The oxidation of alcohols with O-iodoxybenzoic acid (IBX) in aqueous nanomicelles at room temperature

Article abstract of DOI:10.1016/j.tet.2014.03.047

GMPGS-2000, a nonionic amphiphile composed of Guerbet alcohol (2-octyldodecan-1-ol), MPEG-2000 and succinic acid, has been prepared as an effective nanomicelle forming species for the oxidation of alcohols with 2-iodoxybenzoic acid (IBX) in water at room temperature.

Full text of DOI:10.1016/j.tet.2014.03.047

Accepted Manuscript
The Oxidation of Alcohols with O-Iodoxybenzoic Acid (IBX) in Aqueous Nanomicelles
at Room Temperature
Aming Xie, Xiangxiang Zhou, Liandong Feng, Xinyu Hu, Wei Dong
PII:
S0040-4020(14)00381-0
10.1016/j.tet.2014.03.047
TET 25387
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 January 2014
Revised Date: 5 March 2014
Accepted Date: 13 March 2014
Please cite this article as: Xie A, Zhou X, Feng L, Hu X, Dong W, The Oxidation of Alcohols with O-
Iodoxybenzoic Acid (IBX) in Aqueous Nanomicelles at Room Temperature, Tetrahedron (2014), doi:
10.1016/j.tet.2014.03.047.
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The Oxidation of Alcohols with O-Iodoxybenzoic Acid
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(IBX) in Aqueous Nanomicelles at Room Temperature
Aming Xie, Xiangxiang Zhou, Liandong Feng, Xinyu Hu, and Wei Dong
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China

1
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Tetrahedron
journal homepage: www.elsevier.com
The Oxidation of Alcohols with O-Iodoxybenzoic Acid (IBX) in Aqueous
Nanomicelles at Room Temperature
Aming Xie, Xiangxiang Zhou, Liandong Feng, Xinyu Hu, and Wei Dong
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
GMPGS-2000, a nonionic amphiphile composed of Guerbet alcohol (2-octyldodecan-1-ol),
MPEG-2000 and succinic acid, has been prepared as an effective nanomicelle forming species
for the oxidation of alcohols with 2-iodoxybenzoic acid (IBX) in water at room temperature.
2009 Elsevier Ltd. All rights reserved
.
Available online
Keywords:
Amphiphile
2-Iodoxybenzoic acid
Alcohol
Oxidation
Micelle
Bruce H. Lipshutz et al have reported a series of metal-catalyzed
cross-coupling reactions catalyzed by the surfactant PTS or
TPGS-750-M in water at ambient temperature.9 More recently,
we have synthesized some tetrazoles in GPGS-1500/water
micelle system.10
Introduction
The oxidation of alcohols is one of the most fundamental
approaches for the synthesis of carbonyl compounds. During the
past decade, the use of 2-iodoxybenzoic acid (IBX) as the
oxidant has been dramatically increased in synthetic organic
chemistry. K. C. Nicolaou et al have reported a series of IBX-
based synthetic technology: (1) the oxidation of benzylic sites,1
(2) the cyclization of functionalized anilides to their heterocyclic
counterparts, 2 and (3) dehydrogenating ketones, aldehydes, and
silyl enol ethers to their corresponding α, β-unsaturated carbonyl
compounds.3 A mild procedure for the oxidation of alcohols with
IBX in ionic liquid [bmim]Cl and water has been developed by
Z. C. Chen.4 Recently, several IBX or IBX analogues based
methodology in water/organic solvent biphasic system has been
established.5
To further investigate micellar catalysis on organic reactions,
we have synthesized a new nonionic amphiphile (1, GMPGS-
2000, Figure 1) based on the structure of GPGS-1500 (2, Figure
1) and applied this surfactant to the oxidation of alcohols with
IBX in water at room temperature.
Results and discussion
GMPGS-2000 (2, Figure 1) was designed by replacing the
hydrophilic chain of GPGS-1500 (1, Figure 1) with methoxy
polyethylene glycol (MPEG) and synthesized through the
esterification of MPEG-2000 with the acid 3 in the general
condition (cat. TsOH, toluene, reflux, Dean-Stark trap) as a white
wax solid (Scheme 1). This route could be smoothly scaled to
>150 g with comparable yield (89 % yield). In a similar fashion,
GMPGS-1000 was prepared as a slightly yellow wax. All
GMPGS analogues were stable enough to air at room
temperatures.
During recent years, the notion of “green chemistry” has
encouraged many synthetic organic chemists to use water as the
only solvent, because 80% of chemical waste is estimated to be
organic solvents.6 Usually, the main obstacle to prevent reactions
in water is just that most uncharged organic molecules are
insoluble. One approach that circumvents this problem is to use
amphiphiles that formed micelles to accommodate lipophilic
environment for the insoluble reactants or reagents.7 Reaction
rates might be faster than those normally observed in organic
media, because the effective concentration within the micelle
could be quite high. This concept is called micellar catalysis and
y
———
researches in this field have been reported.8 Recently,

