Tsuji-Wacker Oxidation of Terminal Olefins using a Palladium-Carbon Nanotube Nanohybrid

Article abstract of DOI:10.1002/cctc.201500241

Palladium nanoparticles supported on carbon nanotubes were used in the Tsuji-Wacker oxidation. The palladium-based nanohybrid was found to be very active in combination with cuprous chloride for the selective oxidation of terminal olefins into methyl ketones. The co-catalytic system operates under very mild and sustainable conditions (room temperature, atmospheric pressure, low catalyst loading), as opposed to previously reported catalysts, and can be recycled without any loss in activity. Give it a whack: Palladium nanoparticles supported on carbon nanotubes are used in combination with cuprous chloride for the selective Tsuji-Wacker oxidation of terminal olefins into methyl ketones. The co-catalytic system operates under very mild and sustainable conditions and can be recycled without any loss in activity.

Full text of DOI:10.1002/cctc.201500241

DOI: 10.1002/cctc.201500241
Communications
Tsuji–Wacker Oxidation of Terminal Olefins using
a Palladium–Carbon Nanotube Nanohybrid
Simon Donck,[a, b] Edmond Gravel,[b] Nimesh Shah,[a] Dhanaji V. Jawale,[b] Eric Doris,*[b] and
Irishi N. N. Namboothiri*[a]
Palladium nanoparticles supported on carbon nanotubes were
used in the Tsuji–Wacker oxidation. The palladium-based nano-
hybrid was found to be very active in combination with cupr-
ous chloride for the selective oxidation of terminal olefins into
methyl ketones. The co-catalytic system operates under very
mild and sustainable conditions (room temperature, atmos-
pheric pressure, low catalyst loading), as opposed to previously
reported catalysts, and can be recycled without any loss in
activity.
The Tsuji–Wacker oxidation is a practical method for the trans-
formation of terminal olefins into ketones. It usually involves
catalytic amounts of palladium together with stoichiometric
amounts of cuprous salts under aerobic conditions.[1] Recent
Figure 1. Overview of the Tsuji–Wacker oxidation over PdCNT.
efforts have been devoted to improving the process by tuning
the catalysts,[2] oxidants,[3] and/or solvents.[4] To recycle the
costly palladium catalyst and to facilitate isolation of the prod-
ucts, supported catalysis has also been investigated, including
the use of palladium on iron oxide[5] or TiO2,[6] dendrimer–palla-
dium complexes,[7] palladium on montmorillonite,[8] and palla-
dium on charcoal.[9] Although efficient, these heterogeneous
systems suffer from some drawbacks such as high tempera-
tures and/or high catalyst loadings.
The supported palladium catalyst was prepared by using
a layer-by-layer approach.[10b] First, carbon nanotubes were so-
nicated in the presence of amphiphilic nitrilotriacetic-diyne
(DANTA) surfactants in water, and this resulted in the formation
of nanoring-like structures at the surface of the CNTs. The rings
were then polymerized by UV irradiation, which reinforced the
cohesion of the supramolecular assembly. In a second step,
a
polycationic polymer [i.e., polydiallyldimethylammonium
With these critical features in mind, we sought to develop
a catalyst that would operate under mild and sustainable con-
ditions. Our laboratories recently reported supramolecular as-
semblies of metallic nanoparticles on carbon nanotubes (CNTs).
This protocol afforded densely coated CNTs that were used in
the catalysis of various organic transformations.[10] In the
course of our investigations, we demonstrated that CNTs acted
as a synergistic support capable of boosting the performance
of the catalytic metal, as nanotubes provide high specific sur-
face area and excellent nanoparticle dispersion. In addition,
nanotubes are electronically active, and stabilization of transi-
ent higher oxidation states of Pd is anticipated. We therefore
wanted to expand the use of CNT-supported palladium to the
catalysis of the Tsuji–Wacker oxidation reaction (Figure 1).
chloride (PDADMAC)] layer was deposited on the primary coat-
ing, and palladium nanoparticles (PdNPs) were added to afford
the final hybrid (i.e., PdCNT). Although other anchoring meth-
ods of PdNPs on CNTs are described in the literature, they usu-
ally do not provide such a dense and homogeneous covering
of the nanotube surface.[11] Blank experiments were conducted
with either bare nanotubes or DANTA-coated nanotubes. How-
ever, no PdNPs could be detected on the naked nanotubes
and poor Pd-covering was observed with DANTA nanotubes.
