Combination of gold and iridium catalysts for the synthesis of N-alkylated amides from nitriles and alcohols

Article abstract of DOI:10.1039/c4cy01506a

An alternative and efficient approach for the synthesis of N-alkylated amides from nitriles and alcohols was proposed and accomplished. By the combination of [(IPr)Au(NTf₂)] (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and [CpIrCl₂]₂ (Cp = η⁵-pentamethylcyclopentadienyl), a series of nitriles were first hydrated to give amides, in which the resulting amides were further N-alkylated with a variety of alcohols as alkylating agents to afford N-alkylated amides with good to excellent yields. Compared with previous methods for the synthesis of N-alkylated amides from nitriles and alcohols as starting materials, this protocol could be accomplished with high atom economy under more environmentally benign conditions.

Full text of DOI:10.1039/c4cy01506a

View Article Online
View Journal
Catalysis
Science &
Technology
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: F. Li, J. Ma, L. Lu,
X. Bao and W. Tang, Catal. Sci. Technol., 2015, DOI: 10.1039/C4CY01506A.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/catalysis

Catalysis Science & Technology
Page 1 of 7Journal Name
Dynamic Article Links►
View Article Online
DOI: 10.1039/C4CY01506A
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
ARTICLE TYPE
Combination of gold and iridium catalysts for the synthesis of N-
alkylated amides from nitriles and alcohols†
Feng Li,*a Juan Ma,a Lei Lu,a Xiaofeng Baob and Wanying Tanga
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
An alternative and efficient approach for the synthesis of Nꢀalkylated amides from nitriles and alcohols was proposed and accomplished.
By the combination of [(IPr)AuNTf] (IPr
= 1,3ꢀbis(diisopropylphenyl)imidazolꢀ2ꢀylidene) and [Cp*IrCl2]2 (Cp* =
η5ꢀ
pentamethylcyclopentadienyl), a series of nitriles are first hydrated to give amides, followed by the resulting amides were further Nꢀ
alkylated with a variety of alcohols as alkylating agents to afford Nꢀalkylated amides with good to excellent yields. Compared with
10 previous methods for the synthesis of Nꢀalkylated amides from nitriles and alcohols as starting materials, this protocol could be
accomplished with high atom economy under more environmentally benign conditions.
Prevous reports
Introduction
A
The Nꢀalkylated amides constitute one of the most important
O
classes of nitrogenꢀcontaining compounds because they
15 occurred widely in natural products, pharmaceuticals,
agrochemicals, polymers, peptides and
polymers.1
[Ru]
R2
OH
R1
NH2
R2
N
R1
+
H
-[H]
O
-[H]
R2
OH
Traditionally, Nꢀalkylated amides were synthesized via the
coupling of activated carboxylic acid derivatives, such as acid
chlorides, anhydrides and esters, with Nꢀalkylated amines.2
20 However, these procedures are suffering from the use of the
stoichiometric amount of hazardous and/or expensive reagents,
low tolerance to sensitive functional groups, and the
generation of a large amount of harmful byꢀproducts. In recent
years, the synthesis of Nꢀalkylated amides via transition
25 metalꢀcatalyzed dehydrogenative coupling of amines and
alcohols has been developed and attracted much attention due
to the low toxicity of alcohols and high atom economy of
reaction (Scheme 1, A).3 Although significant advances have
been made, Nꢀalkylated amines would be generated inevitably
30 as byꢀproducts (even with high proportion) in above process.
The classical Ritter reaction possesses a long history and
provides a powerful method for the synthesis of Nꢀalkylated
amides from easily available nitriles and alcohols as starting
materials (Scheme 1, B).4 However, this reaction was carried
35 out in the presence of an excess amount of concentrated
sulfuric acid, and thus its application were seriously restricted.
In 2013, Hong and coꢀworkers reported a catalytic strategy
available for the synthesis of Nꢀalkylated amides from nitriles
and alcohols based on “hydrogen transfer” using
40 [RuH2(CO)(PPh3)3] as the catalyst (Scheme 1, C).5 Despite
complete atom efficiency, this procedure has still obvious
limitations and it requires 10 mol% catalyst loading, 10 mol%
ligand (NHC precursor) and 20 mol% inorganic strong base
(NaH). More recently, we demonstrated the synthesis of Nꢀ
45 alkylated amides via iridiumꢀcatalyzed tandem hydration/Nꢀ
+[H]
R2
R2
N
R1
N
R1
R2
N
H
R1
-H2O
H
by-product
B
R3
O
O
H2SO4 (excess)
R1 CN
+
R1
N
R2
R2
OH
OH
R3
C
RuH2(CO)(PPh3)3
NHC precursor
R2
N
R1
R1 CN
R2
+
H
O
D
O
R1
N
H
R3
R1
NH2
R1 CN
OH
N
Hydration
N-alkylation
R2
H2O
[Cp*IrCl2]2
R2CN
by-product
R3
OH
Scheme 1 Strategies for the synthesis of Nꢀalkylated amides from alcohols.
50 alkylation reaction from nitriles, nꢀbutylaldoxime and
alcohols (Scheme 1, D).6 This procedure is attractive due to
the use of low catalyst loading, high yields and operational
convenience. However, 1.1ꢀ1.3 equiv of nꢀbutylaldoxime was
used as the water surrogate, and thus it resulted in the
55 generation of large amount of nꢀbutyronitrile as byꢀproducts
and low atom economy. From the standpoint of sustainable
chemistry, it is necessary to develop a new catalytic system
for the synthesis of Nꢀalkylated amides from nitriles and
alcohols with high atom economy under more
This journal is © The Royal Society of Chemistry [year]
[journal], [year], [vol], 00–00 | 1

Catalysis Science & Technology
Page 2 of 7
View Article Online
DOI: 10.1039/C4CY01506A
Table 1 Synthesis of Nꢀalkylated amides from benzonitrile 1a and a
variety of alcohols 2 a,b
environmentally benign conditions.