2
Tetrahedron
Entry
Substrate
Condition
Yield (%)b
63
ACCEPTED MANUSCRIPT
1
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
4a
6a
6a
6a
6a
5wt% GPGS-1500/H2O
5wt% GPGS-2000/H2O
5wt% GPGS-1000/H2O
5wt% GMPGS-1000/H2O
5wt% GMPGS-2000/H2O
5wt% GMPGS-2000/H2O
2wt% GMPGS-2000/H2O
1wt% GMPGS-2000/H2O
H2O
2
72
3
57
4
90
5
96
6
61c
7
94
8
85
9
23
10
11
12
13
14
15
5wt% Triton X-100/H2O
5wt% Brij-35/H2O
70
67
Figure 1. Structural comparisons between GPGS-1500 and
GMPGS-2000.
2wt% GMPGS-2000/H2O
1wt% GMPGS-2000/H2O
5wt% Triton X-100/H2O
H2O
97
82
65
16
a Reaction conditions: alcohol 4a or 6a (1 mmol), IBX (1.2 mmol),
surfatant/H2O (5 mL), room temperature, 24 h. b Isolated yield.
c MeOPEG-2000 was added.
Under the optimized condition, a series of aryl- and alkyl
primary alcohols were employed to explore the scope of the
oxidation methodology. As shown in Table 2, the benzyl alcohols
bearing none or electron-donating groups on the benzene ring
proceeded well to afford corresponding aldehydes in good yields
(Table 2, entries 1-6). However, no anticipated products have
been isolated when hydroxyl or dimethylamino group was
introduced to the substrates (Table 2, entries 7-8). After IBX was
added, the reaction mixture of phenol 4g changed to red while the
aniline 4h turned to dark. It was probably due to that 4-
(hydroxymethyl)phenol and N,N-dimethylaniline can function
with IBX to prevent the oxidation reactions. Although (3-
chlorophenyl) methanol performed well, only moderate yield of
2-iodobenzaldehyde (5j) was obtained, probably because of the
enhancive steric hindrance effect (Table 2, entries 9-10). With the
increase of electron withdrawing ability, the activities of the
substrates decreased relatively (Table 2, entries 11-12). In
addition, as an allyl alcohol, the reaction of compound 4m with
IBX furnished the target product in good yield (Table 2, entry
13). Also some aliphatic alcohols such as octan-1-ol and nonan-
1-ol were adopted in the oxidation reaction (Table 2, entries 14-
15).
Scheme 1. Synthesis of GMPGS-2000
As model compounds, (4-methoxyphenyl)methanol (4a) and
1-(4-methoxyphenyl)ethanol (6a) were used to investigate the
effect of amphiphiles on the oxidation of alcohols with IBX.
Initially, a series of GPGS was tested in the oxidation of alcohol
4a and only moderate yields were obtained (Table 1, entries 1-3).
It was thought that terminal hydroxyl group of GPGS may
partially function with IBX. To find better amphiphiles, GMPGS-
1000 and GMPGS-2000, analogues of GPGS, were synthesized
for the oxidation. To our delight, excellent yields of products
were obtained (Table 1, entries 4-5). However, the yield of the
aldehyde decreased severely when
a small amount of
methoxypolyethylene glycol-2000 was added to the reaction
mixture (Table 1, entry 6). Therefore, the presence of hydroxyl
group was not favourable to our methodology.
Despite of slightly decrease of the conversion, the lowered
amount of the surfactant 2 would be acceptable (Table 1, entry
7). Continued reduction the amount of GMPGS-2000, the result
was not desirable (Table 1, entry 8). When the surfactant was
removed, the reactants cannot disperse well in water, and hence
the reaction afforded the corresponding product in low yield
(Table 1, entry 9). Moreover, some commercial available
nonionic surfactants such as Triton X-100 and Brij-35 were
employed and found to be inferior to the amphiphile 2 (Table 1,
entries 10-11). The oxidation of substrate 6a was consistent with
that of alcohol 4a (Table 1, entries 12-15).
Table 2 Oxidation of primary alcohols to aldehydes.a
Table 1 Effect of amphiphiles on the oxidation of alcohols.a
Yield
Entry
1
Substrate
Product
(%)b
5a
94
4a

