERS
1
(petroleum ether/diethyl ether=20/1); H NMR (300 MHz,
CDCl3): d=4.46 (s, 2H), 2.54 (t, J=7.4 Hz, 2H), 1.74–1.62
(m, 2H), 1.38–1.22 (m, 8H), 0.96–0.86 (m, 12H), 0.13 (s,
6H); 13C NMR (75.4 MHz, CDCl3): d=187.71, 90.19, 83.88,
51.50, 45.33, 31.59, 28.95, 28.90, 25.70, 23.97, 22.55, 18.22,
14.0, À5.23; IR (neat): n=2929, 2857, 2216, 1679, 1464,
1364, 1255, 1153, 1098 cmÀ1; MS (EI): m/z=296 (M+, 0.15),
239 (M+Àbutyl, 67.49), 75 (100); HR-MS: m/z=296.2174,
calcd. for C17H32O2Si (M+): 296.2172.
0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE (5 mL)
afforded undec-6-yn-5-one[42] as an oil; yield: 152.4 mg
(92%) (petroleum ether/diethyl ether=15/1); 1H NMR
(300 MHz, CDCl3): d=2.52 (t, J=7.4 Hz, 2H), 2.37 (t, J=
6.9 Hz, 2H), 1.71–1.60 (m, 4H), 1.60–1.28 (m, 4H), 0.97–
0.89 (m, 6H); 13C NMR (75.4 MHz, CDCl3): d=188.43,
94.10, 80.87, 45.20, 29.71, 26.19, 22.08, 21.89, 18.57, 13.72,
13.40; IR (neat): n=2959, 2933, 2873, 2213, 1672, 1465,
1243, 1168 cmÀ1; MS (EI): m/z=165 (M+ÀH, 0.07), 151
(M+ÀCH3, 4.57), 109 (M+Àn-butyl, 100).
The reaction of 1-(tert-butyldimethylsilanyloxy)undec-2-
yn-4-ol (292.4 mg, 1.0 mmol), Fe
(NO3)3·9H2O (21.1 mg,
The reaction of undec-6-yn-5-ol (168.0 mg, 1.0 mmol),
0.05 mmol), TEMPO (5.1 mg, 0.03 mmol) and NaCl (3.2 mg,
0.05 mmol) in DCE (5 mL) afforded 1-(tert-butyldimethylsi-
lanyloxy)undec-2-yn-4-one as an oil: yield: 257.9 mg (89%)
(petroleum ether/diethyl ether=30/1).
FeACHTGNUTER(NNUG NO3)3·9H2O (20.4 mg, 0.05 mmol), TEMPO (4.9 mg,
0.03 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE (5 mL)
afforded undec-6-yn-5-one[42] as an oil; yield: 152.2 mg
(92%) (petroleum ether/diethyl ether=25/1).
Synthesis of 1-Phenyl-3-(trimethylsilyl)propynone
Synthesis of Dodec-1-yn-3-one
The reaction of 1-phenyl-3-trimethylsilanylprop-2-yn-1-ol
The reaction of dodec-1-yn-3-ol (182.3 mg, 1.0 mmol),
(201.8 mg, 1.0 mmol), Fe
G
FeACHTGNUTER(NNUG NO3)3·9H2O (20.4 mg, 0.05 mmol), TEMPO (7.9 mg,
TEMPO (8.1 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-phenyl-3-(trimethylsilyl)propy-
none[40] as an oil; yield: 183.5 mg (92%) (petroleum ether/di-
0.05 mmol) and NaCl (3.1 mg, 0.05 mmol) in DCE (5 mL)
afforded dodec-1-yn-3-one[43] as an oil; yield: 167.4 mg
(93%) (petroleum ether/diethyl ether=20/1); 1H NMR
(300 MHz, CDCl3): d=3.20 (s, 1H), 2.58 (t, J=7.4 Hz, 2H),
1.75–1.60 (m, 2H), 1.37–1.20 (m, 12H), 0.88 (t, J=6.3 Hz,
3H); 13C NMR (75.4 MHz, CDCl3): d=187.51, 81.49, 78.18,
45.44, 31.82, 29.33, 29.26, 29.20, 28.87, 23.77, 22.63, 14.04; IR
(neat): n=2925, 2855, 2093, 1681, 1465, 1404, 1377, 1205,
1132, 1089, 1051 cmÀ1; MS (EI): m/z=180 (M+, 0.22), 179
(M+ÀH, 0.85), 53 (100).