In the past decade, homogeneous gold complexes have
emerged as one of the most promising catalysts for the
activation of multiple bonds in organic synthesis.7 Especially,
Nolan and coꢀworkers have demonstrated that cationic gold
O
1) [(IPr)Au(NTf2)] (2 mol%)
THF/H2O(1:1), 130 oC, 12 h
CN
N
R
H
2) [Cp*IrCl2]2 (1 mol%), Cs2CO3 (0.2 equiv)
2 (1.2 equiv), toluene, 130 oC, 12 h
5
complexes
bis(diisopropylphenyl)imidazolꢀ2ꢀylidene,
bis(trifluoromethanesulfonyl)imidate)] is highly effective
catalysts for the hydration of nitriles to amides under
[(IPr)Au(NTf2)]
[IPr
=
NTf
1,3ꢀ
=
1a
4
Entry
Yield (%)b
Alcohol
Product
O
OH
OH
N
H
10 microwave irradiation.8 Encouraged by their research and as
part of our continuing interest in the development of catalytic
transformations with the activation of alcohols as
electrophiles,6,9 we herein wish to report an alternative and
efficient protocol for the synthesis of Nꢀalkylaed amides from
15 nitriles and alcohols by the combination of gold and iridum
catalysts. The proposed reaction pathway is shown in Scheme
2. Nitriles are first hydrated to form amides catalyzed by a
gold complex, and the resulting amides are further Nꢀalkylated
with alcohols to afford Nꢀalkylated amides catalyzed by an
20 iridium complex.
1
85
F
F
2b
4ab
O
N
H
2
84
Cl
Cl
2c
4ac
Cl
O
Cl
OH
OH
N
H
3
4
82
80
Cl
Br
Cl
Br
2d
2e
4ad
O
N
H
This work
4ae
Au
Ir
O
O
O
R1 CN
R1
N
R2
R1
NH2
OH
OH
N
H
H
5
6
81
84
H2O
H2O
R2
OH
F3C
CF3
2f
4af
O
Scheme 2 The alternative protocol for the synthesis of Nꢀalkylated
amides from nitriles and alcohols.
N
H
F3CO
OCF3
Results and discussion
2g
4ag
Me
O
Me
25 Our initial investigation focused on the synthesis of Nꢀ
benzylbenzamide from benzonitrile 1a and benzyl alcohol 2a.
When [(IPr)Au(NTf2)] was used as the catalyst, the hydration
OH
OH
OH
N
H
81
83
7
8
2h
4ah
o
of 1a proceeded in THF/H2O (1:1) at 130 C for 12 h to give
O
benzamide 3a in 90% yield
[
Equation (1)]
.
Using
N
H
30 [(IPr)Au(OTf)] (OTf = triflate) as the alternative catalyst, the
product 3a could be obtained in 83% yield. However, only
10% yield was found when [(Ph3P)Au(NTf2)] was used as a
Me
Me
2i
4ai
O
N
H
9
85
86
O
MeO
OMe
CN
[Au] (2 mol%)
NH2
2j
4aj
THF/H2O (1:1), 130 oC, 12 h
(1)
O
1a
3a
OH
OH
OH
N
H
10
[Au] = [(IPr)Au(NTf2)], 90% yield
[(IPr)Au(OTf)], 83% yield
[[(Ph3P)Au(NTf2)], 10% yield
2k
4ak
O
1) [(IPr)Au(NTf2)] (2 mol%)
THF/H2O (1:1), 130 oC, 12 h
O
CN
S
S
N
H
N
H
(2)
2) [Cp*IrCl2]2 (1 mol%), Cs2CO3 (0.2 equiv)
2a (1.2 equiv), toluene, 130 oC, 12 h
11
12
84
80
2l
4al
1a
4aa, 84% yield
O
O
O
N
H
Cl
Cl
N
N
Ir
Ir
Cl
Cl
2m
4am
Au
NTf2
35
[(IPr)Au(NTf2)]
[Cp*IrCl2]2
2
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 3 of 7
Catalysis Science & Technology
View Article Online
DOI: 10.1039/C4CY01506A
Table 1 (Continued)
Table 2 Synthesis of Nꢀalkylated amides from a series of nitriles 1 and
40 benzyl alcohol 2a a,b
Entry
Yield (%)b
Alcohol
Product
O
O
1) [(IPr)Au(NTf2)] (2 mol%)
THF/H2O(1:1), 130 oC, 12h
R
N
N
H
R
CN
H
OH
2) [Cp*IrCl2]2 (1 mol%), Cs2CO3 (0.2 equiv)
2 (1.2 equiv.), toluene, 130 oC, 12h
13
82
Fe
Fe
1
4
Yield (%)b
Entry
Nitrile
Product
2n
4an
O
O
CN
CN
OH
OH
OH
N
H
N
H
14
15
16
81c
79c
81c
1
85
F
F
2o
2p
2q
4ao
1b
1c
4ba
O
O
N
H
N
H
2
3
88
86
Cl
Cl
4ap
4ca
O
O
Cl
Cl
CN
Cl
Cl
N
H
N
H
1d
1e
4da
4aq
O
O
O
Br
CN
CN
Br
N
H
HO
OH
N
N
4
5
80
84
H
H
17
77d
4ea
2r
4ar
O
a
N
H
Reaction conditions: 1) 1a (1 mmol), [(IPr)Au(NTf2)] (2 mol%), THF
o
(0.5 mL), H2O (0.5 mL), 130 C, 12 h; 2) [Cp*IrCl2]2 (1 mol%), 2 (1.2
Br
F3C
Me
Br
5
mmol), Cs2CO3 (0.2 equiv), toluene (1 mL), 130 oC, 12 h. b Isolated yield.
1f
4fa
c
d
In the step of Nꢀalkylation, 2 (2 mmol), KOH (0.2 equiv).
mmol), the yield is based on 2r.
2r (0.5
O
CN
N
H
6
82
F3C
1g
1h
4ga
catalyst under same reaction conditions. Apparently, the gold
O
10 complex bearing a NHC ligand exhibited higher activity than
one bearing a phosphine ligand under current conditions, and
thus [(IPr)Au(NTf2)] was selected as the catalyst in the step of
the hydration of nitrile. In our previous work,9g [Cp*IrCl2]2
(Cp* = pentamethylcyclopentadienyl) was proven to be the
15 most effective catalyst for the Nꢀalkylation of benzamide with
benzyl alcohol over other commercially available transition
CN
CN
N
H
7
8
80c
Me
4ha
O
N
H
82c
MeO
MeO
1i
4ia
metal complexes, including [Ir(cod)Cl]2 (cod
=
1,5ꢀ
O
cyclooctadienyl), [Cp*RhCl2]2, [Rh(cod)Cl]2 and [Ru(pꢀ
cymene)Cl2]2. As a result of it, [Cp*IrCl2]2 was selected as the
20 catalyst in the step of Nꢀalkylation with alcohol. The
CN
CN
S
S
N
H
9
81
1j
4ja
O
sequential
hydration/Nꢀalkylation
catalyzed
by
the
O
O
combination of [(IPr)Au(NTf2)] and [Cp*IrCl2]2 was then
examined. In the presence of [Cp*IrCl2]2 (1 mol%), Cs2CO3
(0.2 equiv) and benzyl alcohol 2a (1.2 equiv), the resulting
25 intermediate 3a in the step of hydration could be further
converted to the Nꢀalkylated product 4aa in 84% yield
N
H
82d
10
11
12
1k
4ka
Me
Me
H
N
CN
CN
79e
O
[
Equation (2)]
.