3
As shown in Table 3, the oxidation of secondary alcohols to
ACCEPTED MANUSCRIPT
ketones tolerates a wide range of substrate functionalities.
Excellent yields of products were obtained for electron-rich
phenethyl alcohols (Table 3, entries 1-2). Likewise, the reactions
of substrates bearing phenyl or weak electron-withdrawing
groups with IBX furnished the desired ketones in good yields
(Table 3, entries 3-5). However, when strong electron-
withdrawing group like NO2- was used, the yield of product 7f
decreased severely (Table 3, entry 6). A similar result was
obtained from the bromhydrin 6g used as the reactant (Table 3,
entry 7). Benzophenone 7h, a common photosensitizer in
photochemistry, can also be prepared through our protocol (Table
3, entry 7). In addition, cyclohexanol and cyclopentanol moieties
could be smoothly oxidized to corresponding products in
moderate to excellent yields (Table 3, entries 9-14). The aliphatic
secondary alcohols used in our procedure only furnished
moderate yields of ketones (Table 3, entries 15-16).
2
3
5b
90
4b
4c
5c
89
4
5d
95
4d
4e
4f
5
6
5e
5f
93
91
Table 3 Oxidation of secondary alcohols to ketones.a
Entry
1
Substrate
Product
Yield (%)
97
7
8
5g
5h
0
0
4g
4h
7a
6a
6b
2
3
7b
7c
86
91
9
5i
90
4i
4j
10
11
12
13
5j
5k
5l
65
85
57
86
6c
OH
4
5
7d
7e
88
90
Cl
4k
6d
4l
6e
5m
4m
4n
4o
6
7
7f
56
64
14
15
5n
5o
64
71
6f
7g
a Reaction conditions: primary alcohols (1 mmol), IBX (1.2 mmol),
2wt% GMPGS -2000/H2O (5 mL), room temperature, 24 h.
b Isolated yield.
6g

4
Tetrahedron
ACCEPTED MANUSCRIPT
Table 3. Average diameter of GPGS in water.
Amphiphile
Average diameter (nm)a
8
9
7h
90
91
96
GMPGS-1000
GMPGS-2000
GPGS-2000
56
34
14
6h
6i
7i
7j
a Determined by dynamic light scattering (DLS).
Conclusion
10
In summary, we have designed a new nonionic amphiphile by
replacing the hydrophilic chain of GPGS-1500 with methoxy
polyethylene glycol 2000 (MPEG-2000). The optimal amphiphile
(GMPGS-2000) was used for the oxidation of alcohols in water
at ambient temperature. A plausible micelle-catalytic mechanism
was proposed and the diameter of the micelles formed in water
was measured by DLS.
6j
11
7k
93
6k
O
HO
O
O
OH
O
I
I
OH
R1 R2
12
13
7l
54
65
- H2O
O
6l
O
OH
IBX
7m
OH
O
O
GMPGS-2000
nanomicelles
+
6m
R1 R2
4, 6
I
O
R1
O
R2
14
15
7n
7o
83
54
6n
6o
OH
OH
I
O
I
O
O
R2
O
+
R1
O
R1 R2
O
IBA
5, 7
R1 = Aryl-, Alkyl-
16
7p
43
GMPGS-2000
nanomicelles
=
R2 = Aryl-, Alkyl-, H-
6p
Scheme 2 Proposed catalytic process of the GMPGS-2000 for the
oxidation of alcohols.
a Reaction conditions: secondary alcohols (1 mmol), IBX (1.2 mmol),
2wt% GMPGS -2000/H2O (5 mL), room temperature, 24 h.
b Isolated yield.
Experimental section
The catalytic process of the GMPGS-2000 for the oxidation of
alcohols was shown in Scheme 2. Firstly, the hydrophobic
alcohols 4 or 6 and IBX entered into the nano-micelles formed by
GMPGS-2000 in water. Then, the alcohols were oxidized to
aldehydes or ketones with IBX through the mechanism proposed
by T. Wirth.11 Finally, the corresponding products and by-
product IBA got out of the micelles and a catalytic cycle finished.
General Experiments: NMR spectra were obtained with a
Bruker Avance 500 spectrometer or Bruker Avance 300
spectrometer. Flash column chromatography was performed by
employing 200-300 mesh silica gel. Thin-layer chromatography
(TLC) was performed with silica gel HSGF254.
GMPGS-2000 (2), < 15 g scale.
A mixture of 4-(2-octyldodecyloxy)-4-oxobutanoic acid (1.99
Aside from the structures of the surfactants, the size of
micelles may be important factor of that affect the efficiency of
the oxidation. Hence, we investigated the diameter of the
micelles formed upon dissolution of GMPGS-1000 and GMPGS-
2000 in water using dynamic light scattering (DLS). As
demonstrated in Table 3, the average diameters of micelles
formed from GMPGS-1000 and GMPGS-2000 were 46 nm and
34 nm, respectively. The size of the micelles may account for the
superior performance of GMPGS-2000 to GMPGS-1000 toward
the oxidation because of the similarities of the structures.
g,
5
mmol), MPEG-2000 (12 g, ca.
6
mmol), 4-
methylbenzenesulfonic acid (0.17 g, 1 mmol) and toluene (30
mL) was refluxed for 5 h using a Dean-Stark trap. After cooling
to room temperature, the mixture was poured into saturated
NaHCO3 (50 mL) and extracted with CH2Cl2 (3 × 30 mL). The
combined organic layers were washed with saturated NaHCO3 (3
× 30 mL), brine (2 × 30 mL), dried over anhydrous Na2SO4, and
concentrated in vacuo to afford the title compound (11 g, 91 %)
1
as a white waxy solid. H NMR (300 MHz, CDCl3) δ = 4.25 (m,
2H), 3.99 (m, 2H), 3.88 (m, 1H), 3.65 (br, 193H), 3.38 (s, 3H),

