Iron-Catalyzed Aerobic Oxidation of Alcohols: Lower Cost and Improved Selectivity

Article abstract of DOI:10.1021/acs.oprd.8b00374

An aerobic oxidation reaction of alcohols toward aldehydes or ketones using catalytic amounts of Fe(NO₃)₃·9H₂O, 4-OH-TEMPO, and NaCl has been developed. Compared with the former catalytic system with TEMPO developed in this group, the new protocol using 4-OH-TEMPO, which is much cheaper on an industrial scale, accomplished the transformation with a higher selectivity, especially for aliphatic alcohols toward aldehydes. α,β-Unsaturated alkynals or alkynones can be efficiently synthesized from propargyl alcohols, which has been much less studied in the literature.

Full text of DOI:10.1021/acs.oprd.8b00374

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Full Paper
Iron-catalyzed Aerobic Oxidation of Alcohols:
Lower Cost and Improved Selectivity
Xingguo Jiang, Jinxian Liu, and Shengming Ma
Org. Process Res. Dev., Just Accepted Manuscript • DOI: 10.1021/acs.oprd.8b00374 • Publication Date (Web): 13 Mar 2019
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Iron-catalyzed Aerobic Oxidation of Alcohols:
Lower Cost and Improved Selectivity
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Xingguo Jiang,a,c Jinxian Liu,b and Shengming Ma*a,b
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, P. R. China.
b Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University,
38 Zheda Road, Hangzhou 310027, P.R. China.
c University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
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TABLE OF CONTENTS:
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OH
.
Fe(NO3)3 9H2O (5-10 mol%)
4-OH-TEMPO (5-10 mol%)
NaCl (5-10 mol%)
O
OH
R2
N
O
R1
R2
R1
DCE, O2 or air (1 atm)
Room Temperature
R1 = Alkenyl, Alkynyl, Aryl, Allenyl, Akyl, or H;
R2 = H, Aryl, Akyl.
4-OH-TEMPO
Lower cost
High selectivity for aldehyde formation
excellent group tolerance
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ABSTRACT: An aerobic oxidation reaction of alcohols towards aldehydes or ketones using a
catalytic amount each of Fe(NO3)3·9H2O/4-OH-TEMPO/NaCl has been developed. Compared
with the former catalytic system with TEMPO developed in this group, the new protocol using 4-
OH-TEMPO, which is much cheaper in industrial scale, accomplished the transformation with a
higher selectivity, especially for aliphatic alcohols towards aldehydes. -Unsaturated alkynals
or alkynones can be efficiently synthesized from propargyl alcohols, which was much less
studied in the literature.
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KEYWORDS: aerobic oxidation, iron catalysis, 4-OH-TEMPO, aldehydes, ketones
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INTRODUCTION
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Aldehydes and ketones are important chemicals widely used in daily life, industry and
academic research.1 The oxidation of alcohols is a direct and significant way to produce
aldehydes and ketones.2 Traditionally, a stoichiometric amount of oxidants containing heavy
metals (Mn,3 Cr,4 etc.) or expensive hypervalent iodines5 such as Dess-Martin reagent or IBX
reagent have been used in industry and laboratory. Besides the high cost, these methods usually
produce large amount of toxic byproducts during the production process, causing severe
environmental burden, which makes it necessary to develop green oxidation methods using
molecular oxygen, a clean, cheap and sustainable substance, as the oxidant.6 The early reports
focused on noble metal catalysis such as Pd,7 Ru,8 Au,9 Ag,10 etc. The high cost, limited substrate
scope and the harsh conditions are main problems to be solved. In recent years, aerobic oxidation
of alcohols using earth abundant catalysts, such as Fe,11-13 Cu,14 Co15 have received extensive
concern. In 2011, our group developed a highly efficient Fe(NO3)3·9H2O/TEMPO/NaCl-
catalyzed aerobic oxidation reaction of alcohols to aldehydes or ketones under mild conditions
with broad substrate scope (Scheme 1).12 Fe(NO3)3·9H2O and NaCl are both very cheap
chemicals while the price of TEMPO, though much cheaper than many other N-oxyls such as
ABNO and AZADO, is still realtively high for industrial scale production. 4-OH-TEMPO is a
much cheaper N-oxyl even than TEMPO.16 In this work, we used 4-OH-TEMPO instead of
TEMPO as the co-catalyst based on our previous catalytic system for a more cost-effective
reaction (Scheme 1).
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Scheme 1. The iron-catalyzed aerobic oxidations of alcohols to aldehydes or ketones
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Previous work of this group:
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Fe(NO3)3 9H2O (5-10 mol%)
TEMPO (5-10 mol%)
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O
OH
R2(H)
N
O
NaCl (5-10 mol%)
R1
R2(H)
R1
DCE, O2 (1 atm), r.t.
TEMPO
This work:
OH
.
Fe(NO3)3 9H2O (5-10 mol%)
4-OH-TEMPO (5-10 mol%)
O
OH
NaCl (5-10 mol%)
N
O
R1
R2(H)
R1
R2(H)
toluene
O2 or air (1 atm), r.t.
DCE or
4-OH-TEMPO
RESULTS AND DISCUSSION
It should be noticed that the chloride anion has been considered as the ligand to increase the
activity of the iron catalyst12a and the cation of the inorganic chloride plays an important role in
steps of ligand exchange.17a We started our research using 1-dodecanol 1a as the initial substrate
for the aerobic oxidation reaction. With 5 mol% each of Fe(NO3)3·9H2O, 4-OH-TEMPO, and
o
NaCl as the catalysts, the reaction in DCE at 25 C for 20.5 h using molecular oxygen as the
oxidant gave aldehyde 2a in 63% NMR yield as well as 27% NMR recovery of alcohol 1a
(Table 1, entry 1). When the reaction time was extended to 28.5 h, the NMR yield of aldehyde 2a
was improved to 71%, with 14% NMR recovery of alcohol 1a (Table 1, entry 2). When the
loading of 4-OH-TEMPO and NaCl was increased to 10 mol% each, 85% NMR yield of
aldehyde 2a was formed along with 11% NMR yield of acid 3a after 20 h (Table 1, entry 3). We
then shortened the reaction time to 19 h, the NMR yield of aldehyde 2a was 88% with only 3%
NMR yield of acid 3a and 2.5% NMR recovery of alcohol 1a (Table 1, entry 4). 57% NMR
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yield of aldehyde 2a and 34% NMR recovery of substrate 1a was observed in the reaction for 24
h in the absence of NaCl, indicating a significant effect of NaCl for accelerating the reaction
(Table 1, entry 5). We attempted to use 10 mol% each of Fe(NO3)3·9H2O, 4-OH-TEMPO, and
NaCl to shorten the reaction time. However, 10% NMR yield of acid 3a was already observed in
9 h along with 85% NMR yield of aldehyde 2a, 1.5% NMR recovery of substrate 1a (Table 1,
entry 6). We even tried to accomplish the aerobic oxidation of alcohol 1a towards carboxylic
acid 3a with 10 mol% each of Fe(NO3)3·9H2O, 4-OH-TEMPO, and KCl,17 aldehyde 2a remained
to be the main product in 78% NMR yield and 21% NMR yield of acid 3a was formed (Table 1,
entry 7). In our previous report,17 the transformation of alcohol 1a to acid 3a was completed in
12 h (Table 1, entry 8), indicating the reaction using 4-OH-TEMPO could generate aldehydes in
a higher selectivity for the formation of aldehydes.
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Table 1. Optimization of aerobic oxidation reaction of 1aa