1l
4la
With the identified catalytic system in hand, the scope of
O
reaction with respect to alcohols was investigated and these
30 results are summarized in Table 1. Transformations of
benzylic alcohols bearing one or two halogen atoms, such as
fluorine 2b, chlorine 2c, dichloride 2d and bromine 2e, gave
the corresponding products 4ab-4ae in 80ꢀ85% yields (Table
1, entries 1ꢀ4). When benzylic alcohols bearing a more strong
35 electronꢀwithdrawing substituent, such as trifluoromethyl 2f
and trifluoromethoxy 2g, were used as substrates, the desired
products 4af and 4ag were obtained in 81% and 84% yields,
respectively (Table 1, entries 5ꢀ6). Benzylic alcohols bearing
N
H
77e
1m
4ma
a
Reaction conditions: 1) 1a (1 mmol), [(IPr)Au(NTf2)] (2 mol%), THF
o
(0.5 mL), H2O (0.5 mL), 130 C, 12 h; 2) [Cp*IrCl2]2 (1 mol%), 2a (1.2
mmol), Cs2CO3 (0.2 equiv), toluene (1 mL), 130 oC, 12 h. b Isolated yield.
In the step of hydration, 140 C. d In the step of Nꢀalkylation, the use of
c
o
e
45 KOH (0.2 equiv) instead of Cs2CO3.
In the step of hydration,
o
[(IPr)Au(NTf2)] (5 mol%), MW, 140 C, 6 h; In the step of Nꢀalkylation,
[Cp*IrCl2]2 (2 mol%), 2a (2 equiv), Cs2CO3 (0.4 equiv), MW, 130 oC, 3 h.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3

Catalysis Science & Technology
Page 4 of 7
View Article Online
DOI: 10.1039/C4CY01506A
an electronꢀdonating substituent, such as methyl 2h-i and
methoxy 2j, proceeded smoothly as well, giving the
corresponding products 4ah-4aj in 81ꢀ85% yields (Table 1,
entries 7ꢀ9). Furthermore, 2ꢀnaphthalenemethanol 2k,
resonance (13C NMR) spectra were recorded at 125 MHz using a
Bruker Avance 500 spectrometer. Chemical shifts are reported in
delta (δ) units, ppm relative to the center of the triplet at 77.0 ppm
for CDCl3 and 39.5 ppm for DMSOꢀd6. 13C NMR spectra were
5
thiophenꢀ2ꢀylmethanol 2l, 2ꢀfuranylmethanol 2m and 60 routinely run with broadband decoupling. [(IPr)Au(NTf2)]11 and
ferrocenemethanol 2n were also proven to be suitable
substrates and the desired products 4ak-4an were obtained in
80ꢀ86% yield (Table 1, entries 10ꢀ13). Aliphatic alcohols,
such as nꢀhexanol 2o, 3ꢀmethylꢀ1ꢀbutanol 2p and
10 cyclohexylmethanol 2q, could be also converted to the Nꢀ
alkylated products 4ao-4aq in 79ꢀ81% yields, although 2
equiv of alcohols were required (Table 1, entries 14ꢀ16).
When 1,3ꢀbenzenedimethanol 2r was used as the substrate,
the N,N’ꢀdialkylated product 4ar was obtained in 77% yield
15 (Table 1, entry 17).
[Cp*IrCl2]212 were synthesized according to previous reports.
General procedure for the synthesis of N-alkylated amines
from nitriles and alcohols. To a 25 ml ovenꢀdried Schlenk tube
were added nitrile 1 (1 mmol), [(IPr)Au(NTf2)] (0.02 mmol, 2
65 mol%), THF (0.5 mL), H2O (0.5 mL), and the mixture was heated
o
at 130 C for 12 h. The reaction mixture was allowed to cool to
ambient temperature and the solvent was removed under reduced
pressure. Alcohol 2 (1.2 mmol), [Cp*IrCl2]2 (0.01 mmol, 1
mol%), Cs2CO3 (0.2 mmol, 0.2 equiv) and toluene (1 mL) were
o
70 added. The mixture was further heated at 130 C for 12h. The
As shown in Table 2, the scope of reaction with respect to
nitriles was then examined. Reactions of benzonitriles bearing
one or two electronꢀwithdrawing substituents, such as halogen
atoms 1b-f and trifluoromethyl 1g, provided the
20 corresponding products 4ba-4ga in 80ꢀ88% yields (Table 2,
entries 1ꢀ6). Transformations of benzonitriles bearing an
electronꢀdonating substituent, such as methyl 1h and methoxy
1i, afforded also the desired products 4ha and 4ia in 80% and
82% yields, respectively (Table 2, entries 7ꢀ8). In the case of
25 heteroaryl nitriles 1j and 1k, the corresponding products 4ja
and 4ka could be also obtained in 81% and 82% yields,
respectively (Table 2, entries 9ꢀ10). Under microwave
irradiation at 140 oC (a focused singleꢀmode microwave
synthesizer, Discover CEM, USA, 300W), hydrations of
30 aliphatic nitriles 1l and 1m proceeded for 6 h at 140 oC to
afford the corresponding amides, which underwent the Nꢀ
alkylation to give the desired products 4la and 4ma in 79%
and 77% yields, respectively (Table 2, entries 11ꢀ12).10
reaction mixture was cooled to ambient temperature, concentrated
in vacuo and purified by flash column chromatography with
hexanes/ethyl acetate to afford the corresponding product.