5
2.65 (m, 4H), 1.26 (br, 33H), 0.88 (t, 6H). 13C NMR (75 MHz,
CDCl3) δ = 172.06, 172.00, 72.39, 72.20, 71.66, 70.31, 68.79,
68.40, 67.16, 63.54, 61.25, 58.75, 36.96, 31.63, 30.88, 29.66,
29.36, 29.06, 28.79, 26.39, 22.41, 13.92.
2-Iodobenzaldehyde (5j) 17 White solid; mp 36-38 oC (lit. 37-38
ACCEPTED MANUSCRIPT
oC); 1H NMR (300 MHz, CDCl3) δ 10.07 (s, 1H), 7.96 (d,
J=11.1, 1H), 7.88 (dd, J=10.3, 2.3, 1H), 7.47 (t, J=10.0, 1H),
7.29 (m, 1H). 13C NMR (75 MHz, CDCl3) δ 195.75, 140.63,
135.51, 135.05, 130.24, 128.74, 100.81.
GMPGS-2000(2), > 200 g scale.
4-Formylbenzonitrile (5k)18 White solid; mp 83-85 C (lit. 80-81
o
A mixture of 4-(2-octyldodecyloxy)-4-oxobutanoic acid (40 g,
0.1 mol), MPEG-2000 (240 g, ca. 0.12 mol), 4-
methylbenzenesulfonic acid (4.3 g, 25 mmol) and toluene (500
mL) was added to a 1 L single necked round-bottom flask
equipped with a Dean-Stark trap. The mixture was refluxed until
toluene layer in the Dean-Stark trap became clear. After cooling
to rt, the mixture was poured into saturated NaHCO3 (1 L) and
extracted with CH2Cl2 (3 × 500 mL). The combined organic
layers were washed with saturated NaHCO3 (3 × 500 mL), brine
(2 × 500 mL), dried over anhydrous Na2SO4, and concentrated in
vacuo to afford the title compound (210 g, 88 %) as a slightly
yellow waxy solid. The product was identical in all aspects
(1HNMR, 13C NMR) with the sample prepared on the smaller
scale.
oC); H NMR (300 MHz, CDCl3) δ 10.10 (s, 1H), 8.02 (d, 2H),
1
7.87 (d, 2H). 13C NMR (75 MHz, CDCl3) δ 190.59, 138.63,
132.81, 129.79, 117.63, 117.45.
4-Nitrobenzaldehyde (5l)13 Yellow crystal; mp 104-106 C (lit.
105-106 C); H NMR (300 MHz, CDCl3) δ 10.17 (s, 1H), 8.40
(d, J=8.5, 2H), 8.08 (d, J=8.6, 2H). 13C NMR (75 MHz, CDCl3) δ
190.32, 150.97, 139.96, 130.39, 124.18.
o
o
1
12
1
Cinnamaldehyde (5m)
Yellow liquid; H NMR (300 MHz,
CDCl3) δ 9.72 (d, J=7.7, 1H), 7.58 (dd, J=6.5, 2.9, 2H), 7.52 (s,
1H), 7.45 (m, 3H), 6.73 (dd, J=15.9, 7.7, 1H). 13C NMR (75
MHz, CDCl3) δ 190.71, 149.81, 131.04, 128.32, 126.15, 125.56.
12
Octanal (5n)
Slightly yellow liquid; 1H NMR (300 MHz,
CDCl3) δ 9.77 (s, 1H), 2.42 (t, J=7.5, 2H), 1.83 (m, 2H), 1.31 (m,
8H), 0.88 (t, J=6.8, 3H). 13C NMR (75 MHz, CDCl3) δ 202.79,
43.81, 31.52, 29.02, 28.92, 22.48, 21.98, 13.93.
Nonanal (5o)19 Slightly yellow liquid; 1H NMR (300 MHz,
CDCl3) δ 9.77 (s, 1H), 2.42 (m, 2H), 1.63 (m, 2H), 1.28 (m,
10H), 0.88 (m, 3H). 13C NMR (75 MHz, CDCl3) δ 202.86, 43.83,
31.69, 29.21, 29.07, 29.03, 22.52, 21.99, 13.98.
General Procedure for the Oxidation of Alcohols.
A vial was charged with alcohol (1 mmol), IBX (1.2 mmol,
1.2 eq) and 2wt % GMPGS-2000/H2O solution (5 mL). The
o
mixture was stirred for 24 h at 25 C and filtered. The solid was
washed with CH2Cl2 and the filtrate was extracted with CH2Cl2
(3 × 10 mL). Then, the organic phase was combined and dried
with anhydrous Na2SO4, evaporated to dryness. The crude
product was purified was purified by column chromatography on
silica gel eluted with (petroleum ether/EtOAc) to afford the
desired product.
4-Methoxybenzaldehyde (5a)12 Yellow liquid; 1H NMR (500
MHz, CDCl3) δ 9.90 (s, 1H), 7.85 (d, J=8.3, 2H), 7.02 (d, J=8.3,
2H), 3.90 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 190.75, 164.59,
131.92, 129.92, 114.28, 55.53.
1-(4-Methoxyphenyl)ethanone (7a)20 Colourless crystal; mp 35-