1
ethyl ether=20/1); H NMR (300 MHz, CDCl3): d=8.14 (d,
J=8.1 Hz, 2H), 7.61 (t, J=7.4 Hz, 1H), 7.48 (t, J=7.7 Hz,
2H), 0.32 (s, 9H); 13C NMR (75.4 MHz, CDCl3): d=177.64,
136.48, 134.11, 129.60, 128.54, 100.84, 100.49, À0.73; IR
(neat): n=2153, 1643, 1598, 1579, 1450, 1312, 1243, 1173,
1035, 1016 cmÀ1; MS (EI): m/z=202 (M+, 16.37), 187 (100).
The reaction of 1-phenyl-3-trimethylsilanylprop-2-yn-1-ol
(200.6 mg, 1.0 mmol), Fe
N
The reaction of dodec-1-yn-3-ol (182.6 mg, 1.0 mmol),
TEMPO (4.7 mg, 0.03 mmol) and NaCl (3.2 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-phenyl-3-(trimethylsilyl)propy-
none[40] as an oil; yield: 185.5 mg (93%) (petroleum ether/di-
ethyl ether=20/1).
FeACHTGNUTER(NNUG NO3)3·9H2O (20.4 mg, 0.05 mmol), TEMPO (4.7 mg,
0.03 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE (5 mL)
afforded dodec-1-yn-3-one[43] as an oil; yield: 163.2 mg
(91%) (petroleum ether/diethyl ether=25/1).
Synthesis of 1-(4-Methoxyphenyl)hept-2-yn-1-one
Synthesis of (E)-3-Phenyl-2-propen-1-al
The
reaction
of
1-(4-methoxyphenyl)hept-2-yn-1-ol
(NO3)3·9H2O (20.2 mg, 0.05 mmol),
The reaction of (E)-3-phenyl-2-propen-1-ol (1.3492 g,
10.0 mmol), FeACHTNGUTERNNU(G NO3)3·9H2O (207.8 mg, 0.5 mmol), TEMPO
(218.7 mg, 1.0 mmol), Fe
N
TEMPO (7.9 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-(4-methoxyphenyl)hept-2-yn-1-
one[41] as an oil; yield: 181.4 mg (84%) (petroleum ether/di-
(47.7 mg, 0.3 mmol) and NaCl (28.3 mg, 0.5 mmol) in DCE
(4 mL) afforded (E)-3-phenyl-2-propen-1-al[44] as an oil;
yield: 1.1127 g (84%) (petroleum ether/diethyl ether=20/1)
1
1
ethyl ether=10/1); H NMR (300 MHz, CDCl3): d=8.10 (d,
as oil; H NMR (300 MHz, CDCl3): d=9.71 (d, J=7.8 Hz,
J=8.4 Hz, 2H), 6.94 (d, J=8.7 Hz, 2H), 3.87 (s, 3H), 2.48
(t, J=6.9 Hz, 2H), 1.71–1.58 (m, 2H), 1.57–1.42 (m, 2H),
0.96 (t, J=7.2 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d=
176.74, 164.12, 131.70, 130.23, 113.57, 95.69, 79.50, 55.38,
29.76, 21.91, 18.71, 13.35; IR (neat): n=2958, 2934, 2872,
2238, 2199, 1635, 1594, 1573, 1508, 1460, 1421, 1316, 1251,
1164, 1113, 1026 cmÀ1; MS (EI): m/z=216 (M+, 63.27), 135
(100).
1H), 7.61–7.39 (m, 6H), 6.73 (dd, J1 =16.2 Hz, J2 =7.8 Hz,
1H); 13C NMR (75.4 MHz, CDCl3): d=193.7, 152.8, 134.0,
131.3, 129.1, 128.6, 128.5; IR (neat): n=3061, 3028, 2814,
2743, 1670, 1625, 1494, 1450, 1294, 1251, 1120, 971, 745 cmÀ1
;
MS (EI): m/z (%)=132 (M+, 61.81), 131 (100).