N-benzylbenzamide (4aa).6 mp 96ꢀ97 oC; 1H NMR (500 MHz,
75 CDCl3) δ 7.79 (d, J = 7.4 Hz, 2H, ArH), 7.50 (t, J = 7.0 Hz, 1H,
ArH), 7.43 (t, J = 7.3 Hz, 2H, ArH), 7.39ꢀ7.27 (m, 5H, ArH),
6.45 (br s, 1H, NH), 4.65 (d, J = 5.4 Hz, 2H, NCH2); 13C NMR
(125 MHz, CDCl3) δ 167.4, 138.2, 134.3, 131.5, 128.7, 128.5,
127.8, 127.5, 126.9, 44.0.
80
N-(4-fluorobenzyl)benzamide (4ab).6 mp 107ꢀ108 oC; 1H
NMR (500 MHz, CDCl3) δ 7.79 (d, J = 7.4Hz, 2H, ArH), 7.51 (t,
J = 7.4 Hz, 2H, ArH), 7.43 (t, J = 7.6 Hz, 2H, ArH), 7.36ꢀ7.29
(m, 2H, ArH), 7.03 (t, J = 8.6 Hz, 2H, ArH), 6.46 (br s, 1H, NH),
4.61 (d, J = 5.7 Hz, 2H, NCH2); 13C NMR (125 MHz, CDCl3) δ
85 167.4, 162.2 (d, JCꢀF = 244.1 Hz), 134.2, 134.0, 131.6, 129.5 (d,
JCꢀF = 8.0 Hz), 128.6, 126.9, 115.5 (d, JCꢀF = 21.5 Hz), 43.3.
N-(4-chlorobenzyl)benzamide (4ac).6 mp 139ꢀ140 oC; 1H
NMR (500 MHz, CDCl3).δ 7.78 (d, J = 7.4 Hz, 2H, ArH), 7.51 (t,
J = 7.3 Hz, 1H, ArH), 7.43 (t, J = 7.5 Hz, 2H, ArH), 7.34ꢀ7.27
90 (m, 4H, ArH), 6.51 (br s, 1H, NH), 4.61 (d, J = 5.8 Hz, 2H,
NCH2); 13C NMR (125 MHz, CDCl3) δ 167.5, 136.8, 134.1,
133.2, 131.6, 129.1, 128.8, 128.5, 126.9, 43.3.
Conclusion
35 We have established an alternative and efficient approach for
the synthesis of Nꢀalkylated amides from nitriles and alcohols
by the combination of [(IPr)Au(NTf2)] and [Cp*IrCl2]2.
Compared with previous methods for the synthesis of Nꢀ
alkylated amides from nitriles and alcohols as starting
40 materials, this protocol could be accomplished with high atom
N-(2,4-dichlorobenzyl)benzamide (4ad).6 mp 93ꢀ94 oC; 1H
NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.6 Hz, 2H, ArH), 7.51 (t,
economy under more environmentally benign conditions and 95 J = 7.3 Hz, 1H, ArH), 7.47ꢀ7.37 (m, 4H, ArH), 7.23 (dd, J = 8.2
thus it exhibited the significant application potential.
Hz and 1.3 Hz, 1H, ArH), 6.66 (br s, 1H, NH), 4.68 (d, J = 6.0 Hz,
2H, NCH2); 13C NMR (125 MHz, CDCl3) δ 167.4, 134.2, 134.1,
133.99, 133.95, 131.7, 131.0, 129.3, 128.6, 127.3, 126.9, 41.4.
Experimental Section
N-(4-bromobenzyl)benzamide (4ae).6 mp 134ꢀ135 oC; 1H
100 NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.6 Hz, 2H, ArH), 7.51 (t,
J = 7.3 Hz, 1H, ArH), 7.48ꢀ7.41 (m, 4H, ArH), 7.23 (d, J = 8.2
Hz, 2H, ArH), 6.50 (br s, 1H, NH), 4.59 (d, J = 5.8 Hz, 2H,
NCH2); 13C NMR (125 MHz, CDCl3) δ 167.5, 137.3, 134.1,
131.8, 131.6, 129.5, 128.6, 126.9, 121.4, 43.4.
General Experimental Details. Highꢀresolution mass spectra
45 (HRMS) were obtained on
a
HPLCꢀQꢀTof MS(Micro)
spectrometer and are reported as m/z (relative intensity). Accurate
masses are reported for the molecular ion [M+Na].+ Proton
nuclear magnetic resonance (1H NMR) spectra were recorded at
500 MHz using a Bruker Avance 500 spectrometer. Chemical
50 shifts are reported in delta (δ) units, parts per million (ppm)
downfield from tetramethylsilane or ppm relative to the center of
the singlet at 7.26 ppm for CDCl3 and 2.50 ppm for DMSOꢀd6.
Coupling constants J values are reported in Hertz (Hz), and the
splitting patterns were designated as follows: s, singlet; d, doublet;
55 t, triplet; m, multiplet; b, broad. Carbonꢀ13 nuclear magnetic
105
N-(4-(trifluoromethyl)benzyl)benzamide (4af).6 mp 140ꢀ141
oC; 1H NMR (500 MHz, CDCl3) δ 7.80 (d, J = 6.2 Hz, 2H, ArH),
7.60 (t, J = 7.2 Hz, 2H, ArH), 7.55ꢀ7.49 (m, 1H, ArH), 7.49ꢀ7.38
(m, 4H, ArH), 6.74ꢀ6.47 (m, 1H, NH), 4.75ꢀ4.64 (m, 2H, NCH2);
13C NMR (125 MHz, CDCl3) δ 167.6, 142.4, 134.0, 131.7, 129.8
4
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 5 of 7
Catalysis Science & Technology
View Article Online
DOI: 10.1039/C4CY01506A
(q, JCꢀF = 32.2 Hz), 128.6, 127.9, 127.0, 125.6 (q, JCꢀF = 3.5 Hz), 55 H), 4.21 (s, 5H, Ferrocene H), 4.18 (s, 2H, Ferrocene H); 13C
124.0 (q, JCꢀF = 270.4 Hz), 43.5.
NMR (125 MHz, CDCl3) δ 166.8, 134.5, 131.4, 128.6, 126.8,
84.7, 68.5, 68.3, 68.2, 39.3. HRMSꢀEI (70 eV) m/z calcd for
C18H17NOFeNa [M + Na]+ 342.0557, found 342.0567.