o
o
1
36 C (lit. 37-39 C); H NMR (300 MHz, CDCl3) δ 7.94 (d,
J=8.9, 2H), 6.94 (d, J=8.9, 2H), 3.87 (s, 3H), 2.56 (s, 3H). 13C
NMR (75 MHz, CDCl3) δ 196.63, 163.35, 130.46, 130.16,
113.55, 55.33, 26.22.
1
1-(3-Methoxyphenyl)ethanone (7b)21 Slightly yellow liquid; H
NMR (300 MHz, CDCl3) δ 7.54 (d, J=7.5, 1H), 7.49 (s, 1H), 7.37
(t, J=7.9, 1H), 7.11 (dd, J=8.2, 2.6, 1H), 3.86 (s, 3H), 2.60 (s,
3H). 13C NMR (75 MHz, CDCl3) δ 197.79, 159.66, 138.33,
129.44, 120.99, 119.44, 112.22, 55.28, 26.60.
Acetophenone (7c)22 Colourless liquid; 1H NMR (300 MHz,
CDCl3) δ 7.97 (m, 2H), 7.58 (m, 1H), 7.46 (m, 2H), 2.61 (s, 3H).
13C NMR (75 MHz, CDCl3) δ 198.11, 136.96, 133.02, 128.46,
128.19.
2-Methoxybenzaldehyde (5b)13 Colourless crystal; mp 40-42 C
o
(lit. 36-41 oC); 1H NMR (300 MHz, CDCl3) δ 10.48 (s, 1H), 7.86
(m, 1H), 7.56 (m, 1H), 7.03 (m, 2H), 3.94 (s, 3H); 13C NMR (75
MHz, CDCl3) δ 189.66, 161.72, 135.86, 128.36, 124.69, 120.52,
111.54, 55.51.
1
3-Methoxybenzaldehyde (5c)14 Colourless liquid; H NMR (300
MHz, CDCl3) δ 9.98 (s, 1H), 7. 45 (m, 2H), 7.40 (s, 1H), 7.19 (m,
1H), 3.87 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 191.95, 159.98,
137.66, 129.88, 123.24, 121.21, 112.00, 55.22.
1
1-(2-Chlorophenyl)ethanone (7d)22 Colourless liquid; H NMR
(300 MHz, CDCl3) δ 7.54 (m, 1H), 7.40 (m, 2H), 7.35 (m, 1H),
2.65 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 200.37, 139.01,
131.93, 131.17, 130.56, 129.32, 126.86, 30.63.
3,4-Dimethoxybenzaldehyde (5d)15 White solid; mp 42-43 oC (lit.
o
41-43 C);1H NMR (300 MHz, CDCl3) δ 9.85 (s, 1H), 7.46 (dd,
1
1-(4-Chlorophenyl)ethanone (7e)22 Colourless liquid; H NMR
J=8.2, 1.7, 1H), 7.41 (s, 1H), 6.98 (d, J=8.2, 1H), 3.97 (s, 3H),
3.94 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 190.67, 154.26,
149.39, 129.91, 126.65, 110.24, 108.71, 55.98, 55.78.
Benzaldehyde (5e)12 Colourless liquid; 1H NMR (300 MHz,
CDCl3) δ 10.03 (s, 1H), 7.88 (m, 2H), 7.64 (m, 1H), 7.54 (m,
2H). 13C NMR (75 MHz, CDCl3) δ 192.23, 134.33, 129.61,
128.88.
(300 MHz, CDCl3) δ 7.90 (d, J=8.6, 2H), 7.44 (d, J=8.6, 2H),
2.59 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 196.68, 139.40,
135.28, 129.61, 128.75, 26.46.
1-(4-Nitrophenyl)ethanone (7f)23 Slightly yellow crystal; mp 75-
1
77 °C (lit. 75-79 °C); H NMR (300 MHz, CDCl3) δ 8.33 (d,
J=8.7, 2H), 8.12 (d, J=8.7, 2H), 2.69 (s, 3H). 13C NMR (75 MHz,
CDCl3) δ 196.28, 150.21, 141.26, 129.22, 123.73, 26.89.
4-Methylbenzaldehyde (5f)13 Colourless liquid; 1H NMR (300
MHz, CDCl3) δ 9.97 (s, 1H), 7.78 (d, J=8.0, 2H), 7.33 (d, J=7.9,
2H), 2.44 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 191.89, 145.44,
134.09, 129.75, 129.61, 21.78.
2-Bromo-1-phenylethanone (7g)24 White solid; mp 45-47 °C (lit.
1
47-48 °C); H NMR (300 MHz, CDCl3) δ 8.00 (d, J=7.3, 2H),
7.82 (m, 1H), 7.52 (m, 2H), 4.47 (s, 2H). 13C NMR (75 MHz,
CDCl3) δ 191.17, 133.88, 128.80, 31.07.
3-Chlorobenzaldehyde (5i)16 Slightly yellow liquid; 1H NMR
(300 MHz, CDCl3) δ 9.99 (s, 1H), 7.87 (s, 1H), 7.77 (d, J=7.5,
1H), 7.60 (m, 1H), 7.49 (t, J=7.7, 1H). 13C NMR (75 MHz,
CDCl3) δ 190.71, 137.69, 135.29, 134.25, 130.27, 129.12,
127.88.
Benzophenone (7h)25 White solid; mp 51-53 °C (lit. 50-51 °C);
1H NMR (300 MHz, CDCl3) δ 7.80 (m, 4H), 7.58 (m, 2H), 7.49
(m, 4H). 13C NMR (75 MHz, CDCl3) δ 196.64, 137.49, 132.36,
129.98, 128.22.