Synthesis of (E)-4-Methyl-1-phenylpent-1-en-3-one
The reaction of (E)-4-methyl-1-phenylpent-1-en-3-one
(1.7630 g, 10.0 mmol), Fe(NO3)3·9H2O (202.0 mg, 0.5 mmol),
The reaction of 1-(4-methoxyphenyl)hept-2-yn-1-ol
(218.5 mg, 1.0 mmol), FeACTHNUTRGNE(NUG NO3)3·9H2O (20.1 mg, 0.05 mmol),
AHCTUNGTRENNUNG
TEMPO (46.9 mg, 0.3 mmol) and NaCl (29.2 mg, 0.5 mmol)
in DCE (4 mL) afforded (E)-4-methyl-1-phenylpent-1-en-3-
one45 as an oil; yield: 1.4985 g (86%) (petroleum ether/di-
TEMPO (4.7 mg, 0.03 mmol) and NaCl (3.0 mg, 0.05 mmol)
in DCE (5 mL) afforded 1-(4-methoxyphenyl)hept-2-yn-1-
one[41] as an oil; yield: 183.1 mg (85%) (petroleum ether/di-
ethyl ether=10/1).
1
ethyl ether=20/1); H NMR (300 MHz, CDCl3): d=7.61 (d,
J=16.2 Hz, 1H), 7.57–7.52 (m, 2H), 7.41–7.34 (m, 3H), 6.82
(d, J=7.8 Hz, 1H), 2.93 (hept, J=6.9 Hz, 1H), 1.19 (s, 3H),
1.17 (s, 3H); 13C NMR (75.4 MHz, CDCl3): d=203.62,
142.27, 134.59, 130.21, 128.79, 128.16, 124.36, 39.14, 18.37;
IR (neat): n=3028, 1687, 1662, 1610, 1576, 1495, 1465, 1449,
Synthesis of Undec-6-yn-5-one
The reaction of undec-6-yn-5-ol (168.0 mg, 1.0 mmol),
FeACHTUNGTRENNUNG(NO3)3·9H2O (20.4 mg, 0.05 mmol), TEMPO (7.9 mg,
1014
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
1383, 1348, 1301, 1201, 1147, 1120, 1087, 1054 cmÀ1; MS
Synthesis of 4-Nitrobenzaldehyde
(EI): m/z=159 (M+ÀCH3, 7.13), 41 (100).
The reaction of (4-nitrophenyl)methanol (152.6 mg,
1.0 mmol), Fe(NO3)3·9H2O (20.6 mg, 0.05 mmol), TEMPO
AHCTUNGTRENNUNG
Synthesis of 2-Phenylcyclohex-2-enone
(8.1 mg, 0.05 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE
(5 mL) afforded 4-nitrobenzaldehyde[48] as a solid; yield:
139.1 mg (92%) (petroleum ether/diethyl ether=5/1);
1H NMR (300 MHz, CDCl3): d=10.16 (s, 1H), 8.39 (d, J=
8.4 Hz, 2H), 8.07 (d, J=8.4 Hz, 2H); 13C NMR (75.4 MHz,
CDCl3): d=190.23, 140.07, 130.45, 124.28; IR (neat): n=
2852, 1707, 1606, 1539, 1382, 1346, 1325, 1287, 1198, 1105,
1008 cmÀ1; MS (EI): m/z=151 (M+, 73.95), 51 (100).
The reaction of (4-nitrophenyl)methanol (11.5304 g,
10.0 mmol), FeACTHNUTRGNEUNG(NO3)3·9H2O (202.5 mg, 0.5 mmol), TEMPO
(47.7 mg, 0.3 mmol) and NaCl (29.5 mg, 0.5 mmol) in DCE
(4 mL) afforded 4-nitrobenzaldehyde[48] as a solid; yield:
1.3114 g (87%) (petroleum ether/ethyl acetate=5/1).