N-(4-(trifluoromethoxy)benzyl)benzamide (4ag).6 mp 134ꢀ
o
1
135 C; H NMR (500 MHz, CDCl3) δ 7.79 (d, J = 7.6Hz, 2H,
ArH), 7.52 (t, J = 7.3 Hz, 1H, ArH), 7.44 (t, J = 7.5 Hz, 2H, ArH),
o
5
N-hexylbenzamide (4ao).6 mp 41ꢀ42 C; 1H NMR (500 MHz,
7.38 (d, J = 8.4 Hz, 2H, ArH), 7.19 (d, J = 8.2 Hz, 2H, ArH), 6.50 60 CDCl3) δ 7.76 (d, J = 7.6 Hz, 2H, ArH), 7.49 (t, J = 7.2 Hz, 1H,
(br s, 1H, NH), 4.65 (d, J = 5.8 Hz, 2H, NCH2); 13C NMR (125
MHz, CDCl3) δ 167.5, 148.6, 137.1, 134.1, 131.7, 129.2, 128.6,
127.0, 121.2, 120.4 (q, JCꢀF = 255.6 Hz), 43.2.
ArH), 7.42 (t, J = 7.5 Hz, 2H, ArH), 6.14 (br s, 1H, NH), 3.45 (q,
J = 6.7 Hz, 2H, NCH2), 1.61 (quint, J = 7.3 Hz, 2H, CH2), 1.42ꢀ
1.29 (m, 6H, 3xCH2), 0.89 (t, J = 6.4 Hz, 3H, CH3); 13C NMR
(125 MHz, CDCl3) δ 167.5, 134.9, 131.2, 128.4, 126.8, 40.1, 31.5,
65 29.6, 26.6, 22.5, 14.0.
10
N-(2-methylbenzyl)benzamide (4ah).13 mp 113ꢀ114 oC; 1H
NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.8 Hz, 2H, ArH), 7.50 (t,
J = 7.2 Hz, 1H, ArH), 7.42(t, J = 7.6 Hz, 2H, ArH), 7.30 (d, J =
7.0 Hz, 1H, ArH), 7.25ꢀ7.17 (m, 3H, ArH), 6.22 (br s, 1H, NH),
4.65 (d, J = 5.3 Hz, 2H, NCH2), 2.38 (s, 3H, CH3); 13C NMR
N-isopentylbenzamide (4ap).9g oil; 1H NMR (500 MHz,
CDCl3) δ 7.75 (d, J = 7.5 Hz, 2H, ArH), 7.49 (t, J = 7.3 Hz, 1H,
ArH), 7.42 (t, J = 7.5 Hz, 2H, ArH), 6.10 (br s, 1H, NH), 3.48
(quart, J = 6.8 Hz, 2H, NCH2), 1.69 (sept, J = 6.6 Hz, 1H, CH),
70 1.51 (quart, J = 7.3 Hz, 2H, CH2), 0.96 (d, J = 6.6 Hz, 6H,
2xCH3); 13C NMR (125 MHz, CDCl3) δ 167.5, 134.8, 131.2,
128.4, 126.8, 38.5, 38.3, 25.9, 22.4.
15 (125 MHz, CDCl3) δ 167.2, 136.6, 135.7, 134.3, 131.5, 130.6,
128.6, 128.5, 127.9, 126.9, 126.2, 42.3, 19.0.
N-(4-methylbenzyl)benzamide (4ai).6 mp 140ꢀ141 oC; 1H
NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.7 Hz, 2H, ArH), 7.49 (t,
J = 7.3 Hz, 1H, ArH), 7.42 (t, J = 7.6 Hz, 2H, ArH), 7.25 (d, J =
20 7.9 Hz, 2H, ArH), 7.16 (d, J = 7.7 Hz, 2H, ArH), 6.38 (br s, 1H,
o
1
N-(cyclohexylmethyl)benzamide (4aq).6 mp 103ꢀ104 C; H
NMR (500 MHz, CDCl3) δ 7.76 (d, J = 7.3 Hz, 2H, ArH), 7.49 (t,
NH), 4.60 (d, J = 5.5 Hz, 2H, NCH2), 2.34 (s, 3H, CH3); 13C 75 J = 7.1 Hz, 1H, ArH), 7.43 (t, J = 7.3 Hz, 2H, ArH), 6.21 (br s,
NMR (125 MHz, CDCl3) δ 167.3, 137.3, 135.1, 134.4, 131.4,
129.4, 128.5, 127.9, 126.9, 43.8, 21.0.
1H, NH), 3.30 (t, J = 6.3 Hz, 2H, NCH2), 1.82ꢀ1.71 (m, 4H,
2xCH2), 1.70ꢀ1.64 (m, 1H, CH), 1.63ꢀ1.54 (m, 1H, CH), 1.30ꢀ
1.12 (m, 3H, CH and CH2), 1.00 (q, J = 11.7 Hz, 2H, CH2); 13
C
N-(4-methoxybenzyl)benzamide (4aj).6 mp 97ꢀ98 oC; 1H
25 NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.5 Hz, 2H, ArH), 7.49 (t,
J = 7.2 Hz, 1H, ArH), 7.42 (t, J = 7.4 Hz, 2H, ArH), 7.29 (d, J =
8.2 Hz, 2H, ArH), 6.88 (d, J = 8.3 Hz, 2H, ArH), 6.36 (br s, 1H,
NH), 4.58 (d, J = 5.4 Hz, 2H, NCH2), 3.80 (s, 3H, OCH3); 13C
NMR (125 MHz, CDCl3) δ 167.2, 159.0, 134.4, 131.4, 130.3,
30 129.2, 128.5, 126.9, 114.1, 55.2, 43.5.
NMR (125 MHz, CDCl3) δ 167.5, 134.9, 131.2, 128.5, 126.8,
80 46.2, 38.0, 30.9, 26.3, 25.8.
o
1
N,N'-m-xylylene-bis-benzamide (4ar).14 mp 170ꢀ171 C; H
NMR (500 MHz, DMSOꢀd6) δ 9.04 (t, J = 5.3 Hz, 2H, ArH), 7.86
(d, J = 7.4 Hz, 4H, ArH), 7.52 (t, J = 7.0 Hz, 2H, ArH), 7.45 (t, J
= 7.4 Hz, 4H, ArH), 7.32ꢀ7.25 (m, 2H, ArH), 7.23ꢀ7.17 (m, 2H,
85 ArH), 4.47 (d, J = 5.4 Hz, 4H, NCH2); 13C NMR (125 MHz,
DMSOꢀd6) δ 166.2, 139.8, 134.4, 131.1, 128.2, 127.2, 125.8,
125.6, 42.5.