These control experiments highlight the importance of the
layer-by-layer assembly, for which the polyammonium network
provided robust anchoring and stabilization of the palladium
nanoparticles.
Transmission electron microscopy (TEM) indicated that the
PdNPs were of spherical shape, and size evaluation by statisti-
cal measurement gave a mean particle diameter of approxi-
mately 2 nm (Figure S1, Supporting Information). The volume
of the aqueous PdCNT suspension was adjusted to a Pd con-
centration of 14 mm [as determined by inductively coupled
plasma mass spectrometry (ICP-MS)]. X-ray photoelectron spec-
troscopy (XPS) analysis indicated that the particles were com-
posed of a mixture of palladium metal and palladium oxide in
an approximate ratio of 1:1 (Figure S2).
[a] S. Donck, Dr. N. Shah, Prof. Dr. I. N. N. Namboothiri
Department of Chemistry, Indian Institute of Technology Bombay
Mumbai 400 076 (India)
E-mail: irishi@chem.iitb.ac.in
[b] S. Donck, Dr. E. Gravel, Dr. D. V. Jawale, Dr. E. Doris
CEA, iBiTecS, Service de Chimie Bioorganique et de Marquage
91191 Gif-sur-Yvette (France)
E-mail: eric.doris@cea.fr
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Communications
Preliminary studies on the catalytic activity of the PdCNT
nanohybrid in the Tsuji–Wacker oxidation were conducted by
using styrene as a model substrate. Its conversion into aceto-
phenone was investigated under different conditions (Table 1).
Table 2. PdCNT-catalyzed Tsuji–Wacker oxidation of styrene derivatives.[a]
Entry
1
R
Atmosphere
Time
[h]
Yield of
2[b] [%]
Selectivity
2/3[c]
Table 1. Optimization of the Tsuji–Wacker oxidation of styrene into
acetophenone.[a]
1
2
3
4
5
6
7
8
9
10
O2
air
O2
air
O2
air
O2
air
O2
air
24
48
36
48
36
48
36
48
36
48
93
82
67
89
69
89
39
76
73
96
100:0
100:0
68:32
94:6
71:29
95:5
46:54
81:19
77:23
99:1
1a
1b
1c
1d
1e
H
4-CH2Cl
4-Cl
Entry
Solvent
Co-catalyst
[mol%]
Atmosphere
Time
[h]
Yield
[%][b]
3-NO2
4-tBu
1
2
3
4
5
6
7[c]
8[c]
9[e]
10
THF/H2O (4:1)
THF/H2O (4:1)
THF/H2O (4:1)
EtOH/H2O (1:1)
toluene/H2O (1:1)
DMF/H2O (8:1)
THF/H2O (4:1)
THF/H2O (4:1)
THF/H2O (4:1)
THF/H2O (4:1)
KBrO3 (100)
CuBr2 (10)
CuCl (10)
CuCl (10)
CuCl (10)
CuCl (10)
CuCl (5)
CuCl (5)
CuCl (10)
–
air
air
air
air
air
air
air
36
48
48
48
48
48
48
24
36
36
–
59
85
–
[a] Conditions: 1 (0.1 mmol), CuCl (5 mol%), PdCNT (0.56 mol%), THF/H2O
(4:1, 0.5 mL), RT. [b] Yield of isolated product. [c] Determined by analysis
of the crude mixture by H NMR spectroscopy.