The reaction of 2-phenylcyclohex-2-enol (175.0 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (20.2 mg, 0.05 mmol), TEMPO
(15.6 mg, 0.10 mmol) and NaCl (5.9 mg, 0.10 mmol) in DCE
(5 mL) afforded 2-phenylcyclohex-2-enone[46] as an oil;
yield: 149.2 mg (86%) (petroleum ether/diethyl ether=20/
1
1); H NMR (300 MHz, CDCl3): d=7.34–7.20 (m, 5H), 6.95
(t, J=4.1 Hz, 1H), 2.56–2.40 (m, 4H), 2.08–1.96 (m, 2H);
13C NMR (75.4 MHz, CDCl3): d=197.47, 147.75, 139.92,
136.32, 128.31, 127.61, 127.16, 38.73, 26.22, 22.57; IR (neat):
n=2948, 2930, 1661, 1553, 1491, 1443, 1427, 1357, 1315,
1279, 1261, 1208, 1155, 1119, 1071, 1032 cmÀ1; MS (EI):
m/z=172 (M+, 59.46), 115 (100).
The reaction of 2-phenylcyclohex-2-enol (1.7440 g,
10.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (202.0 mg, 0.5 mmol), TEMPO
Synthesis of Acetophenone
(46.9 mg, 0.3 mmol) and NaCl (29.3 mg, 0.5 mmol) in DCE
(4 mL) afforded 2-phenylcyclohex-2-enone[46] as an oil;
yield: 1.3963 g (81%) (petroleum ether/ethyl acetate=20/1).
The reaction of 1-phenylethanol (121.2 mg, 1.0 mmol),
FeACHTUNRTGNE(NUG NO3)3·9H2O (20.6 mg, 0.05 mmol), TEMPO (7.8 mg,
0.05 mmol) and NaCl (2.9 mg, 0.05 mmol) in DCE (5 mL)
afforded acetophenone[48] as an oil; yield: 103.4 mg (87%)
Synthesis of 4-Chlorobenzaldehyde
1
(petroleum ether/diethyl ether=15/1); H NMR (300 MHz,
The reaction of 4-chlorophenyl)methanol (142.6 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (20.0 mg, 0.05 mmol), TEMPO
CDCl3): d=7.96 (d, J=7.8 Hz, 2H), 7.56 (t, J=7.4 Hz, 1H),
7.46 (t, J=7.7 Hz, 2H), 2.60 (s, 3H); 13C NMR (75.4 MHz,
CDCl3): d=198.09, 137.15, 133.05, 128.54, 128.27, 26.53; IR
(neat): n=1681, 1598, 1582, 1448, 1358, 1263, 1180, 1078,
1024 cmÀ1; MS (EI): m/z=120 (M+, 33.35), 77 (100).
(8.4 mg, 0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE
(5 mL) afforded 4-chlorobenzaldehyde[44] as a white solid;
yield: 122.2 mg (87%) (petroleum ether/diethyl ether=20/
1); 1H NMR (300 MHz, CDCl3): d=9.98 (s, 1H), 7.82 (d,
J=7.5 Hz, 2H), 7.51 (d, J=7.8 Hz, 2H); 13C NMR
(75.4 MHz, CDCl3): d=190.75, 140.91, 134.72, 130.85,
129.42; IR (neat): 2856, 1699, 1588, 1575, 1485, 1385, 1295,
1264, 1205, 1165, 1092, 1012 cmÀ1; MS (EI): m/z=142
To a 500-mL, dried, three-necked flask were added
FeACHTUNRTGNE(NUG NO3)3·9H2O (8.0782 g, 20 mmol), TEMPO (3.1221 g,
20 mmol), NaCl (1.6731 g, 20 mmol) and DCE (100 mL)
under an atmosphere of oxygen. This resulting suspension
was stirred at room temperature for 5 min under oxygen. 1-
Phenylethanol (120 mL, 1.0 mol) was then added to the sus-
pension dropwise and the resulting mixture was stirred at
room temperature under the atmosphere of oxygen until the
reaction was complete as monitored by TLC (eluent: petro-
leum ether/ethyl acetate=10:1). The resulting mixture was
then distilled under the atmospheric pressure to remove 1,2-
dichloroethane and water. Then, the residue was distilled
under the reduced pressure to afford phenyl methyl ketone
(bp 98~100 8C/20 mmHg); yield: 109.7478 g (91%).