N-(naphthalen-2-ylmethyl)benzamide (4ak).6 mp 141ꢀ142 oC;
1H NMR (500 MHz, CDCl3) δ 7.88ꢀ7.76 (m, 6H, ArH), 7.52ꢀ7.39
(m, 6H, ArH), 6.54 (br s, 1H,NH), 4.80 (d, J = 5.0 Hz, 2H,
NCH2); 13CNMR (125 MHz, CDCl3) δ 167.4, 135.6, 134.3, 133.3,
35 132.8, 131.5, 128.6, 127.7, 127.6, 127.0, 126.5, 126.3, 125.94,
125.91, 44.2.
N-benzyl-4-fluorobenzamide (4ba).6 mp 141ꢀ142 oC; 1H
NMR (500 MHz, CDCl3) δ 7.83ꢀ7.76 (m, 2H, ArH), 7.40ꢀ7.27 (m,
90 5H, ArH), 7.10 (t, J = 8.6 Hz, 2H, ArH), 6.38 (br s, 1H, NH),
4.63 (d, J = 5.6 Hz, 2H, NCH2); 13C NMR (125 MHz, CDCl3) δ
N-(thiophen-2-ylmethyl)benzamide (4al).6 mp 119ꢀ120 oC;
1H NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.5 Hz, 2H, ArH),
7.50 (t, J = 7.4 Hz, 1H, ArH), 7.43 (t, J = 7.6 Hz, 2H, ArH), 7.25
40 (d, J = 5.3 Hz, 1H, ArH), 7.05 (d, J = 3.0 Hz, 1H, ArH), 6.98 (dd,
166.3, 164.7 (d, JCꢀF = 251.0 Hz), 138.0, 130.5,129.3 (d, JCꢀF
9.0 Hz), 128.8, 127.8, 127.6, 115.5 (d, JCꢀF = 21.7 Hz), 44.1.
=
N-benzyl-4-chlorobenzamide (4ca).6 mp 162ꢀ163 oC; 1H
J = 4.8 Hz and 3.7 Hz, 1H, ArH), 6.45 (br s, 1H, NH), 4.82 (d, J 95 NMR (500 MHz, CDCl3) δ 7.73 (d, J = 8.2 Hz, 2H, ArH), 7.40 (d,
= 5.6 Hz, 2H, NCH2); 13C NMR (125 MHz, CDCl3) δ 167.1,
140.8, 134.1, 131.6, 128.5, 127.0, 126.9, 126.2, 125.3, 38.8.
J = 8.2 Hz, 2H, ArH), 7.38ꢀ7.28 (m, 5H, ArH), 6.40 (br s, 1H,
NH), 4.63 (d, J = 5.6 Hz, 2H, NCH2); 13C NMR (125 MHz,
CDCl3) δ 166.3, 137.9, 137.7, 132.7, 128.8, 128.4, 127.9, 127.7,
44.2.
N-(furan-2-ylmethyl)benzamide (4am).6 mp 98ꢀ99 oC; 1H
45 NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.4 Hz, 2H, ArH), 7.50 (t,
J = 7.3 Hz, 1H, ArH), 7.43 (t, J = 7.5 Hz, 2H, ArH), 7.38 (s, 1H, 100 N-benzyl-3,4-dichlorobenzamide (4da).6 mp 105ꢀ106 C; H
o
1
ArH), 6.44 (br s, 1H, NH), 6.34 (m, 1H, ArH), 6.30 (m, 1H, ArH),
4.65 (d, J = 5.4 Hz, 2H, NCH2); 13C NMR (125 MHz, CDCl3) δ
167.2, 151.2, 142.2, 134.1, 131.6, 128.5, 127.0, 110.5, 107.6,
NMR (500 MHz, CDCl3) δ 7.88 (s, 1H, ArH), 7.60 (d, J = 7.8 Hz,
1H, ArH), 7.50 (d, J = 8.2 Hz, 1H, ArH), 7.41ꢀ7.29 (m, 5H, ArH),
6.45 (br s, 1H, NH), 4.62 (d, J = 5.3 Hz, 2H, NCH2); 13C NMR
(125 MHz, CDCl3) δ 165.2, 137.6, 135.9, 134.1, 133.0, 130.6,
105 129.2, 128.8, 127.9, 127.7, 126.1, 44.2.
50 37.0.
N-(ferrocenemethyl)benzamide (4an). mp 165ꢀ166 oC; 1H
NMR (500 MHz, CDCl3) δ 7.78 (d, J = 7.4 Hz, 2H, ArH), 7.51 (t,
J = 7.3 Hz, 1H, ArH), 7.44 (t, J = 7.4 Hz, 2H, ArH), 6.30 (br s,
1H, NH), 4.34 (d, J = 5.2 Hz, 2H, NCH2), 4.27 (s, 2H, Ferrocene
o
1
N-benzyl-3-bromobenzamide (4ea).13 mp 87ꢀ88 C; H NMR
(500 MHz, CDCl3): δ 7.93 (s, 1H, ArH), 7.70 (d, J = 7.7 Hz, 1H,
ArH), 7.64ꢀ7.62 (m, 1H, ArH), 7.38ꢀ7.29 (m, 6H, ArH), 6.40 (s,
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 5

Catalysis Science & Technology
Page 6 of 7
View Article Online
DOI: 10.1039/C4CY01506A
br, 1H, NH), 4.63 (d, J = 5.6 Hz, 2H, CH2); 13C NMR (125 MHz,
CDCl3): δ 165.9, 137.8, 136.3, 134.5, 130.2, 130.1, 128.8, 127.9,
Acknowledgements
55 Financial support by National Natural Science Foundation of
China (No. 21272115) and Fundamental Research Funds for
the Central Universities (No. 30920130111005) is greatly
appreciated.
127.7, 125.5, 122.7, 44.2.
N-benzyl-4-bromobenzamide (4fa).15 mp 169ꢀ170 oC; 1H
NMR (500 MHz, CDCl3) δ 7.66 (d, J = 8.4 Hz, 2H, ArH), 7.56 (d,
J = 8.4 Hz, 2H, ArH), 7.39ꢀ7.28 (m, 5H, ArH), 6.38 (br s, 1H,
NH), 4.63 (d, J = 5.6 Hz, 2H, NCH2); 13C NMR (125 MHz,
CDCl3) δ 166.4, 137.9, 133.2, 131.8, 128.8, 128.6, 127.9, 127.7,
126.2, 44.2.