Fe(NO3)3 9H2O (x mol%)
4-OH-TEMPO (y mol%)
NaCl (z mol%)
+
n-C11H23CH2OH
n-C11H23CHO
n-C11H23COOH
DCE, O2 bag, 25 oC, t (h)
3a
1a
2a
Recovery of 1a
Yield
Entry
x
y
z
t (h)
(%)b
2a (%)b
3a (%)b
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2
5
5
5
5
5
5
5
5
5
20.5
28.5
20
63
71
85
88
57
85
78
-
trace
27
14
-
1
11
3
3
10 10
10 10
4
19
2.5
34
1.5
-
5
10
0
24
-
6
10 10 10
10 10 10
10 10 10
9
10
21
100
7c
8c,d
12
12
-
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b
a The reaction was carried out on a 1.0 mmol scale of 1a in 4.0 mL of DCE with a bag of O2.
NMR yield. c KCl was used instead of NaCl. d TEMPO was used instead of 4-OH-TEMPO.
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Then, we conducted the screening of other solvents. The reaction in CH3CN, THF, EtOAc, and
dioxane for 24 h only gave 18-31% NMR yield of aldehyde 2a (Table 2, entries 1-4). The
reaction could proceed smoothly in other chlorinated solvents such as DCM and CHCl3, with
~30% NMR recovery of alcohol 1a after 24 h (Table 2, entries 5 and 6). In toluene, the reaction
gave 77% NMR yield of aldehyde 2a along with 14% NMR recovery of alcohol 1a (Table 2,
entry 7). Thus, DCE is the optimal solvent.
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Table 2. Screening of solvents for aerobic oxidation reaction of 1aa

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
n-C11H23CHO
n-C11H23CH2OH
solvent, O2 bag, 25 oC, 24 h
2a
1a
Entry
Solvent
Yield of 2a (%)b
Recovery of 1a (%)b
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2
3
4
5
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7
CH3CN
THF
31
18
22
24
65
65
77
61
76
70
70
28
31
14
EtOAc
Dioxane
DCM
CHCl3
Toluene
a The reaction was carried out on a 1.0 mmol scale of 1a in 4.0 mL of solvent with a bag of O2.
b NMR yield.
With the standard conditions in hand, we investigated the oxidation reaction of different
alcohols using molecular oxygen as the oxidant. Aliphatic alcohols could be oxidized to
aldehydes in a high selectivity (Table 3, entries 1 and 2). The aliphatic alcohol 1c with an ester
group was transformed into aldehyde 2c smoothly (Table 3, entries 3). The allylic alcohol E-1d
and propargyl alcohol 1e could also be oxidized to aldehydes in a high selectivity (Table 3,
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entries 4 and 5). For benzylic alcohols, which are usually more reactive in such reaction, only 5
mol% each of Fe(NO3)3·9H2O, 4-OH-TEMPO, and NaCl were required with a much shorter
reaction time. For example, 4-nitrobenzylic alcohol 1f was converted into 4-nitrobenzaldehyde
2f in 91% yield in 5 h. According to the guideline of residual solvents in pharmaceutical industry
(ICH Q3C), 1,2-dichloroethane is listed as hazardous solvent to be avoided (concentration limit:
5 ppm) whereas toluene was much safer (concentration limit: 890 ppm), we have also carried out
the oxidation of E-1d using toluene as solvent, affording E-2d with 92% yield (Table 3, entries
7).
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Table 3. Scope of the aerobic oxidation reaction of alcohols under O2 conditionsa

Fe(NO3)3 9H2O (x mol%)
4-OH-TEMPO (y mol%)
NaCl (z mol%)
RCH2OH
RCHO
RCOOH
+
DCE, O2 bag, 25 oC, t (h)
2
3
1
Recovery
Yield
2 (%)b
Entry
Substrate
x
y
z t (h)
of 1 (%)c
3 (%)c
1
2
3
n-C11H23CH2OH (1a)
n-C15H31CH2OH (1b)
5 10 10 19 89 (2a)
5 10 10 16 87 (2b)
3
2.5
3
trace
3.5
MeOOC
OH
5 10 10 16
63 (2c)
-
(1c)
CH2OH
4
5
5 10 10 19 87 (E-2d)
-
-
-
(E-1d)
OH (1e)
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5
5
5
5 13
92 (2e)
91 (2f)
2
CH OH (1f)
O2N
2
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5
5
1.5
-
7d
E-1d
5 10 10 24 92 (E-2d)
-
b
a The reaction was carried out on a 1.0 mmol scale of 1 in 4.0 mL of DCE with a bag of O2.
Isolated yield. c NMR yield. d toluene was used instead of DCE.
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The reaction could also be conducted under air conditions. Benzylic alcohols 1g-1k with
different substituents could be oxidized into aldehydes in high yields and high selectivity in 5-9 h
(Table 4, entries 1-4). A variety of synthetically useful functional groups such as iodo, chloro,
methoxyl group, ester group, and nitro group were well tolerated in the reaction. Interestingly,
for biomass-based substrate 5-hydroxymethylfurfural 1k (HMF),18 the reaction produced 2,5-
diformylfuran 2k (DFF) in 90% yield exclusively. The reaction could also be applied to the
selective oxidation of terminal alkynol 1l and allenol 1m to the corresponding aldehydes when
increasing the loading of catalysts.
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Table 4. Scope of the aerobic oxidation reaction of alcohols under air conditionsa

Fe(NO3)3 9H2O (x mol%)
4-OH-TEMPO (y mol%)
NaCl (z mol%)
RCH2OH
RCHO
DCE, air bag, 25 oC, t (h)
2
1
Entry
1
Substrate
x
5
y
5
z t (h) Yield of 2 (%)b
I
CH2OH
5
5
99 (2g)
(1g)
MeO
CH OH (1h)
2
2
3
5
5
5
5
5
5
9
6
98 (2h)
95 (2i)
MeOOC
Cl
CH OH (1i)
2
CH2OH
NO2
4
5
5
5
5
5
5
6
9
99 (2j)
(1j)
5
90 (2k)
79 (2l)
CH OH (1k)
OHC
2
O
CH2OH
6c
10 10 10 11.5
(1l)
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n-C11H23
H
H
7
5 10 10 12
77 (2m)
CH OH (1m)
2
a The reaction was carried out on a 1.0 mmol scale of 1 in 4.0 mL of DCE with a bag of air. b
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Isolated yield. c 6% NMR yield of 10-undecynoic acid and 2% NMR recovery of substrate.
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The oxidation of propargyl alcohols to aldehydes and ketones using molecular oxygen as the
oxidant was less studied in literature. We investigated different primary and secondary propargyl
alcohols. For primary propargyl alcohols, apart from alkyl substituted propargyl alcohol 1e
(Table 3, entry 5), aryl substituted propargyl alcohols could also be oxidized into aldehydes in
high selectivity (Table 5, entries 1 and 2). For substrate 1o with electron-donating OMe group on
the phenyl ring, aldehyde 2o was obtained in 77% yield using 10 mol% each of the catalysts
(Table 5, entry 2). Aryl and alkyl substituted secondary propargyl alcohols 1p-1r could be
oxidized to ketones in high yields (Table 5, entries 3-5). The cyano group was well tolerated in
the reaction (Table 5, entry 5). To our delight, 1p could be oxidized to 4p in toluene using air as
terminal oxidant with comparable yield in 8 hours (Table 5, entry 6).
Table 5. Scope of propargyl alcohols under air conditionsa