6
Tetrahedron
ACCEPTED MANUSCRIPT
1
Cyclohexanone (7i)26 Colourless liquid; H NMR (300 MHz,
6. Shaughnessy, K. H.; DeVasher, R. B. Cur. Org. Chem. 2005, 9,
CDCl3) δ 2.33 (t, J=6.6, 4H), 1.85 (m, 4H), 1.72 (m, 2H). 13C
NMR (75 MHz, CDCl3) δ 212.05, 41.80, 26.87, 24.82.
585-604.
7. Khan, M. N. Micellar Catalysis, CRC Press: Boca Raton, FL,
2006.
3,4-Dihydronaphthalen-1(2H)-one (7j)24 Colourless liquid; 1H
NMR (300 MHz, CDCl3) δ 8.03 (m, 1H), 7.47 (m, 1H), 7.30 (m,
2H), 2.97 (t, J=5.5, 2H), 2.66 (m, 2H), 2.15 (m, 2H). 13C NMR
(75 MHz, CDCl3) δ 198.24, 144.39, 133.29, 132.46, 128.69,
126.99, 126.49, 39.05, 29.57, 23.17.
8. Dwars, T.; Paetzold, E.; Shaughnessy, G. O. Angew. Chem. Int.
Ed. 2005, 44, 7174-7199.
9. (a) Lipshutz, B. H.; Chung, D. W.; Rich. B. Org. Lett. 2008, 10,
3793-3796; (b) Lipshutz, B. H.; Abela, A. R. Org. Lett. 2008, 10,
5329-5332; (c) Lipshutz, B. H.; Taft, B. R. Org. Lett. 2008, 10,
1329-1332; (d) Lipshutz, B. H.; Petersen, T. B.; Abela, A. R. Org.
Lett. 2008, 10, 1333-1336; (d) Lipshutz, B. H.; Ghorai, S.; Abela,
A. R.; Moser, R.; Nishikata, T.; Duplais, C.; Krasovskiy, A. J.
Org. Chem. 2011, 76, 4379-4391.
10. Xie, A. M.; Cao, M. P.; Liu, Y. Y.; Feng, L. D.; Hu, X.Y.; Dong,
W. Eur. J. Org. Chem. 2014, 436-441.
11. Wirth, T. Angew. Chem. Int. Ed. 2001, 40, 2812-2814.
12. Hoover, J. M.; Stahl, S. S. J. Am. Chem. Soc. 2011, 133, 16901–
16910.
6-Methoxy-3,4-dihydronaphthalen-1(2H)-one (7k)27 Yellow
o
o
1
solid; mp 77-79 C (lit. 78 C); H NMR (300 MHz, CDCl3) δ
7.66 (d, J=7.7, 1H), 7.28 (t, J=7.9, 1H), 7.03 (d, J=7.6, 1H), 3.87
(s, 3H), 2.90 (m, 2H), 2.84 (m, 2H), 2.13 (m, 2H). 13C NMR (75
MHz, CDCl3) δ 198.53, 156.65, 133.49, 133.41, 126.61, 118.58,
114.13, 55.57, 38.73, 22.69.
13. Lin, C. K.; Lu, T. J. Tetrahedron 2010, 66, 9688-9693.
14. Lee, K.; Maleczka, R. E. Org. Lett. 2006, 8, 1887-1888.
15. (a) Kamimura, A.; Komatsu, H.; Moriyama, T.; Nozaki Y.
Tetrahedron 2013, 69, 5968-5972; (b) Maras, N.; Polanc, S.;
Kocevar, M. Tetrahedron 2008, 64, 11618-11624.
16. Jiang, N.; Ragauskas, A. J. J. Org. Chem. 2006, 71, 7087-7090.
17. (a) Arvela, R. K.; Leadbeater, N. E. J. Org. Chem. 2003, 68, 9122-
9125; (b) Balducci, E.; Attolino, E.; Taddei, M. Eur. J. Org. Chem.
2011, 311-318.
18. Olivera, R.; SanMartin, R.; Dominguez, E.; Solans, X.; Urtiaga, M.
K.; Arriortua, M. I. J. Org. Chem. 2000, 65, 6398-6411.
19. Petricci, E.; Mann. A.; Schoenfelder, A.; Rota, A. Taddei, M.
Org. Lett. 2006, 8, 3725-3727.
20. Qian, W.; Jin, E.; Bao, W.; Zhang, Y. Tetrahedron 2006, 62, 556-
562.
21. (a) Zhang, G.; Han, X.; Luan, Y.; Wang, Y.; Wen, X.; Ding, C.
Chem. Commun, 2013, 49, 7908-7910.
22. Ruan, J.; Iggo, J. A.; Berry, N. G. Xiao, J. L. J. Am. Chem. Soc.
2010, 132, 16689-16699.
23. Kirihara, M.; Noguchi, T.; Okajima, N.; Naito, S.; Ishizuka, Y.;
Harano, A.; Tsukiji, H.; Takizawa R. Tetrahedron 2012, 68,
1515-1520.
24. (a) Kavala, V.; Naik, S.; Patel, B. K. J. Org. Chem. 2005, 70,
4267-4271. (b) Pravst, I.; Zupan, M.; Stavber, S. Tetrahedron,
2008, 64, 5191-5199.
25. Alagiri, K.; Prabhu, K. R. Tetrahedron 2011, 67, 8544-8551.
26. Sedelmeier, J.; Ley, S. V.; Baxendale, I. R.; Baumann, M. Org.
Lett, 2010, 12, 3618-3621.
27. (a) Gogoi, P.; Hazarika, P.; Konwar, D. J. Org. Chem. 2005, 70,
1934-1936; (b) Gogoi, P.; Sarmah, Ga. K.; Konwar, D. J. Org.