5
Notes and references
a
60 Key Laboratory for Soft Chemistry and Functional Materials, Ministry
of Education, Nanjing University of Science and Technology, Nanjing
210094, P. R. China. Fax: +86ꢀ25ꢀ84431939; Tel: +86ꢀ25ꢀ84317316; Eꢀ
mail: fengli@njust.edu.cn
10
N-benzyl-4-(trifluoromethyl)benzamide (4ga).6 mp 170ꢀ171
oC; 1H NMR (500 MHz, CDCl3) δ 7.90 (d, J = 8.0 Hz, 2H, ArH),
7.69 (d, J = 8.0 Hz, 2H, ArH), 7.41ꢀ7.29 (m, 5H, ArH), 6.48 (br s,
1H, NH), 4.66 (d, J = 5.6 Hz, 2H, NCH2); 13C NMR (125 MHz,
CDCl3) δ 166.1, 137.8, 137.7, 133.3 (q, JCꢀF = 32.5 Hz), 128.8,
b
Department of Biochemical Engineering, Nanjing University of Science
65 and Technology, Nanjing 210094, P. R. China
† Electronic Supplementary Information (ESI) available: Experimental
procedures and analytical data for products. See DOI: 10.1039/b000000x/
1
2
(a) J. M. Humphrey and A. R. Chamberlin, Chem. Rev., 1997, 97,
2243; (b) T. Cupido, J. TullaꢀPuche, J. Spengler and F. Albericio,
Curr. Opin. Drug Discovery Dev., 2007, 10, 768; (c) C. L. Allen and
J. M. J. Williams, Chem. Soc. Rev., 2011, 40, 3405; (d) V. R.
Pattabiraman and J. W. Bode, Nature, 2011, 480, 471.
(a) M. B. Smith and J. March, March’s Advanced Organic Chemistry:
Reactions, Mechanisms, and Structure, 6th ed., Wiley, Hoboken, NJ,
2007; (b) M. B. Smith, Organic Synthesis, 2nd ed., McꢀGrawꢀHill
Companies, New York, 2002; (c) E. Valeur and M. Bradley, Chem.
Soc. Rev., 2009, 38, 606.
15 127.9, 127.8, 127.4, 125.6, 123.6 (q, JCꢀF = 271.1 Hz), 44.3.
N-benzyl-4-methylbenzamide (4ha).6 mp 132ꢀ133 oC; 1H
NMR (500 MHz, CDCl3) δ 7.69 (d, J = 8.0 Hz, 2H, ArH), 7.38ꢀ
7.27 (m, 5H, ArH), 7.22 (d, J = 6.8 Hz, 2H, ArH), 6.50ꢀ6.30 (m,
1H, NH), 4.64 (dd, J = 5.3 Hz and 3.4 Hz, NCH2), 2.39 (s, 3H,
20 CH3); 13C NMR (125 MHz, CDCl3) δ 167.3, 141.9, 138.3, 131.5,
129.2, 128.7, 127.8, 127.5, 126.9, 44.0, 21.4.
70
75
N-benzyl-4-methoxybenzamide (4ia).6 mp 121ꢀ122 oC; 1H
NMR (500 MHz, CDCl3) δ 7.76 (d, J = 8.6 Hz, 2H, ArH), 7.39ꢀ
7.27 (m, 5H, ArH), 6.91 (d, J = 8.6 Hz, 2H, ArH), 6.36 (br s, 1H,
25 NH), 4.63 (d, J = 5.6 Hz, 2H, NCH2), 3.84 (s, 3H, CH3); 13C
NMR (125 MHz, CDCl3) δ 166.9, 162.2, 138.4, 128.8, 128.7,
127.8, 127.4, 126.6, 113.7 , 55.3, 44.0.
3
4
(a) J. J. Ritter and P. P. Minieri, J. Am. Chem. Soc., 1948, 70, 4045;
(b) F. R. Benson and J. J. Ritter, J. Am. Chem. Soc., 1949, 71, 4128;
(c) H. Plaut and J. J. Ritter, J. Am. Chem. Soc., 1951, 73, 4076; (d) L.
I. Krimen and D. J. Cota, Org. React., 1969, 17, 213.
80
For selected examples, see: (a) C. Gunanathan, Y. BenꢀDavid and D.
Milstein, Science, 2007, 317, 790; (b) L. U. Nordstrøm, H. Vogt and
R. Madsen, J. Am. Chem. Soc., 2008, 130, 17672; (c) S. C. Ghosh, S.
Muthaiah, Y. Zhang, X. Xu and S. H. Hong, Adv. Synth. Catal., 2009,
351, 2643; (d) K. Shimizu, K. Ohshima and A. Satsuma, Chem.ꢀEur.
J., 2009, 15, 9977; (e) J. H. Dam, G. Osztrovszky, L. U. Nordstrom
and R. Madsen, Chem.ꢀEur. J., 2010, 16, 6820; (f) S. Muthaiah, S. C.
Ghosh, J. E. Jee, C. Chen, J. Zhang and S. H. Hong, J. Org. Chem.,
2010, 75, 3002; (g) S. C. Ghosh and S. H. Hong, Eur. J. Org. Chem.,
2010, 4266; (h) A. Nova, D. Balcells, N. D. Schley, G. E.
Dobereiner, R. H. Crabtree and O. Eisenstein, Organometallics,
2010, 29, 6548; (i) C. Chen, Y. Zhang and S. H. Hong, J. Org. Chem.,
2011, 76, 10005; (j) N. D. Schley, G. E. Dobereiner and R. H.
Crabtree, Organometallics, 2011, 30, 4174; (k) I. S. Makarov, P.
Fristrup and R. Madsen, Chem.ꢀEur. J., 2012, 49, 15683; (l) D.
Srimani, E. Balaraman, P. Hu, Y. B. David and D. Milstein, Adv.
Synth. Catal., 2013, 355, 2525; (m) E. Sindhuja, R. Ramesh, S. Balaji
and Y. Liu, Organometallics, 2014, 33, 4269.