Fe(NO3)3 9H2O (x mol%)
4-OH-TEMPO (y mol%)
NaCl (z mol%)
OH
R2
O
R1
R1
R2
: R = H
1
DCE, air bag, 25 oC, t (h)
2
2
2
4
: R  H
Yield of
2 or 4 (%)b
81 (2n)
77 (2o)
1
Entry
x
5
y
z
t (h)
R1
Ph
R2
1
2
H (1n)
5
5
10
5
7
9.5
4
4-MeOC6H4
H (1o)
Ph (1p)
10 10
3
H
5
5
5
5
5
5
5
5
89 (4p)
92 (4q)
91 (4r)
4
n-C4H9
n-C4H9
H
n-C7H15 (1q)
5
7
5
4-NCC6H4 (1r)
Ph (1p)
5
7
6 c
5
8
85 (4p)
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a The reaction was carried out on a 1.0 mmol scale of 1 in 4.0 mL of DCE with a bag of air. b
Isolated yield. c toluene was used instead of DCE.
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In order to show the practicality in an academic synthetic laboratory, a 100-mmol scale
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reaction of 1a applying a slow air flow was demonstrated (eq. 1 and Fig. 1).
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
Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
(1)
+
n-C11H23CH2OH
n-C11H23CHO
2a
n-C11H23COOH
3a
DCE, air flow (30 mL/min)
25 oC, 15.5 h
1a
100 mmol
1.5% by NMR
88.5% by NMR
88% by isolation
Figure 1. The apparatus and reaction for the aerobic reaction of 1a on 100 mmol scale with a
slow air flow (30 mL/min).
In addition, we also conducted a 0.5 mol scale reaction of 1s in toluene with a slow air flow,
corresponding product 4s was isolated by simple distillation with 84% yield conveniently (eq. 2).
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
Fe(NO3)3 9H2O (5 mol%)
O
OH
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
toluene, air flow (30 mL/min), 25 oC, 42 h
Ph
(2)
Ph
4s
1s
0.5 mol
84% by distillation
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CONCLUSIONS
In summary, an iron-catalyzed aerobic oxidation reaction of alcohols to aldehydes and ketones
using Fe(NO3)3·9H2O/NaCl as the catalytic system with the cheaper 4-OH-TEMPO replacing
TEMPO while improving the selectivity of forming aldehydes. The reaction may be conducted in
both O2 or air conditions at room temperature with broad substrate scope with the demonstration
of up to 0.5 mmol scale reactions. Further studies in this area are being actively pursued in this
laboratory.
EXPERIMENTAL SECTION
General Information. Fe(NO3)3·9H2O was purchased from Energy Chemical or J&K. 4-OH-
TEMPO was purchased from Adamas. NaCl was purchased from Sinopharm. DCE was used
directly without further treatment. Other reagents were used as received without further
treatment. Substrates 1c,22 1e,26 1l,36 1m,39 1o,40 1q,42 and 1r44 were synthesized according to the
o
literature method. Petroleum ether (60-90 C) was used for chromatography. Gas bags for
reactions with O2 or air were obtained from Wattcas. Melting points were recorded using a Stuart
SMP30 melting point apparatus. IR spectra were obtained using a Bruker Tensor 27
1
13
spectrometer. H and C spectra were obtained using an Agilent (400 MHz), Varian Mercury
(400 MHz), or Bruker (400 MHz) spectrometer. The mass spectra were recorded using an
Agilent 5973N instrument. Caution: Oxygen in use in combination with organic solvents;
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remove all ignition sources including sources of sparks, static, or flames since oxygen increases
intensity of any fire. Inhalation of pure oxygen should be avoided as well.
n-Dodecanal (2a) (jxg-5-192)
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
Fe(NO3)3 9H2O (5 mol%)
n-C11H23CHO
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
DCE, O2 bag, 25 oC, 19 h
n-C11H23COOH
3a
3% NMR yield
2a
+
n-C11H23CH2OH
88% NMR yield
89% yield
1a
1a
+
(2.5% NMR recovery)
Typical Procedure I: To a Schlenk tube were added Fe(NO3)3·9H2O (20.3 mg, 0.05 mmol), 4-
OH-TEMPO (17.2 mg, 0.1 mmol), NaCl (5.9 mg, 0.1 mmol), 1a (188.0 mg, 99% purity, 1.0
mmol), and DCE (4.0 mL) sequentially under the atmosphere of oxygen from a gas bag
o
(commercial size: 2 L, could be expanded to 5 L). The Schlenk tube was then stirred at 25 C
until completion of the reaction as monitored by TLC (petroleum ether/ ethyl acetate = 5/1) (19
h). The crude reaction mixture was filtrated through a short column of silica gel (height: 2 cm, Φ:
3 cm) eluted with diethyl ether (3 × 25 mL). After evaporation, the residue was purified by
chromatography on silica gel to afford 2a19 (164.6 mg, 89%) (eluent: petroleum ether/ethyl
acetate = 100/1) (88% of 2a, 3% of 3a,20 and 2.5% of 1a were observed by NMR analysis of
1
crude product using CH2Br2 as internal standard) as an oil: H NMR (400 MHz, CDCl3) δ 9.77
(t, J = 1.8 Hz, 1 H, CHO), 2.42 (td, J1 = 7.3 Hz, J2 = 2.1 Hz, 2 H, CH2), 1.63 (quint, J = 7.2 Hz, 2
H, CH2), 1.38-1.20 (m, 16 H, 8 × CH2), 0.88 (t, J = 6.8 Hz, 3 H, CH3); 13C NMR (100 MHz,
CDCl3) δ 202.9, 43.9, 31.9, 29.6, 29.5, 29.4, 29.33, 29.29, 29.1, 22.6, 22.0, 14.1; IR (neat, cm-1)
2922, 2853, 2713, 1726, 1464, 1411, 1389; MS (EI, 70 eV): 184 (M+, 0.19), 57 (100).
n-Hexadecanal (2b) (jxg-6-4)
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
Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
1b
n-C15H31CHO
n-C15H31CH2OH
+
DCE, O2 bag, 25 oC, 16 h
3% NMR recovery
2b
7
1b
89% NMR yield
87% yield
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Following Typical Procedure I, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (17.3 mg, 0.1 mmol), NaCl (5.8 mg, 0.1 mmol), and 1b (247.2 mg, 98% purity, 1.0
mmol) in DCE (4.0 mL) for 16 h afford 2b21 (209.9 mg, 87%) (eluent: petroleum ether/ethyl
acetate = 100/1 (500 mL) (89% of 2b, 3% of 1b were observed by NMR analysis of crude
product using CH2Br2 as internal standard) as a solid: m.p. 35.1-36.4 °C (ethyl acetate/petroleum
ether) (reported:21 35-36 oC); 1H NMR (400 MHz, CDCl3) δ 9.76 (t, J = 1.8 Hz, 1 H, CHO), 2.42
(td, J1 = 7.2 Hz, J2 = 2.0 Hz, 2 H, CH2), 1.63 (quint, J = 7.2 Hz, 2 H, CH2), 1.37-1.19 (m, 24 H,
12 × CH2), 0.88 (t, J = 6.8 Hz, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 202.9, 43.9, 31.9,
29.67, 29.65, 29.64, 29.63, 29.61, 29.55, 29.4, 29.3, 29.1, 22.7, 22.0, 14.1; IR (neat, cm-1) 2913,
2848, 2750, 1704, 1470, 1410, 1392, 1372, 1067; MS (EI, 70 eV): 240 (1.32), 82 (100).
Methyl 6-oxohexanoate (2c) (jxg-6-2)
Fe(NO3)39H2O (5 mol%)
4-OH-TEMPO (10 mol%)
MeOOC
MeOOC
NaCl (10 mol%)
MeOOC
COOH
CHO
CH2OH
+
DCE, O2 bag, 25 oC, 16 h
2c
3c
3.5% NMR yield
1c
74% NMR yield
63%
Following Typical Procedure I, the reaction of Fe(NO3)3·9H2O (20.3 mg, 0.05 mmol), 4-OH-
TEMPO (17.4 mg, 0.1 mmol), NaCl (5.8 mg, 0.1 mmol), and 1c22 (146.0 mg, 1.0 mmol) in DCE
(4.0 mL) for 16 h afford 2c23 (91.1 mg, 63%) (eluent: petroleum ether/ethyl acetate = 15/1 (800
mL)) (74% of 2c and 3.5% of 3c24 were observed by NMR analysis of crude product using