[M
The reaction of 4-chlorophenyl)methanol (1.4259 g,
10.0 mmol), Fe(NO3)3·9H2O (203.1 mg, 0.5 mmol), TEMPO
CHTUNGTRENNUNG CHTUNGTRENNUGN
+A(37Cl), 10.04], 140 [M+A(35Cl), 35.62], 41 (100).
ACHTUNGTRENNUNG
(47.5 mg, 0.3 mmol) and NaCl (29.7 mg, 0.5 mmol) in DCE
(4 mL) afforded 4-chlorobenzaldehyde[44] as a white solid:
yield: 1.1675 g (83%) (petroleum ether/diethyl ether=20/1).
Synthesis of 4-Methoxybenzaldehyde
The reaction of (4-methoxyphenyl)methanol (137.6 mg,
1.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (21.0 mg, 0.05 mmol), TEMPO
For a 4.0-mol scale reaction with 1 mol% of each cata-
lyst.; to a 2000-mL, three-necked flask equipped with a ther-
mometer and an addition funnel were added Fe-
(7.6 mg, 0.05 mmol) and NaCl (3.1 mg, 0.05 mmol) in DCE
(5 mL) afforded 4-methoxybenzaldehyde[47] as an oil; yield:
126.2 mg (93%) (petroleum ether/diethyl ether=15/1);
1H NMR (300 MHz, CDCl3): d=9.87 (s, 1H), 7.82 (d, J=
8.4 Hz, 2H), 6.99 (d, J=8.4 Hz, 2H), 3.87 (s, 3H); 13C NMR
(75.4 MHz, CDCl3): d=190.24, 164.13, 131.45, 129.49,
113.84, 55.09; IR (neat): n=2840, 2739, 1680, 1595, 1576,
1510, 1460, 1426, 1393, 1314, 1255, 1214, 1182, 1157, 1108,
1021 cmÀ1; MS (EI): m/z 136 (M+, 69.21), 135 (100).
The reaction of (4-methoxyphenyl)methanol (1.3799 g,
10.0 mmol), FeACHTUNGTRENNUNG(NO3)3·9H2O (203.4 mg, 0.5 mmol), TEMPO
(46.6 mg, 0.3 mmol) and NaCl (29.3 mg, 0.5 mmol) in DCE
(4 mL) afforded 4-methoxybenzaldehyde[47] as an oil; yield:
1.200 g (88%) (petroleum ether/diethyl ether=15/1).
AHCTNUGTERN(GNNU NO3)3·9H2O (16.1607 g, 40.0 mmol, 1 mol%), TEMPO
(6.2510 g, 40.0 mmol, 1 mol%), NaCl (2.3377 g, 40 mmol,
1 mol%), and DCE (400 mL) under an atmosphere of air at
room temperature. Then the air atmosphere was replaced
with oxygen and the suspension was stirred at room temper-
ature for 10 min. 1-Phenylethyl alcohol (484 mL, d=1.01,
488.64 g, 4.0 mol) was then added to the suspension drop-
wise with stirring at room temperature. The reaction was
exothermic, thus, the addition rate of the alcohol was con-
trolled to keep the inside temperature around 45~508C.
The addition lasted ~1.5 h. After the addition, the tempera-
ture of the resulting mixture dropped a little bit, then start-
ed to rise to> 408C, and lasted at 42~528C for 9 h without
external heating. After that, the temperature dropped to
room temperature, which indicated the completion of the re-
action as confirmed by TLC analysis. During all the process
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1015

Shengming Ma et al.
FULL PAPERS
the flask was connected to a line to supply 1 atm of oxygen References
without releasing the oxygen to air. The resulting mixture
was then distilled under atmospheric pressure to affordd a
mixture of 1,2-dichloroethane and water, which separated
into two layers to recover 350 mL. of the solvent (88% re-
covery) and collect 59 mL of water. Then the residue was
distilled under the reduced pressure to afford phenyl methyl
ketone (bp 98~100 8C//20 mmHg); yield: 436.6414 g (91%).