B. Kang, Z. Fu and S. H. Hong, J. Am. Chem. Soc., 2013, 135, 11704.
N. Wang, X. Zou, J. Ma and F. Li, Chem. Commun., 2014, 50, 8303.
(a) A. S. K. Hashmi and G. J. Hutchings, Angew. Chem. Int. Ed.,
2006, 45, 7896; (b) A. S. K. Hashmi, Chem. Rev., 2007, 107, 3180; (c)
Z. Li, C. Brouwer and C. He, Chem. Rev., 2008, 108, 3239; (d) E.
JiménezꢀNúñez and A. M. Echavarren, Chem. Rev., 2008, 108, 3326;
(e) S. P. Nolan, Acc. Chem. Res., 2011, 44, 91; (f) A. Corma, A.
LeyvaꢀPérez and M. J. Sabater, Chem. Rev., 2011, 111, 1657; (g) N.
Krause and C. Winter, Chem. Rev., 2011, 111, 1994.
85
N-benzylthiophene-2-carboxamide (4ja).6 mp 117ꢀ118 oC;
1H NMR (500 MHz, CDCl3) δ 7.51 (d, J = 3.8 Hz, 1H, ArH),
30 7.47 (d, J = 5.0 Hz, 1H, ArH), 7.38ꢀ7.33 (m, 4H, ArH), 7.33ꢀ7.27
(m, 1H, ArH), 7.06 (t, J = 4.3 Hz, 1H, ArH), 6.30 (br s, 1H, NH),
4.62 (d, J = 5.7 Hz, 2H, NCH2); 13C NMR (125 MHz, CDCl3) δ
161.8, 138.8, 138.0, 130.0, 128.7, 128.1, 127.8, 127.6, 127.5,
43.9.
90
N-benzylfuran-2-carboxamide (4ka).6 mp 105ꢀ106 oC; 1H
NMR (500 MHz, CDCl3): δ 7.42ꢀ7.41(m, 1H, ArH), 7.36ꢀ7.35
(m, 4H, ArH), 7.32ꢀ7.28 (m, 1H, ArH), 7.15 (dd, J = 3.5 Hz and
0.6 Hz, 1H, ArH), 6.64 (s, br, 1H, NH), 6.64 (dd, J = 3.5 Hz and
1.8 Hz, 1H, ArH), 4.62 (d, J = 5.9 Hz, 2H, CH2); 13C NMR (125
95
35
100
105
110
115
120
5
6
7
40 MHz, CDCl3): δ 158.2, 147.9, 143.8, 138.0, 128.7, 127.9, 127.6,
114.3, 112.1, 43.1.
N-benzyl-2-phenylpropanamide (4la).6 mp 76ꢀ77 oC; 1H
NMR (500 MHz, CDCl3) δ 7.39ꢀ7.20 (m, 8H, ArH), 7.14 (d, J =
7.0 Hz, 2H, ArH), 5.65 (br s, 1H, NH), 4.45ꢀ4.33 (m, 2H, NCH2),
45 3.60 (q, J = 6.9 Hz, 2H, CH), 1.56 (d, J = 7.0 Hz, 3H, CH3); 13C
NMR (125 MHz, CDCl3) δ 174.0, 141.3, 138.3, 128.9, 128.5,
127.6, 127.4, 127.3, 127.2, 47.1, 43.5, 18.5.
8
9
R. S. Ramon, N. Marion and S. P. Nolan, Chem.ꢀEur. J., 2009, 15,
8695.
(a) F. Li, H. Shan, Q. Kang and L. Chen, Chem. Commun., 2011, 47,
5058; (b) F. Li, H. Shan, L. Chen, Q. Kang and P. Zou, Chem.
Commun., 2012, 48, 603; (c) F. Li, Q. Kang, H. Shan, L. Chen and J.
Xie, Eur. J. Org. Chem., 2012, 5085; (d) F. Li, J. Xie, H. Shan, C.
Sun and L. Chen, RSC Adv., 2012, 2, 8645; (e) F. Li, L. Chen, Q.
Kang, J. Cai and G. Zhu, New J. Chem., 2013, 37, 624; (f) F. Li, C.
Sun, H. Shan, X. Zou and J. Xie, ChemCatChem, 2013, 5, 1543; (g)
F. Li, P. Qu, J. Ma, X. Zou and C. Sun, ChemCatChem, 2013, 5,
2178; (h) C. Sun, X. Zou and F. Li, Chem.ꢀEur. J., 2013, 19, 14030;
(i) J. Ma, N. Wang and F. Li, Asian J. Org. Chem., 2014, 3, 940ꢀ937;
N-benzylbutyramide (4ma).6 mp 47ꢀ48 oC; 1H NMR (500
MHz, CDCl3) δ 7.37ꢀ7.31 (m, 2H, ArH), 7.31ꢀ7.24 (m, 3H, ArH),
50 5.74 (br s, 1H, NH), 4.45 (d, J = 4.7 Hz, 2H, NCH2), 2.19 (t, J =
7.4 Hz, 2H, CH2), 1.70 (sext, J = 7.2 Hz, 2H, CH2), 0.96 (t, J =
7.3 Hz, 3H, CH3); 13C NMR (125 MHz, CDCl3) δ 172.8, 138.4,
128.6, 127.7, 127.4, 43.5, 38.6, 19.1, 13.7.
6
|
Journal Name, [year], [vol], 00–00
This journal is © The Royal Society of Chemistry [year]

Page 7 of 7
Catalysis Science & Technology
View Article Online
DOI: 10.1039/C4CY01506A
(j) P. Qu, C. Sun, J. Ma and F. Li, Adv. Synth. Catal., 2014, 356, 447;
(k) F. Li, C. Sun and N. Wang, J. Org. Chem., 2014, 79, 8031; (l) F.
Li, J. Ma and N. Wang, J. Org. Chem., 2014, 79, 10447.
10 Under magnetic stirrer, the hydration of aliphatic nitriles 1l and 1m
were carried out at 140 oC for 12 h and none of products were found.
11 L. Ricard and F. Gagosz, Organometallics, 2007, 26, 4704.
12 N. A. Owston, A. J. Parker, J. M. J. Williams, Org. Lett., 2007, 9, 73.
13 G. A. Molander and M. A. Hiebel, Org. Lett., 2010, 12, 4876.
14 S. Cellamare, A. Stefanachi, D. A. Stolfa, T. Basile, Marco Catto, F.
Campagna, E. Sotelo, P. Acquafredda and A. Carotti, Bioorg. Med.
Chem., 2008, 16, 4810.
5
10
15 E. Petricci, C. Mugnaini, M. Radi, F. Corelli and M. Botta, J. Org.
Chem., 2004, 69, 7880.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 7