1
CH2Br2 as internal standard) as an oil: H NMR (400 MHz, CDCl3) δ 9.78 (t, J = 1.6 Hz, 1 H,
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CHO), 3.68 (s, 3 H, CH3), 2.52-2.44 (m, 2 H, CH2), 2.39-2.32 (m, 2 H, CH2), 1.72-1.62 (m, 4 H,
2 × CH2); 13C NMR (100 MHz, CDCl3) δ 202.0, 173.6, 51.5, 43.4, 35.6, 24.2, 21.4; IR (neat, cm-
1) 2952, 2725, 1721, 1437, 1365, 1197, 1155, 1093, 1008; MS (EI, 70 eV): 144 (M+, 0.57), 114
(100).
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3-Phenyl-2(E)-propenal (E-2d) (jxg-6-1)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
CHO
CH2OH
NaCl (10 mol%)
DCE, O2 bag, 25 oC, 19 h
-1d
E
-2d
E
87%
Following Typical Procedure I, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (17.3 mg, 0.1 mmol), NaCl (5.9 mg, 0.1 mmol), and 1d (135.0 mg, 99% purity, 1.0
mmol) in DCE (4.0 mL) for 19 h afforded E-2d25 (114.8 mg, 87%) (eluent: petroleum ether/ethyl
ether = 20/1 (600 mL)) as an oil: 1H NMR (400 MHz, CDCl3) δ 9.70 (d, J = 7.6 Hz, 1 H, CHO),
7.60-7.53 (m, 2 H, Ar-H), 7.51-7.40 (m, 4 H, 3 × Ar-H and =CH), 6.72 (dd, J1 = 16.2 Hz, J2 =
13
7.8 Hz, 1 H, =CH); C NMR (100 MHz, CDCl3) δ 193.7, 152.8, 133.9, 131.2, 129.0, 128.5,
128.4; IR (neat, cm-1) 2812, 2741, 1668, 1623, 1574, 1493, 1449, 1393, 1328, 1294, 1249, 1119,
1072, 1006; MS (EI, 70 eV): 132 (M+, 59.43), 131 (100).
2-Undecynal (2e) (jxg-6-3)
CHO
Fe(NO3)39H2O (5 mol%)
2e
CH2OH
96% NMR yield
92%
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
+
DCE, O2 bag, 25 oC, 13 h
1e
COOH
3e
2% NMR yield
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Following Typical Procedure I, the reaction of Fe(NO3)3·9H2O (20.2 mg, 0.05 mmol), 4-OH-
TEMPO (8.7 mg, 0.05 mmol), NaCl (3.0 mg, 0.05 mmol), and 1e26 (167.6 mg, 1.0 mmol) in
DCE (4.0 mL) for 13 h afforded 2e27 (152.9 mg, 92%) (eluent: petroleum ether/ethyl acetate =
100/1 (400 mL)) (96% of 2e and 2% of 3e28 were observed by NMR analysis of crude product
using CH2Br2 as internal standard) as an oil: 1H NMR (400 MHz, CDCl3) δ 9.18 (s, 1 H, CHO),
2.41 (t, J = 7.0 Hz, 2 H, CH2), 1.60 (quint, J = 7.4 Hz, 2 H, CH2), 1.46-1.35 (m, 2 H, CH2), 1.35-
1.20 (m, 8 H, 4 × CH2), 0.89 (t, J = 6.8 Hz, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 177.2,
99.3, 81.6, 31.7, 29.0, 28.9, 28.8, 27.5, 22.6, 19.1, 14.0; IR (neat, cm-1) 2925, 2855, 2280, 2199,
1669, 1464, 1424, 1387, 1326, 1136; MS (EI, 70 eV): 166 (M+, 0.45), 55 (100).
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4-Nitrobenzaldehyde (2f) (jxg-5-147)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
O2N
CH2OH
+
O2N
CHO
O2N
COOH
DCE, O2 bag, 25 oC, 5 h
1f
2f
3f
1.5% NMR
98% NMR
91%
Following Typical Procedure I, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (8.7 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1f (154.7 mg, 99% purity, 1.0
mmol) in DCE (4.0 mL) for 5 h afforded 2f29 (151.4 mg, 91%) (eluent: petroleum ether/ethyl
ether = 5/1 (400 mL)) (98% of 2f and 1.5% of 3f30 were observed by NMR analysis of crude
product using CH2Br2 as internal standard) as a solid: m.p. 105.4-106.6 °C (ethyl
o
1
acetate/petroleum ether) (reported:29 104-106 C); H NMR (400 MHz, CDCl3) δ 10.18 (s, 1 H,
CHO), 8.41 (d, J = 8.4 Hz, 2 H, Ar-H), 8.10 (d, J = 8.0 Hz, 2 H, Ar-H); 13C NMR (100 MHz,
CDCl3) δ 190.3, 151.1, 140.0, 130.4, 124.2; IR (neat, cm-1) 3106, 2850, 1703, 1604, 1532, 1343,
1324, 1286, 1194, 1103, 1006; MS (EI, 70 eV) m/z (%): 151 (M+, 100).
4-Iodobenzaldehyde (2g) (jxg-6-8)
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
Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
DCE, air bag, 25 oC, 5 h
I
CH2OH
I
CHO
1g
2g
99%
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Typical Procedure II: To a Schlenk tube were added Fe(NO3)3·9H2O (20.3 mg, 0.05 mmol), 4-
OH-TEMPO (8.7 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), 1g (238.6 mg, 98% purity, 1.0
mmol), and DCE (4.0 mL) sequentially. The Schlenk tube was then connected with a gas bag
o
(commercial size: 2 L, could be expanded to 5 L) of air stirred at 25 C until completion of the
reaction as monitored by TLC (petroleum ether/ethyl acetate = 5/1) (5 h). The crude reaction
mixture was filtrated through a short column of silica gel (height: 2 cm, Φ: 3 cm) eluted with
diethyl ether (3 × 25 mL). After evaporation, the residue was purified by chromatography on
silica gel to afford 2g31 (230.3 mg, 99%) (eluent: petroleum ether/ethyl acetate = 20/1 (400 mL))
o
1
as a solid: m.p. 77.0-78.3 °C (ethyl acetate/petroleum ether) (reported:31 77-78 C); H NMR
(400 MHz, CDCl3) δ 9.96 (s, 1 H, CHO), 7.92 (d, J = 8.4 Hz, 2 H, Ar-H), 7.60 (d, J = 8.0 Hz, 2
H, Ar-H); 13C NMR (100 MHz, CDCl3) δ 191.4, 138.4, 135.5, 130.8, 102.8; IR (neat, cm-1) 2825,
2733, 1683, 1656, 1579, 1561, 1473, 1403, 1377, 1274, 1202, 1160, 1048, 1003; MS (EI, 70 eV)
m/z (%): 232 (100).
4-Methoxybenzaldehyde (2h) (jxg-6-9)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
DCE, air bag, 25 oC, 9 h
MeO
CH2OH
MeO
CHO
1h
2h
98%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.1 mg, 0.05 mmol), 4-OH-
TEMPO ((8.7 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1h (141.6 mg, 98% purity, 1.0
mmol) in DCE (4 mL) for 9 h afforded 2h32 (133.6 mg, 98%) (eluent: petroleum ether/ethyl ether
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= 15/1 (650 mL)) as an oil: H NMR (400 MHz, CDCl3) δ 9.88 (s, 1 H, CHO), 7.84 (d, J = 8.8
Hz, 2 H, Ar-H), 7.01 (d, J = 8.8 Hz, 2 H, Ar-H), 3.89 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3)
δ 190.8, 164.5, 131.9, 129.8, 114.2, 55.5; IR (neat, cm-1) 2840, 2737, 1680, 1595, 1575, 1509,
1460, 1426, 1393, 1314, 1254, 1214, 1182, 1156, 1108, 1021; MS (EI, 70 eV) m/z (%): 136 (M+,
72.67), 135 (100).
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Methyl 4-formylbenzoate (2i) (jxg-6-22)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
MeOOC
CH2OH
MeOOC
CHO
DCE, air bag, 25 oC, 6 h
1i
2i
95%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (8.7 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1i (169.2 mg, 98% purity, 1.0
mmol) in DCE (4.0 mL) for 6 h afforded 2i33 (156.2 mg, 95%) (eluent: petroleum ether/ethyl
acetate = 20/1) as a solid: m.p. 61.7-62.9 °C (ethyl acetate/petroleum ether) (reported:33 61-63
oC); 1H NMR (400 MHz, CDCl3) δ 10.11 (s, 1 H, CHO), 8.20 (d, J = 8.0 Hz, 2 H, Ar-H), 7.96 (d,
J = 8.4 Hz, 2 H, Ar-H), 3.97 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 191.6, 165.9, 139.0,
135.0, 130.1, 129.4, 52.5; IR (neat, cm-1) 2962, 2887, 1722, 1682, 1575, 1502, 1434, 1391, 1280,
1199, 1106, 1012; MS (EI, 70 eV) m/z (%): 164 (M+, 59.96), 133 (100).
5-Chloro-2-nitrobenzaldehyde (2j) (jxg-6-23)