–
68
82
93
–
1
[d]
O2
O2
[d]
[d]
O2
–
The selectivity of the catalytic oxidation of aliphatic alkenes,
on the other hand, followed another trend: experiments con-
ducted in air led mainly to isomerization of the double bond,
whereas reactions run under an O2 atmosphere afforded the
desired ketones. For example, the reaction of tetradec-1-ene
with PdCNT and CuCl in air afforded a 30:70 mixture of tetra-
decan-2-one (5a) and isomeric alkene 6a in 90% yield (Table 3,
entry 1). The same reaction conducted under an oxygen at-
mosphere afforded exclusively the Tsuji–Wacker oxidation
product (i.e., 5a) in 95% yield (Table 3, entry 2). It thus clearly
appeared that dioxygen was needed for substrates bearing an
isomerizable double bond. With these reaction conditions in
hand, we further examined the scope of the reaction of termi-
nal olefins.
[a] Conditions: 1a (0.1 mmol), co-catalyst (5–100 mol%), PdCNT (1 mol%),
solvent (0.5 mL), RT. [b] Yield of purified, isolated product. [c] Reaction
was performed with 0.56 mol% of PdCNT. [d] O2 (101.3 kPa). [e] Reaction
was performed without PdCNT.
We first looked at the nature of the co-catalysts; whereas no
product was detected with KBrO3 in THF/H2O (Table 1, entry 1),
cupric and cuprous salts proved to be better co-catalysts, as
acetophenone was isolated in moderate (CuBr2; Table 1,
entry 2) to good yields (CuCl; Table 1, entry 3). CuCl was select-
ed as the co-catalyst, and solvent effects were investigated,
but neither EtOH/H2O nor toluene/H2O gave satisfactory con-
version after 48 h (Table 1, entries 4 and 5). DMF/H2O (Table 1,
entry 6) was found to be more efficient (68% conversion), but
the best system remained THF/H2O. Using this solvent system,
the catalyst and co-catalyst loadings (initially 1 and 10 mol%,
respectively) could be lowered to 0.56 and 5 mol%, respective-
ly (Table 1, entry 7). Working under an oxygen atmosphere
gave optimal results with 93% conversion after 24 h of reac-
tion (Table 1, entry 8). Control experiments run in the absence
of either the catalyst (Table 1, entry 9) or the co-catalyst
(Table 1, entry 10) led to no product formation, highlighting
the cooperative effect between the two metals.
Table 3. Scope of the PdCNT-catalyzed Tsuji–Wacker oxidation.[a]
Entry
4
R
Product Time Yield[b] Selectivity
[h]
[%]
5/6[c,d]
1[e]
2
3
4
5
6
7
8
4a Me(CH2)10
4a Me(CH2)10
4b MeO2C(CH2)7 5b
5a; 6a
5a
36
36
36
36
36
36
36
36
36
36
90
92
96
92
97
93
93
95
94
93
30:70
100:0
98:2
95:5
100:0
98:2
96:4
99:1
100:0
98:2
We next expanded the scope of the above process to the
oxidation of variously substituted styrenes. Surprisingly, the
Tsuji–Wacker oxidation of substituted styrenes under an
oxygen atmosphere led to some side formation of benzalde-
hyde derivatives resulting from oxidative cleavage of the
alkene unit (Table 2, entries 3, 5, 7, and 9). The formation of
these unwanted products could, however, be minimized by
working in air, as we observed in this case better selectivity to-
wards acetophenone, although longer reaction times were re-
quired to reach satisfactory conversion yields (Table 2, en-
tries 4, 6, 8, and 10).
4c
HO2C(CH2)7
5c
5d
5e
5 f
5g
5h
5i
4d OHC(CH2)7
4e HO(CH2)8
4 f
Br(CH2)8
4g N3(CH2)8
4h O2N(CH2)8
9
10
4i
I(CH2)8
[a] Conditions: 4 (0.1 mmol), CuCl (5 mol%), PdCNT (0.56 mol%), THF/H2O
(4:1, 0.5 mL), RT, O2 (101.3 kPa). [b] Yield of isolated product. [c] Deter-
mined by analysis of the crude mixture by 1H NMR spectroscopy. [d] Com-
pound 6 was obtained as a mixture of isomeric alkenes. [e] Reaction was
performed in air.