[1] S. Caron, R. W. Dugger, S. G. Ruggeri, J. A. Ragan,
D. H. B. Ripin, Chem. Rev. 2006, 106, 2943.
[2] G. Tojo, M. I. Fernandez, (Eds.), Oxidation of Alcohols
to Aldehydes and Ketones:
A Guide to Current
Common Practice, Springer, Berlin, Heidelberg, 2006.
[3] For a seminal report, see: T. F. Blackburn, J. Schwartz,
J. Chem. Soc. Chem. Commun. 1977, 157.
Synthesis of Hexadecanal
[4] For a representative report, see: K. B. Peterson, R. C.
Larock, J. Org. Chem. 1998, 63, 3185.
The reaction of hexadecan-1-ol (241.7 mg, 1.0 mmol),
FeACHTUNGTRENNUNG(NO3)3·9H2O (20.5 mg, 0.05 mmol), TEMPO (8.2 mg,
[5] For a representative report, see: G. T. Brink, I. W. C. E.
Arends, R. Sheldon, Science 2000, 287, 1636.
[6] For a representative report, see: D. R. Jensen, M. J.
Schultz, J. A. Mueller, M. S. Sigman, Angew. Chem.
2003, 115, 3940; Angew. Chem. Int. Ed. 2003, 42, 3810.
[7] For a seminal report, see: M. Matsumoto, S. Ito, J.
Chem. Soc. Chem. Commun. 1981, 907.
[8] For a supported Ru-catalysis, see: K. Yamaguchi, N.
Mizuno, Angew. Chem. 2002, 114, 4720; Angew. Chem.
Int. Ed. 2002, 41, 4538.
0.05 mmol) and NaCl (3.1 mg, 0.05 mmol) in DCE (5 mL)
afforded hexadecanal[48,49] as a solid; yield: 160.4 mg (67%);
1H NMR (300 MHz, CDCl3): d=9.76 (s, 1H), 2.41 (t, J=
7.4 Hz, 2H), 1.68–1.56 (m, 2H), 1.36–1.18 (m, 24H), 0.88 (t,
J=6.2 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d=202.82,
43.89, 31.91, 29.64, 29.56, 29.40, 29.33, 29.16, 22.66, 22.08,
14.06; IR (neat): n=2912, 2849, 1729, 1704, 1470, 1411,
1392, 1373 cmÀ1; MS (EI): m/z=240 (M+, 2.20), 57 (100).
The reaction of hexadecan-1-ol (2.4269 g, 10.0 mmol),
[9] For Ru-TEMPO-cocatalyzed oxidation, see: A. Dijks-
man, I. W. C. E. Arends, R. A. Sheldon, Chem.
Commun. 1999, 1591.
FeACHTUNGTRENNUNG(NO3)3·9H2O (209.0 mg, 0.5 mmol), TEMPO (48.0 mg,
0.3 mmol) and NaCl (58.2 mg, 1.0 mmol) in DCE (10 mL)
afforded hexadecanal[48,49] as a solid; yield: 1.8371 g (76%).
[10] C. Y. Lorber, S. P. Smidt, J. A. Osborn, Eur. J. Inorg.
Chem. 2000, 655.
[11] T. Iwahama, S. Sakaguchi, Y. Nishiyama, Y. Ishii, Tetra-
hedron Lett. 1995, 36, 6923.
Synthesis of Tridecan-2-one
The reaction of tridecan-2-ol (201.1 mg, 1.0 mmol),
FeACHTUNGTRENNUNG(NO3)3·9H2O (20.7 mg, 0.05 mmol), TEMPO (15.4 mg,
[12] C. G. Jia, F. Y. Jing, W. D. Hu, M. Y. Huang, Y. Y.
0.10 mmol) and NaCl (6.0 mg, 0.10 mmol) in DCE (5 mL)
afforded tridecan-2-one[50] as a solid; yield: 186.4 mg (94%);
1H NMR (300 MHz, CDCl3): d=2.31 (t, J=7.4 Hz , 2H),
2.02 (s, 3H), 1.53–1.42 (m, 2H), 1.27–1.10 (m, 16H), 0.78 (t,
J=6.3 Hz, 3H); 13C NMR (75.4 MHz, CDCl3): d=208.60,
43.52, 31.71, 29.47, 29.42, 29.29, 29.22, 29.14, 28.99, 23.66,
22.47, 13.84; IR (neat): n=2923, 2853, 1717, 1465, 1411,
1358, 1260, 1226, 1162 cmÀ1; MS (EI): m/z=198 (M+, 2.18),
43 (100).