Chem. 2004, 69, 5153-5154.
1
3,4-Dihydronaphthalen-2(1H)-one (7l)28 Yellow liquid; H NMR
(500 MHz, CDCl3) δ 7.22 (m, 3H), 7.13 (m, 1H), 3.59 (s, 2H),
3.07 (t, J=6.7, 2H), 2.56 (t, J=6.7, 2H). 13C NMR (126 MHz,
CDCl3) δ 210.67, 136.75, 133.30, 128.21, 127.61, 126.90,
126.84, 45.10, 38.13, 28.32.
Cyclopentanone (7m)29 Colourless liquid; H NMR (300 MHz,
1
CDCl3) δ 2.15 (m, 4H), 1.95 (m, 4H).13C NMR (75 MHz, CDCl3)
δ 220.66, 38.15, 23.04.
2,3-Dihydro-1H-inden-1-one (7n)30 Yellow solid; mp 37-39 C
o
o
1
(lit. 37.5-38.5 C); H NMR (300 MHz, CDCl3) δ 7.77 (d, J=7.7,
1H), 7.59 (t, J=7.3, 1H), 7.49 (d, J=7.7, 1H), 7.37 (t, J=7.4, 1H),
3.16 (t, 2H), 2.70 (t, 2H). 13C NMR (75 MHz, CDCl3) δ 207.00,
155.08, 136.94, 134.51, 127.16, 126.61, 123.56, 36.11, 25.70.
Octan-2-one (7o)31 Slightly yellow liquid; H NMR (300 MHz,
CDCl3) δ 2.41 (t, J=7.4, 2H), 2.13 (s, 3H), 1.58 (t, 2H), 1.27 (br,
6H), 0.87 (t, J=6.5, 3H). 13C NMR (75 MHz, CDCl3) δ 209.14,
43.62, 31.44, 29.66, 28.69, 23.66, 22.34, 13.85.
4-Phenylbutan-2-one (7p)32 Colourless liquid; 1H NMR (300
MHz, CDCl3) δ 7.29 (m, 2H), 7.10 (m, 3H), 2.91 (t, 2H), 2.77 (t,
2H), 2.15 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 207.88, 140.91,
128.41, 128.21, 126.02, 45.07, 30.00, 29.65.
1
Acknowledgments
28. Li, L. Z.; Cai, P. J.; Guo, Q. X.; Xue, S. J. Org. Chem, 2008, 73,
3516-3522.
29. Zhang, G.; Wen, X.; Wang, Y.; Mo, W.; Ding, C. J. Org. Chem.
2011, 76, 4665-4668.
30. Nakamura, S.; Sugimoto, H.; Ohwada, T. J. Org. Chem. 2008, 73,
4219-4224.
31. Landers, B.; Berini, C.; Wang, C.; Navarro, O. J. Org. Chem.
2011, 76, 1390-1397.
Financial supports by the the Priority Academic Program
Development of Jiangsu Higher Education Institutions (PAPD)
and the National Nature Science Foundation of China (NSFC)
(grant number 30870625) are gratefully acknowledged.
References and notes
32. Nakao, Y.; Chen. J.; Imanka, H.; Hiyama T.; Ichikawa, Y.; Duan.
W. L.; Shintani, R.; Hayashi, T. J. Am. Chem. Soc. 2007, 129,
9137-9143.
1. (a) Nicolaou, K. C.; Montagnon, T.; Baran, P. S.; Zhong, Y. L. J.
Am. Chem. Soc. 2002, 124, 2245; (b) Nicolaou, K. C.; Baran, P.
S.; Zhong, Y. L. J. Am. Chem. Soc. 2001, 123, 3183.
2. (a) Nicolaou, K. C.; Zhong, Y. L.; Baran, P. S. Angew. Chem., Int.
Ed. 2000, 39, 625; (b) Nicolaou, K. C.; Baran, P. S.; Kranich, R.;
Zhong, Y. L.; Sugita, K.; Zou, N. Angew. Chem., Int. Ed. 2001,
40, 202; (c) Nicolaou, K. C.; Baran, P. S.; Zhong, Y. L.; Vega, J.
A. Angew. Chem., Int. Ed. 2000, 39, 2525; (d) Nicolaou, K. C.;
Baran, P. S.; Zhong, Y. L.; Barluenga, S.; Hunt, K. W.; Kranich,
R.; Vega, J. A. J. Am. Chem. Soc. 2002, 124, 2233.
Supplementary Material
Copies of 1H and 13C NMR spectra of all the products.
3. (a) Nicolaou, K. C.; Zhong, Y. L.; Baran, P. S. J. Am. Chem. Soc.
2000, 122, 7596; (b) Nicolaou, K. C.; Montagnon, T.; Baran, P. S.
Angew. Chem., Int. Ed. 2002, 41, 993; (c) Nicolaou, K. C.; Gray,
D. L. F.; Montagnon, T.; Harrison, S. T. Angew. Chem., Int. Ed.
2002, 41, 996.
4. Liu, Z.; Chen, Z. C.; Zheng, Q. G. Org. Lett. 2003, 5, 3321- 3323.
5.
(a) Thottumkara, A. P.; Bowsher, M. S.; Vinod, T. K. Org. Lett.
2005, 7, 2933; (b) Schulze, A.; Giannis, A. Synthesis 2006, 257;
(c) Muhammet, U.; Matsujiro, A.; Kazuaki, I. J. Am. Chem. Soc.
2009, 131, 251-262.