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The process was found to tolerate a large number of func-
tional moieties such as ester (Table 3, entry 3), carboxylic acid
(Table 3, entry 4), aldehyde (Table 3, entry 5), alcohol (Table 3,
entry 6), bromide (Table 3, entry 7), azide (Table 3, entry 8),
nitro (Table 3, entry 9), and iodide (Table 3, entry 10) groups.
Products were obtained in excellent yields with high selectivity.
Noteworthy, no alcohol or aldehyde oxidation was detected
(Table 3, entries 5 and 6) under the PdCNT/CuCl-mediated con-
ditions.
CNTs could be detected by ICP-MS analysis of the above mix-
tures. In addition, TEM analysis of the catalyst after the fifth
cycle indicated no morphological alteration, except for some
occasional bare areas. These results substantiate the robust-
ness of the Pd tethering.
A
proposed
mechanism
(Scheme 2) for the above co-cata-
lytic transformation involves initial
aerobic oxidation of CuI into CuII
(path A), followed by the copper(-
II)-mediated oxidation of Pd0
(path B). The activated PdII species
then undergoes complexation with
the olefinic substrate before nucle-
ophilic attack of water (path C)
The observed selectivity towards methyl ketone formation
was good to excellent in all the above cases. However, the re-
action of (allyloxy)methylbenzene with PdCNT/CuCl under an
O2 atmosphere afforded a 60:40 mixture of expected methyl
ketone 5j and aldehyde 6j (Scheme 1) that resulted from oxi-
dation of the terminal carbon atom (93% yield, 24 h). The for-
mation of the aldehyde can be ascribed to palladium coordina-
tion to the allylic oxygen atom, which causes water to attack
the terminal position.[12]
Scheme 2. Proposed mecha-
nism for the PdCNT/CuCl-
mediated Tsuji–Wacker oxida-
tion of terminal olefins.
and subsequent release of the ketone product together with
Pd0, which then enters a new catalytic cycle.
In summary, a heterogeneous catalyst was assembled by sta-
bilization of palladium nanoparticles on carbon nanotubes.[11]
The resulting nanohybrid was used in the co-catalytic Tsuji–
Wacker oxidation of olefins in the presence of cuprous chlo-
ride. The system proved very efficient on all the investigated
substrates, demonstrated high selectivity toward methyl
ketone formation, tolerated various functional groups, operat-
ed with minimal amounts of the co-catalysts at room tempera-
ture, and could be readily recycled.
Scheme 1. Reactivity of (allyloxy)methylbenzene in the Tsuji–Wacker oxida-
tion.
The performance of our PdCNT/CuCl system was compared
to that of a reference system. An oxidation reaction of tetra-
dec-1-ene was thus set with PdCl2/CuCl/O2 in THF/H2O. Under
these conditions, the PdCl2-based system afforded a 1:2 mix-
ture of expected methyl ketone 5a and isomerized olefin 6a
in approximately 90% yield after 36 h of reaction. Although
the yields of products were satisfactory, selectivity was poor.
This selectivity has to be compared to that of PdCNT (5a/6a=
100:0), which highlights the superiority of the CNT-supported
palladium catalyst.
Experimental Section
Typical procedure for Tsuji–Wacker oxidation
Pd/CNT (40 mL of a 14 mm suspension, 0.56 mol%) and CuCl
(0.5 mg, 5 mol%) were added to THF/H2O (4:1, 0.5 mL). Oxygen
was bubbled into the mixture for 15 min and styrene (10.4 mg,
0.1 mmol) was added. The mixture was stirred at room tempera-
ture under an oxygen (balloon) atmosphere until completion.
Water (2 mL) was added, and the aqueous phase was extracted
with EtOAc (3”3 mL). The combined organic layer was dried
(Na2SO4), filtered, and concentrated under reduced pressure. The
crude product was purified by chromatography (silica gel, petrole-
um ether/EtOAc=90:10) to afford 2a as a colorless oil (11.2 mg,
93%).