Fe(NO3)3 9H2O (5 mol%)
NO2
NO2
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
DCE, air bag, 25 oC, 6 h
CHO
CH2OH
Cl
Cl
2j
1j
99%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (8.6 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1j (191.2 mg, 98% purity, 1.0
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mmol) in DCE (4.0 mL) for 6 h afforded 2j34 (183.1 mg, 99%) (eluent: petroleum ether/ethyl
5
6
o
acetate = 20/1) as a solid: m.p. 75.6-76.7 °C (ethyl acetate/petroleum ether) (reported:34 74 C
7
8
9
1
(ethyl acetate/n-hexane)); H NMR (400 MHz, CDCl3) δ 10.42 (s, 1 H, CHO), 8.13 (d, J = 8.8
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Hz, 1 H, Ar-H), 7.90 (d, J = 2.4 Hz, 1 H, Ar-H), 7.73 (dd, J1 = 8.4 Hz, J2 = 2.4 Hz, 1 H, Ar-H);
13C NMR (100 MHz, CDCl3) δ 186.8, 147.4, 141.2, 133.4, 132.7, 129.6, 126.1; IR (neat, cm-1)
3095, 1693, 1563, 1528, 1505, 1462, 1385, 1342, 1305, 1256, 1179, 1151, 1103, 1071; MS (EI,
70 eV) m/z (%): 187 ([M(37Cl)]+, 0.32), 185 ([M(35Cl)]+, 0.71), 155 (100).
Furan-2,5-dicarbaldehyde (2k) (jxg-6-25)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
HOH2C
NaCl (5 mol%)
OHC
CHO
CHO
O
O
2k
DCE, air bag, 25 oC, 9 h
1k
90%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.3 mg, 0.05 mmol), 4-OH-
TEMPO (8.7 mg, 0.05 mmol), NaCl (3.0 mg, 0.05 mmol), and 1k (129.5 mg, 98% purity, 1.0
mmol) in DCE (4.0 mL) for 9 h afforded 2k35 (112.2 mg, 90%) (eluent: petroleum ether/ethyl
acetate = 5/1 (800 mL)): m.p. 110.0-111.4 °C (ethyl acetate/petroleum ether) (reported:35 108-
o
1
110 C); H NMR (400 MHz, CDCl3) δ 9.87 (s, 2 H, 2 × CHO), 7.37 (s, 2 H, two protons of
furanyl); 13C NMR (100 MHz, CDCl3) δ 179.2, 154.1, 119.4; IR (neat, cm-1) 3126, 3104, 1662,
1561, 1510, 1409, 1264, 1236, 1170, 1043, 1021, 1003; MS (EI, 70 eV) m/z (%): 124 (M+, 100).
10-Undecynal (2l) (jxg-6-21)
CHO
Fe(NO3)39H2O (10 mol%)
2l
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
83% NMR yield
79%
CH2OH
DCE, O2 bag, 25 oC, 11.5 h
+
1l
COOH
3l
6% NMR yield
1l
+
(2% NMR recovery)
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Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (40.5 mg, 0.1 mmol), 4-OH-
TEMPO (17.4 mg, 0.1 mmol), NaCl (5.8 mg, 0.1 mmol), and 1l36 (168.3 mg, 1.0 mmol) in DCE
(4.0 mL) for 11.5 h afforded 2l37 (131.8 mg, 79%) (eluent: petroleum ether/ethyl ether = 25/1
(500 mL)) (83% of 2l, 6% of 3l,38 and 2% of 1l were observed by NMR analysis of crude
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product using CH2Br2 as internal standard) as an oil: H NMR (400 MHz, CDCl3) δ 9.77 (t, J =
1.8 Hz, 1 H, CHO), 2.43 (td, J1 = 7.3 Hz, J2 = 1.6 Hz, 2 H, CH2), 2.18 (td, J1 = 7.0 Hz, J2 = 2.7
Hz, 2 H, CH2), 1.95 (t, J = 2.4 Hz, 1 H, ≡CH), 1.63 (quint, J = 7.2 Hz, 2 H, CH2), 1.52 (quint, J =
7.3 Hz, 2 H, CH2), 1.45-1.25 (m, 8 H, 4 × CH2); 13C NMR (100 MHz, CDCl3) δ 202.8, 84.6,
68.1, 43.8, 29.1, 29.0, 28.8, 28.5, 28.3, 21.9, 18.3; IR (neat, cm-1) 3291, 2929, 2856, 2720, 2117,
1723, 1462, 1410, 1391, 1353; MS (EI, 70 eV): 166 (M+, 0.15), 81 (100).
Pentadeca-2,3-dienal (2m) (jxg-6-26)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
n-C11H23
H
n-C11H23
H
H
OH
H
CHO
DCE, air bag, 25 oC, 12 h
1m
2m
77%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (17.2 mg, 0.1 mmol), NaCl (5.9 mg, 0.1 mmol), and 1m39 (225.1 mg, 1.0 mmol) in
DCE (4.0 mL) for 12 h afforded 2m (172.8 mg, 77%) (eluent: petroleum ether/ethyl ether =
1
50/1) as an oil: H NMR (400 MHz, CDCl3) δ 9.49 (d, J = 7.6 Hz, 1 H, CHO), 5.85-5.73 (m, 2
H, HC=C=CH), 2.19 (qd, J1 = 7.1 Hz, J2 = 3.0 Hz, 2 H, CH2), 1.48 (quint, J = 7.2 Hz, 2 H, CH2),
1.40-1.20 (m, 16 H, 8 × CH2), 0.88 (t, J = 6.8 Hz, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ
219.1, 192.3, 98.6, 96.3, 31.9, 29.57, 29.55, 29.5, 29.29, 29.25, 28.9, 28.8, 27.4, 22.6, 14.1; IR
(neat, cm-1) 2922, 2853, 1943, 1689, 1463, 1357, 1108, 1084; MS (EI, 70 eV) m/z (%): 222 (M+,
3.75), 81 (100); HRMS calcd. for C15H26O (M+): 222.1984; Found: 222.1982.
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3-Phenylpropynal (2n) (jxg-6-16)
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8