The reaction of tridecan-2-ol (201.1 mg, 1.0 mmol),
FeACHTUNGTRENNUNG(NO3)3·9H2O (20.4 mg, 0.05 mmol), TEMPO (7.8 mg,
0.05 mmol) and NaCl (3.0 mg, 0.05 mmol) in DCE (5 mL)
afforded tridecan-2-one[50] as a solid; yield: 186.0 mg (94%).
The reaction of tridecan-2-ol (1.9974 g, 10.0 mmol), Fe-
Jiang, J. Mol. Catal. 1994, 91, 139.
[13] K. S. Coleman, M. Coppe, C. Thomas, J. A. Osborn,
Tetrahedron Lett. 1999, 40, 3723.
[14] C. Dçbler, G. M. Mehltretter, U. Sundermeier, M.
Eckert, H. C. Militzer, M. Beller, Tetrahedron Lett.
2001, 42, 8447.
[15] B. M. Choudary, M. L. Kantam, A. Rahman, C. V.
Reddy, K. K. Rao, Angew. Chem. 2001, 113, 785;
Angew. Chem. Int. Ed. 2001, 40, 763.
[16] M. F. Semmelhack, C. R. Schmid, D. A. Cortes, S.
Chou, J. Am. Chem. Soc. 1984, 106, 3374. This aerobic
reaction with 10 mol% CuCl was conducted in DMF at
258C within 1–24 h and was limited to non-sterically
hindered alcohols.
ACHTUNGTRENNUNG(NO3)3·9H2O (202.3 mg, 0.5 mmol), TEMPO (46.6 mg,
[17] I. E. Marko, P. R. Giles, M. Tsukazaki, S. M. Brown,
0.3 mmol) and NaCl (29.2 mg, 0.5 mmol) in DCE (4 mL) af-
C. J. Urch, Science 1996, 274, 2044.
forded tridecan-2-one[50] as a solid; yield: 1.9630 g (99%).
[18] For a representative recent report, see: I. E. Marko, A.
Gautier, R. Dumeunier, K. Doda, F. Philippart, S. M.
Brown, C. J. Urch, Angew. Chem. 2004, 116, 1614;
Angew. Chem. Int. Ed. 2004, 43, 1588.
Acknowledgements
[19] P. Gamez, I. W. C. E. Arends, J. Reedijk, R. A. Shel-
don, Chem. Commun. 2003, 2414.
[20] M. Higuchi, I. Ikeda, T. Hirao, J. Org. Chem. 1997, 62,
1072.
[21] S. E. Martꢂn, D. F. Suꢃrez, Tetrahedron Lett. 2002, 43,
4475.
We greatly acknowledge the financial support from the Major
State Basic Research Development Program of China (No.
2009CB825300) and the NSF of China (20732005). We thank
Mr. Guofei Chen in this group for reproducing the results
presented in Eq. (2).
[22] For a quick reaction completed within 5–90 min with
10 mol% of tungstophosphoric acid and 50~62.5 mol%
of FeACTHNUTGRENUNG(NO3)3, see: H. Firouzabadi, N. Iranpoor, K.
Amani, Synthesis 2003, 408.
[23] V. V. Namboodiri, V. Polshettiwar, R. S. Varma, Tetra-
hedron Lett. 2007, 48, 8839. The reaction was conduct-
1016
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1005 – 1017

Development of a General and Practical Iron Nitrate/TEMPO-Catalyzed Aerobic Oxidation
ed at 60~808C at a very high loading of iron nitrate
(0.66~1 equiv.).
M.-a. Kakimoto, Adv. Synth. Catal. 2010, 352, 2635.
Over oxidation (10~29%) to acids were observed for
primary alcohols.
[24] X. Wang , X. Liang Chin, J. Catal. 2008, 29, 935.