To better understand the nature of the catalysis, an oxida-
tion reaction of tetradec-1-ene was set up under the above-
mentioned conditions (0.56 mol% PdCNT, 5 mol% CuCl, O2 at-
mosphere). After stirring for 12 h, the PdCNT catalyst was re-
moved by centrifugation. At this point, approximately 40%
1
conversion was reached, as determined by H NMR spectrosco-
py. The catalyst-free supernatant was then stirred for an addi-
tional 24 h, but no further conversion was detected, which
thus demonstrated the heterogeneous nature of the catalyst.
Finally, the recyclability of the palladium catalyst was as-
sessed by using styrene as the substrate. At the end of the re-
action, the mixture was centrifuged and the supernatant was
worked-up to isolate acetophenone. The Pd/CNT catalyst was
washed with water and THF and resuspended in THF/H2O. Sty-
rene and CuCl were added, and the mixture was stirred for
24 h at room temperature under an O2 atmosphere. The over-
all process was repeated four times. No significant decrease in
the catalytic activity was observed throughout the five cycles,
as the yields of the isolated product remained nearly constant
(90–93%). No palladium that might have leached out of the
Characterization data
Acetophenone (2a): 1H NMR (500 MHz, CDCl3) d=7.95 (d, J=
7.4 Hz, 2H), 7.55 (t, J=7.4 Hz, 1H), 7.45 (t, J=7.4 Hz, 2H), 2.59 ppm
(s, 3H); 13C NMR (125 MHz, CDCl3) d=198.3, 137.2, 133.2, 128.7,
128.4, 26.7 ppm.
1
4-(Chloromethyl)acetophenone (2b): H NMR (400 MHz, CDCl3) d=
7.95 (d, J=8.4 Hz, 2H), 7.49 (d, J=8.4 Hz, 2H), 4.62 (s, 2H),
2.61 ppm (s, 3H); 13C NMR (100 MHz, CDCl3) d=197.7, 142.6, 137.2,
129.4, 128.9, 45.5, 26.9 ppm.
1
4-Chloroacetophenone (2c): H NMR (400 MHz, CDCl3) d=7.87 (dt,
J=8.6 Hz, J=2.0 Hz, 2H), 7.42 (dt, J=8.6 Hz, J=2.0 Hz, 2H),
2.58 ppm (s, 3H); 13C NMR (100 MHz, CDCl3) d=197.0, 139.7, 135.6,
129.9, 129.0, 26.7 ppm.
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1
3-Nitroacetophenone (2d): H NMR (400 MHz, CDCl3) d=8.77–8.76
11-Nitroundecan-2-one (5h): 1H NMR (400 MHz, CDCl3) d=4.37 (t,
J=7.1 Hz, 2H), 2.41 (t, J=7.4 Hz, 2H), 2.13 (s, 3H), 1.99 (quint., J=
7.2 Hz, 2H), 1.61–1.52 (m, 2H), 1.38–1.21 ppm (m, 10H); 13C NMR
(100 MHz, CDCl3) d=209.5, 75.9, 43.9, 31.1, 29.9, 29.4, 29.2, 28.9,
27.6, 26.4, 23.9 ppm.
(m, 1H), 8.42 (d, J=8.0 Hz, 1H), 8.28 (d, J=8.0 Hz, 1H), 7.69 (t, J=
8.0 Hz, 1H), 2.69 ppm (s, 3H); 13C NMR (100 MHz, CDCl3) d=195.8,
148.4, 138.4, 133.9, 130.0, 127.6, 123.4, 26.6 ppm.
1
4-(tert-Butyl)acetophenone (2e): H NMR (400 MHz, CDCl3) d=7.90
(d, J=8.4 Hz, 2H), 7.48 (d, J=8.4 Hz, 2H), 2.59 (s, 3H), 1.35 ppm (s,
9H); 13C NMR (100 MHz, CDCl3) d=197.8, 156.8, 134.6, 128.2, 125.4,
35.1, 31.0, 26.5 ppm.