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
CH2OH
CHO
DCE, air bag, 25 oC, 7 h
9
2n
1n
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81%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.1 mg, 0.05 mmol), 4-OH-
TEMPO (8.6 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1n (132.3 mg, 1.0 mmol) in DCE
(4.0 mL) for 7 h afforded 2n12a (106.0 mg, 81%) (eluent: petroleum ether/ethyl ether = 20/1 (400
1
mL)) as an oil: H NMR (400 MHz, CDCl3) δ 9.42 (s, 1 H, CHO), 7.63-7.57 (m, 2 H, Ar-H),
13
7.52-7.45 (m, 1 H, Ar-H), 7.44-7.37 (m, 2 H, Ar-H); C NMR (100 MHz, CDCl3) δ 176.8,
133.2, 131.2, 128.7, 119.3, 95.1, 88.3; IR (neat, cm-1) 2853, 2239, 2185, 1653, 1488, 1443, 1387,
1259, 1160, 1069, 1027, 1002; MS (EI, 70 eV) m/z (%): 130 (100).
3-(4-Methoxyphenyl)propynal (2o) (jxg-6-19)

Fe(NO3)3 9H2O (10 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
MeO
CH2OH
MeO
CHO
DCE, air bag, 25 oC, 9.5 h
1o
2o
77%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (40.4 mg, 0.1 mmol), 4-OH-
TEMPO (17.2 mg, 0.1 mmol), NaCl (5.9 mg, 0.1 mmol), and 1o40 (162.1 mg, 1.0 mmol) in DCE
(4.0 mL) for 9.5 h afforded 2o41 (123.6 mg, 77%) (eluent: petroleum ether/ethyl ether = 20/1
(500 mL)) as a solid: m.p. 47.1-47.9 °C (ethyl acetate/petroleum ether) (reported:41 47-48 oC); 1H
NMR (400 MHz, CDCl3) δ 9.39 (s, 1 H, CHO), 7.56 (d, J = 8.8 Hz, 2 H, Ar-H), 6.91 (d, J = 8.8
Hz, 2 H, Ar-H), 3.85 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 176.7, 162.0, 135.4, 114.4,
111.0, 96.5, 88.7, 55.4; IR (neat, cm-1) 2933, 2839, 2249, 2177, 1641, 1596, 1566, 1506, 1463,
1416, 1387, 1302, 1253, 1174, 1112, 1020; MS (EI, 70 eV) m/z (%): 160 (M+, 100).
1-Phenylprop-2-yn-1-one (4p) (jxg-6-10)
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
Fe(NO3)3 9H2O (5 mol%)
O
OH
Ph
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
DCE, air bag, 25 oC, 4 h
Ph
7
4p
1p
8
89%
9
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-
TEMPO (8.5 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1p (135.5 mg, 97% purity, 1.0
mmol) in DCE (4.0 mL) for 4 h afforded 4p12b (115.5 mg, 89%) (eluent: petroleum ether/ethyl
ether = 20/1 (400 mL)) as a solid: m.p. 50.1-51.1 °C (ethyl acetate/petroleum ether) (reported:12b
50-51 oC); 1H NMR (400 MHz, CDCl3) δ 8.20-8.13 (m, 2 H, Ar-H), 7.64 (t, J = 7.4 Hz, 1 H, Ar-
H), 7.50 (t, J = 7.6 Hz, 2 H, Ar-H), 3.47 (s, 1 H, ≡CH); 13C NMR (100 MHz, CDCl3) δ 177.4,
136.0, 134.5, 129.6, 128.6, 80.8, 80.1; IR (neat, cm-1) 3230, 2090, 1639, 1594, 1576, 1451, 1415,
1313, 1259, 1172, 1030, 1003; MS (EI, 70 eV) m/z (%): 130 (M+, 53.22), 102 (100).
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Tetradec-5-yn-7-one (4q) (jxg-6-34)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
O
OH
n-C7H15
n-C7H15
n-C4H9
n-C4H9
DCE, air bag, 25 oC, 7 h
4q
92%
1q
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.2 mg, 0.05 mmol), 4-OH-
TEMPO (8.6 mg, 0.05 mmol), NaCl (2.9 mg, 0.05 mmol), and 1q42 (210.6 mg, 1.0 mmol) in
DCE (4.0 mL) for 7 h afforded 4q43 (192.4 mg, 92%) (eluent: petroleum ether/ethyl ether = 40/1
(500 mL)) as an oil: 1H NMR (400 MHz, CDCl3) δ 2.52 (t, J = 7.6 Hz, 2 H, CH2), 2.37 (t, J = 7.0
Hz, 2 H, CH2), 1.66 (quint, J = 7.1 Hz, 2 H), 1.62-1.53 (m, 2 H, CH2), 1.49-1.38 (m, 2 H, CH2),
1.37-1.20 (m, 8 H, 4 × CH2), 0.93 (t, J = 7.4 Hz, 3 H, CH3), 0.88 (t, J = 6.8 Hz, 3 H, CH3); 13C
NMR (100 MHz, CDCl3) δ 188.5, 94.1, 80.8, 45.5, 31.6, 29.7, 28.93, 28.87, 24.1, 22.5, 21.9,
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18.6, 14.0, 13.4; IR (neat, cm-1) 2957, 2928, 2858, 2212, 1672, 1463, 1407, 1378, 1356, 1325,
1299, 1247, 1226, 1162, 1106, 1053, 1000; MS (EI, 70 eV) m/z (%): 208 (M+, 0.32), 109 (100).
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1-(4-Cynophenyl)hept-2-yn-1-one (4r) (jxg-6-35)
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
Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
O
OH
n-C4H9
n-C4H9
DCE, air bag, 25 oC, 7 h
CN
CN
4r
1r
91%
Following Typical Procedure II, the reaction of Fe(NO3)3·9H2O (20.3 mg, 0.05 mmol), 4-OH-
TEMPO (8.6 mg, 0.05 mmol), NaCl (3.0 mg, 0.05 mmol), and 1r44 (213.0 mg, 1.0 mmol) in
DCE (4.0 mL) for 7 h afforded 4r45 (192.5 mg, 91%) ((eluent: petroleum ether/ethyl ether = 20/1
1
(500 mL) to 15/1 (300 mL)) as an oil: H NMR (400 MHz, CDCl3) δ 8.23 (d, J = 8.8 Hz, 2 H,
Ar-H), 7.80 (d, J = 8.4 Hz, 2 H, Ar-H), 2.55 (t, J = 7.0 Hz, 2 H, CH2), 1.73-1.64 (m, 2 H, CH2),
1.57-1.45 (m, 2 H, CH2), 0.98 (t, J = 7.2 Hz, 3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 176.3,
139.5, 132.3, 129.7, 117.8, 116.8, 99.0, 79.2, 29.6, 22.0, 18.9, 13.4; IR (neat, cm-1) 2959, 2933,
2871, 2231, 2198, 1647, 1605, 1566, 1463, 1404, 1309, 1293, 1257, 1175, 1110, 1017; MS (EI,
70 eV) m/z (%): 211 (M+, 5.56), 169 (100).
Aerobic oxidation of alcohols in toluene
1. 3-Phenyl-2(E)-propenal (E-2d) (ljx-2-56)

Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
CHO
CH2OH
o
toluene
, O2 bag, 25 C, 24 h
-2d
E
-1d
E
92%
To a Schlenk tube were added Fe(NO3)3·9H2O (20.4 mg, 0.05 mmol), 4-OH-TEMPO (17.2
mg, 0.1 mmol), NaCl (5.7 mg, 0.1 mmol), E-1d (134.5 mg, 1.0 mmol), and toluene (4.0 mL)
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sequentially under the atmosphere of oxygen from a gas bag (commercial size: 2 L). The Schlenk
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o
tube was then stirred at 25 C until completion of the reaction as monitored by TLC (petroleum
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8
9
ether/ ethyl acetate = 3/1) (24 h). The crude reaction mixture was filtrated through a short
column of silica gel (height: 2 cm, Φ: 3 cm) eluted with diethyl ether (3 × 25 mL). After
evaporation, the residue was purified by chromatography on silica gel to afford E-2d19 (122.5
mg, 92%) (eluent: petroleum ether/ethyl acetate = 10/1) (95% of E-2d were observed by NMR
analysis of crude product using CH2Br2 as internal standard) as an oil.
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2. 1-Phenylprop-2-yn-1-one (4p) (ljx-2-46)

Fe(NO3)3 9H2O (5 mol%)
O
OH
Ph
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
Ph
o
toluene
, air bag, 25 C, 8 h
4p
1p
85%
To a Schlenk tube were added Fe(NO3)3·9H2O (20.2 mg, 0.05 mmol), 4-OH-TEMPO (8.8 mg,
0.05 mmol), NaCl (2.7 mg, 0.05 mmol), 1p (132.1 mg, 1.0 mmol), and toluene (4.0 mL)
sequentially. The Schlenk tube was then connected with a gas bag (commercial size: 2 L) of air
o
stirred at 25 C until completion of the reaction as monitored by TLC (petroleum ether/ethyl
acetate = 5/1) (8 h). The crude reaction mixture was filtrated through a short column of silica gel
(height: 2 cm, Φ: 3 cm) eluted with diethyl ether (3 × 25 mL). After evaporation, the residue was
purified by chromatography on silica gel to afford 4p31 (110.5 mg, 85%) (eluent: petroleum
ether/ethyl acetate = 20/1 (200 mL)) as a solid.
100 mmol scale reaction with a slow air flow (jxg-6-121):
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
Fe(NO3)3 9H2O (5 mol%)
4-OH-TEMPO (10 mol%)
NaCl (10 mol%)
+
n-C11H23CH2OH
n-C11H23CHO
n-C11H23COOH
3a
DCE, air flow (30 mL/min)
25 oC, 15.5 h
2a
1a
100 mmol
1.5% by NMR
88.5% by NMR
88% by isolation
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To a 1 L three-neck flask were added Fe(NO3)3·9H2O (2.0210 g, 5.0 mmol), 4-OH-TEMPO
(1.7212 g, 10.0 mmol), NaCl (0.5846 g, 10.0 mmol), and DCE (200 mL) sequentially. After
stirring for 10 min, 1a (18.8203 g, 99% purity, 100.0 mmol) and DCE (100 mL) were then
added. A slow flow of air directly from an air cylinder (99.99%, 30 mL/min) was then connected
to the flask (Fig. 1). The resulting mixture was stirred at 25 oC until completion of the reaction as
monitored by TLC (petroleum ether/ethyl acetate = 5/1) (15.5 h). The crude reaction mixture was
filtrated through a short column of silica gel (height: 3 cm, Φ: 7.5 cm) eluted with ethyl ether
(300 mL). After evaporation, the residue was purified by chromatography on silica gel to afford
2a (16.3054 g, 88%) (petroleum ether/ethyl acetate = 100/1 (3.2 L)) (88.5% of 2a and 1.5% of 3a
were observed by NMR analysis of crude product using CH2Br2 as internal standard) as an oil:
1H NMR (400 MHz, CDCl3) δ 9.76 (t, J = 1.6 Hz, 1 H, CHO), 2.42 (td, J1 = 7.3 Hz, J2 = 1.7 Hz,
2 H, CH2), 1.63 (quint, J = 7.3 Hz, 2 H, CH2), 1.38-1.16 (m, 16 H, 8 × CH2), 0.88 (t, J = 7.0 Hz,
3 H, CH3); 13C NMR (100 MHz, CDCl3) δ 202.9, 43.9, 31.9, 29.6, 29.4, 29.32, 29.29, 29.1, 22.6,
22.1, 14.1.
0.5 mol scale reaction with a slow air flow (ljx-2-115):