ACCEPTED MANUSCRIPT
Copies of 1H and 13C NMR spectra of all the products.
GMPGS-2000 (2)

ACCEPTED MANUSCRIPT
4-methoxybenzaldehyde (5a)

ACCEPTED MANUSCRIPT
2-methoxybenzaldehyde (5b)

ACCEPTED MANUSCRIPT
3-methoxybenzaldehyde (5c)

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3,4-dimethoxybenzaldehyde (5d)

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Benzaldehyde (5e)

ACCEPTED MANUSCRIPT
4-methylbenzaldehyde (5f)

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3-chlorobenzaldehyde (5i)

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2-iodobenzaldehyde (5j)

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4-formylbenzonitrile (5k)

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4-nitrobenzaldehyde (5l)

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Cinnamaldehyde (5m)

ACCEPTED MANUSCRIPT
Octanal (5n)

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Nonanal (5o)

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1-(4-methoxyphenyl)ethanone (7a)

ACCEPTED MANUSCRIPT
1-(3-methoxyphenyl)ethanone (7b)

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Acetophenone (7c)

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1-(2-chlorophenyl)ethanone (7d)

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1-(4-chlorophenyl)ethanone (7e)

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1-(4-nitrophenyl)ethanone (7f)

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2-bromo-1-phenylethanone (7g)

ACCEPTED MANUSCRIPT
Benzophenone (7h)