11-Iodoundecan-2-one (5i): 1H NMR (400 MHz, CDCl3) d=3.18 (t,
J=7.0 Hz, 2H), 2.41 (t, J=7.4 Hz, 2H), 2.13 (s, 3H), 1.81 (quint., J=
7.2 Hz, 2H), 1.59–1.54 (m, 2H), 1.39–1.22 ppm (m, 10H); 13C NMR
(100 MHz, CDCl3) d=209.2, 43.7, 33.5, 33.0, 30.4, 29.8, 29.2, 29.1,
29.0, 28.4, 23.7 ppm.
1
4-(Chloromethyl)benzaldehyde (3b): H NMR (400 MHz, CDCl3) d=
10.0 (s, 1H), 7.88 (d, J=8.2 Hz, 2H), 7.56 (d, J=8.2 Hz, 2H),
4.63 ppm (s, 2H).
4-Chlorobenzaldehyde (3c): 1H NMR (400 MHz, CDCl3) d=9.98 (s,
1H), 7.83 (dt, J=8.6 Hz, J=2.0 Hz, 2H), 7.51 ppm (dt, J=8.6 Hz, J=
1.7 Hz, 2H); 13C NMR (100 MHz, CDCl3) d=191.1, 141.2, 134.9,
129.7, 129.1 ppm.
Recycling experiment
A typical oxidation reaction of styrene was set up as above starting
from styrene (0.1 mmol), CuCl (5 mol%), and PdCNT (0.56 mol%) in
THF/H2O (4:1, 0.5 mL). The mixture was stirred at room tempera-
ture under an oxygen atmosphere for 24 h. The catalyst was recov-
ered by centrifugation, and the supernatant was worked up as
above. The recovered catalyst was washed with water and reused
in a subsequent oxidation reaction of styrene with added CuCl.
3-Nitrobenzaldehyde (3d): 1H NMR (400 MHz, CDCl3) d=10.13 (s,
1H), 8.73 (t, J=1.6 Hz, 1H), 8.49 (dd, J=7.8 Hz, J=1.6 Hz, 1H), 8.24
(dd, J=7.8 Hz, J=1.6 Hz, 1H), 7.77 ppm (t, J=7.8 Hz, 1H); 13C NMR
(100 MHz, CDCl3) d=189.6, 148.7, 137.3, 134.5, 130.3, 128.5,
124.5 ppm.
1
4-tert-Butylbenzaldehyde (3e): H NMR (400 MHz, CDCl3) d=9.99 (s,
Acknowledgements
1H), 7.82 (d, J=8.4 Hz, 2H), 7.55 (d, J=8.4 Hz, 2H), 1.36 ppm (s,
9H); 13C NMR (100 MHz, CDCl3) d=192.0, 158.4, 134.0, 129.6, 125.9,
35.3, 31.0 ppm.
Support from the Indo-French Centre for the Promotion of Ad-
vanced Research (IFCPAR)/Centre Franco-Indien pour la Promo-
tion de la Recherche AvancØe (CEFIPRA) is gratefully acknowl-
edged (Project no. 4705-1). S.D. thanks the Department of Science
and Technology (Government of India) and the Science & Tech-
nology Department (French Embassy in India) for the award of
a Raman-Charpak fellowship. The TEM-team platform (CEA,
iBiTec-S) is acknowledged for help with TEM images. The “Service
de Chimie Bioorganique et de Marquage” belongs to the Labora-
tory of Excellence in Research on Medication and Innovative
Therapeutics (ANR-10-LABX-0033-LERMIT).
2-Tetradecanone (5a): 1H NMR (400 MHz, CDCl3) d=2.41 (t, J=
7.5 Hz, 2H), 2.13 (s, 3H), 1.55–1.60 (m, 2H), 1.20–1.32 (m, 18H),
0.87 ppm (t, J=8.6 Hz, 3H); 13C NMR (100 MHz, CDCl3) d=209.7,
44.0, 32.1, 30.4, 30.0, 29.8, 29.8, 29.7, 29.6, 29.5, 29.4, 24.1, 22.9,
14.3 ppm.