[25] For a room temperature reaction with trifluoromethyl-
benzene as the solvent, see: N. Wang, R. Liu, J. Chen,
X. Liang, Chem. Commun. 2005, 5322. For a modified
procedure conducted at 508C with 0.4 MPa of oxygen,
see: W. Yin, C. Chu, Q. Lu, J. Tao, X. Liang, R. Liu,
Adv. Synth. Catal. 2010, 352, 113.
[33] P. Bar-On, M. Mohsen, R. Zhang, E. Feigin, M. Che-
vion, A. Samuni, J. Am. Chem. Soc. 1999, 121, 8070.
[34] A. S. K. Hashmi, T. L. Ruppert, T. Knçfel, J. W. Bats, J.
Org. Chem. 1997, 62, 7295.
[35] F.-T. Luo, A. C. Bajji, A. Jeevanandam, J. Org. Chem.
1999, 64, 1738.
[26] For a most recent comprehensive review, see: J. Piera,
J.-E. Bꢄckvall, Angew. Chem. 2008, 120, 3558; Angew.
Chem. Int. Ed. 2008, 47, 3506.
[36] M. Noro, T. Masuda, A. S. Ichimura, N. Koga, H. Iwa-
mura, J. Am. Chem. Soc. 1994, 116, 6179.
[37] K. Kondo, T. Fujitani, N. Ohnishi, J. Mater. Chem.
1997, 7, 429.
[27] For a recent review, see: R. A. Sheldon, I. W. C. E.
Arends, Adv. Synth. Catal. 2004, 346, 1051.
[38] D. H. Wadsworth, S. M. Geer, M. R. Detty, J. Org.
[28] For a representative recent report at room temperature
for 10~24 h with HCl and TEMPO/HCl/NaNO2 cata-
lyst, see: X. Wang, R. Liu, Y. Jin, X. Liang, Chem. Eur.
J. 2008, 14, 2679.
[29] For reports on Cu(II)-TEMPO-catalyzed aerobic oxi-
dations, see: E. T. T. Kumpulatinen, A. M. P. Koskinen,
Chem. Eur. J. 2009, 15, 10901; M. M. Hossain, S. S.
Shyu, Adv. Synth. Catal. 2010, 352, 3061. The limitation
on primary electron-deficient benzylic alcohols, secon-
dary allylic alcohols, and primary alkanols is obvious
based on the examples presented inside.
Chem. 1987, 52, 3662.
[39] L. Delaude, A. M. Masdeu, H. Alper, Synthesis 1994,
1149.
[40] M. W. Logue, G. L. Moore, J. Org. Chem. 1975, 40, 131.
[41] R. Shintani, T. Hayashi, Org. Lett. 2005, 7, 2071.
[42] R. Gleiter, M. Merger, Synthesis 1995, 969.
[43] E. C. McLaughlin, M. P. Doyle, J. Org. Chem. 2008, 73,
4317.
[44] V. Zeng, T. E. Ballard, C. Melander, Tetrahedron Lett.
2006, 47, 5923.
[45] K. Tanaka, T. Shoji, Org. Lett. 2005, 7, 3561.
[46] S. Danishefsky, P. Cain, J. Org. Chem. 1975, 40, 3606.
[47] V. P. Baillargeon, J. K. Stille, J. Am. Chem. Soc. 1986,
108, 452.
[30] X. He, Z. Shen, W. Mo, W. N. Sun, B. Hu, X. Hu, Adv.
Synth. Catal. 2009, 351, 89. The reaction does not work
for cinamyl alcohol.
[31] E. W. Abel, F. G. A. Stone, G. Wilkinson, (Eds.), Com-
prehensive Organometallic Chemistry II, Vol. 7, Perga-
mon, 1995, pp 78–79.
[32] For studies on the HNO3-catalyzed related reaction,
see: Y. Kuang, H. Rokubuichi, Y. Nabae, T. Hayakawa,
[48] C. O. D. Kangani, E. Kelley, B. W. Day, Tetrahedron
Lett. 2006, 47, 6289.
[49] N. Kornblum, A. S. Erickson, W. J. Kelly, B. Henggeler,
J. Org. Chem. 1982, 47, 4534.
[50] C. N. Cornell, M. S. Sigman, Org. Lett. 2006, 8, 4117.
Adv. Synth. Catal. 2011, 353, 1005 – 1017
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1017