Fe(NO3)3 9H2O (5 mol%)
O
OH
4-OH-TEMPO (5 mol%)
NaCl (5 mol%)
Ph
Ph
1s
0.5 mol
toluene, air flow (30 mL/min), 25 oC, 42 h
4s
84% by distillation
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To a 500 mL three-neck flask were added Fe(NO3)3·9H2O (10.1407 g, 25.1 mmol), 4-OH-
TEMPO (4.3114 g, 25.0 mmol), NaCl (1.4754 g, 25.2 mmol), 1s (61.0180 g, 0.5 mol), and
toluene (100 mL) sequentially. A slow flow of air directly from an air cylinder (30 mL/min) was
o
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then connected to the flask and the temperature went up to 35 C. The resulting mixture was
o
stirred at 25 C until completion of the reaction as monitored by TLC (petroleum ether/ethyl
acetate = 5/1) (42 h). The liquid layer was transferred to a 500 mL flask for distillation, the
residue was washed with DCM (10 ml x 3) and combined to the distillation flask, the resulting
mixture was distilled in reduced pressure to afford 4s12a in 84% yield (50.2509 g, yellow oil, b.p.
98-100 oC/7.5 Torr). 1H NMR (300 MHz, CDCl3) δ 7.96 (d, J = 7.2 Hz, 2 H, Ar-H), 7.57 (t, J =
7.2 Hz, 1 H, Ar-H), 7.47 (t, J = 7.2 Hz, 2 H, Ar-H), 2.61 (s, 3 H, CH3); 13C NMR (75 MHz,
CDCl3) δ 198.1, 137.1, 133.1, 128.5, 128.3, 26.6; IR (neat, cm-1) 3062, 1682, 1599, 1582, 1449,
1429, 1359, 1266, 1180, 1079, 1025; MS (EI, 70 eV) m/z (%): 120 (M+, 34.07), 105 (100).
ASSOCIATED CONTENT
Supporting Information. The Supporting Information is available free of charge on the ACS
Publications website at DOI:
1H, 13C NMR spectra of all the products (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: masm@sioc.ac.cn
Notes
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The authors declare no competing financial interest.
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ACKNOWLEDGMENT
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Financial support from National Basic Research Program of China (2015CB856600) is greatly
appreciated. We thank Mr. Yulong Song in this group for reproducing the preparation of 2c, 2h,
and 4r.
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REFERENCES
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Oxidations in the Pharmaceutical Industry. Chem. Rev. 2006, 106, 2943.
2. Tojo, G.; Fernández, M. Oxidation of Alcohols to Aldehydes and Ketones: A Guide to
Current Common Practice; Springer: New York, 2006.
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Alcohols to Carbonyl Compounds with CrO3•SiO2 in Supercritical Carbon Dioxide. J. Org.
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Catalytic Oxidation of Organic Substrates by Molecular Oxygen and Hydrogen Peroxide by
Multistep Electron Transfer-A Biomimetic Approach. Angew. Chem. Int. Ed. 2008, 47,
3506. (b) Ryland, B. L.; Stahl, S. S. Practical Aerobic Oxidations of Alcohols and Amines
with Homogeneous Copper/TEMPO and Related Catalyst Systems. Angew. Chem. Int. Ed.
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2014, 53, 8824. (c) Cao, Q.; Dornan, L. M.; Rogan, L.; Hughes, N. L.; Muldoon, M. J.
Aerobic Oxidation Catalysis with Stable Radicals. Chem. Commun. 2014, 50, 4524. (d)
Sheldon, R. A.; Arends, I. W. C. E. Organocatalytic Oxidations Mediated by Nitroxyl
Radicals. Adv. Synth. Catal. 2004, 346, 1051.
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7. (a) Lloyd, W. G. Homogeneous Oxidations of Alcohols with Palladium(II) Salts. J. Org.
Chem. 1967, 32, 2816. (b) Blackburn, T. F.; Schwartz, J. Homogeneous Catalytic Oxidation
of Secondary Alcohols to Ketones by Molecular Oxygen under Mild Conditions. J. Chem.
Soc. Chem. Commun. 1977, 157. (c) Peterson, K. P.; Larock, R. C. Palladium-Catalyzed
Oxidation of Primary and Secondary Allylic and Benzylic Alcohols. J. Org. Chem. 1998, 63,
3185. (d) Wang, L.-Y.; Li, J.; Lv, Y.; Zhang, H.-Y.; Gao, S. Aerobic Alcohol Oxidation
Using a PdCl2/N,N-dimethylacetamide Catalyst System under Mild Conditions. J.
Organometal. Chem. 2011, 696, 3257. (e) Nishimura, T.; Onoue, T.; Ohe, K.; Uemura, S.
Palladium(II)-Catalyzed Oxidation of Alcohols to Aldehydes and Ketones by Molecular
Oxygen. J. Org. Chem. 1999, 64, 6750. (f) Schultz, M. J.; Park, C. C.; Sigman, M. S. A
Convenient Palladium-Catalyzed Aerobic Oxidation of Alcohols at Room Temperature.
Chem. Commun. 2002, 3034. (g) Jensen, D. R.; Schultz, M. J.; Mueller, J. A.; Sigman, M. S.
A Well-Defined Complex for Palladium-Catalyzed Aerobic Oxidation of Alcohols: Design,
Synthesis, and Mechanistic Considerations. Angew. Chem. Int. Ed. 2003, 42, 3810. (h)
Gowrisankar, S.; Neumann, H.; Gördes, D.; Thurow, K.; Jiao, H.; Beller, M. A Convenient
and Selective Palladium-Catalyzed Aerobic Oxidation of Alcohols. Chem. Eur. J. 2013, 19,
15979. (i) Veisi, H.; Hemmati, S.; Qomi, M. Aerobic Oxidation of Benzyl Alcohols through
Biosynthesized Palladium Nanoparticles Mediated by Oak Fruit Bark Extract as an Efficient
Heterogeneous Nanocatalyst. Tetrahedron Lett. 2017, 58, 4191. (j) Verma, S.; Baig, R. B.
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