1
Methyl 10-oxoundecanoate (5b): H NMR (400 MHz, CDCl3) d=3.64
(s, 3H), 2.39 (t, J=7.4 Hz, 2H), 2.27 (t, J=7.4 Hz, 2H), 2.11 (s, 3H),
1.61–1.51 (m, 4H), 1.29–1.22 ppm (m, 8H); 13C NMR (100 MHz,
CDCl3) d=209.5, 174.5, 51.6, 43.9, 34.2, 30.0, 29.3, 29.2 (3C), 25.0,
23.9 ppm.
1
10-Oxoundecanoic acid (5c): H NMR (500 MHz, CDCl3) d=2.41 (t,
Keywords: heterogeneous catalysis · olefins · nanoparticles ·
nanotubes · oxidation
J=7.4 Hz, 2H), 2.36 (t, J=7.4 Hz, 2H), 2.13 (s, 3H), 1.64–1.54 (m,
4H), 1.31–1.24 ppm (m, 8H); 13C NMR (125 MHz, CDCl3) d=209.6,
178.7, 43.9, 30.0, 29.9, 29.3, 29.2 (2C), 29.1, 24.8, 24.0 ppm.
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Chem. Int. Ed. 2013, 52, 9751; Angew. Chem. 2013, 125, 9933; f) T. Mitsu-
dome, S. Yoshida, T. Mizugaki, K. Jitsukawa, K. Kaneda, Angew. Chem. Int.
Ed. 2013, 52, 5961; Angew. Chem. 2013, 125, 6077.
10-Oxoundecanal (5d): 1H NMR (500 MHz, CDCl3) d=9.76 (t, J=
1.8 Hz, 1H), 2.43–2.39 (m, 4H), 2.13 (s, 3H), 1.65–1.54 (m, 4H),
1.33–1.24 ppm (m, 8H); 13C NMR (125 MHz, CDCl3) d=209.5, 203.1,
44.0, 43.9, 30.0, 29.3 (2C), 29.2 (2C), 23.9, 22.2 ppm.
11-Hydroxyundecan-2-one (5e): 1H NMR (500 MHz, CDCl3) d=3.62
(t, J=6.6 Hz, 2H), 2.40 (t, J=7.5 Hz, 2H), 2.12 (s, 3H), 1.74 (br s,
1H), 1.56–1.51 (m, 4H), 1.37–1.22 ppm (m, 10H); 13C NMR
(125 MHz, CDCl3) d=209.7, 63.2, 44.0, 32.9, 30.1, 29.6, 29.5, 29.5,
29.3, 25.9, 25.0 ppm.
1
11-Bromoundecan-2-one (5 f): H NMR (400 MHz, CDCl3) d=3.40 (t,
J=6.9 Hz, 2H), 2.41 (t, J=7.4 Hz, 2H), 2.13 (s, 3H), 1.84 (quint., J=
7.2 Hz, 2H), 1.60–1.54 (m, 2H), 1.44–1.38 (m, 2H), 1.32–1.22 ppm
(m, 8H); 13C NMR (100 MHz, CDCl3) d=209.6, 44.0, 34.2, 33.0, 30.1,
29.4 (2C), 29.3, 28.9, 28.3, 24.0 ppm.
1
11-Azidoundecan-2-one (5g): H NMR (400 MHz, CDCl3) d=3.24 (t,
J=7.0 Hz, 2H), 2.41 (t, J=7.4 Hz, 2H), 2.13 (s, 3H), 1.62–1.54 (m,
4H); 1.38–1.25 ppm (m, 10H); 13C NMR (100 MHz, CDCl3) d=209.6,
51.6, 43.9, 30.0, 29.4 (2C), 29.3, 29.2, 29.0, 26.8, 24.0 ppm.
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Received: March 6, 2015
Published online on July 17, 2015
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