Nickel (II)-Catalyzed efficient aminocarbonylation of unreactive alkanes with formanilides—Exploiting the deformylation behavior of imides

Article abstract of DOI:10.1016/j.tet.2018.05.045

Challenging functionalization of C(sp³)-H has recently attracted much attention of organic chemists. In this paper, we developed a Ni(acac)₂-catalyzed activation of unreactive alkanes with formanilides in the presence of carbon monoxide to furnish moderate to excellent yields of amides. This is the first example of aminocarbonylation of inert alkanes using nickel-based catalyst, and formanilides is disclosed to be an interesting amine source owing to the peculiar deformylation nature of imide intermediates.

Full text of DOI:10.1016/j.tet.2018.05.045

Accepted Manuscript
Nickel (II)-Catalyzed efficient aminocarbonylation of unreactive alkanes with
formanilides—Exploiting the deformylation behavior of imides
Zhang Han, Dai Chaowei, Liu Lice, Ma Hongfei, Bu Hongzhong, Li Yufeng
PII:
S0040-4020(18)30580-5
10.1016/j.tet.2018.05.045
TET 29552
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 April 2018
Revised Date: 14 May 2018
Accepted Date: 16 May 2018
Please cite this article as: Han Z, Chaowei D, Lice L, Hongfei M, Hongzhong B, Yufeng L, Nickel
(II)-Catalyzed efficient aminocarbonylation of unreactive alkanes with formanilides—Exploiting the
deformylation behavior of imides, Tetrahedron (2018), doi: 10.1016/j.tet.2018.05.045.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Nickel (II)-Catalyzed Efficient
Leave this area blank for abstract info.
Aminocarbonylation of Unreactive Alkanes
with Formanilides—Exploiting the
Deformylation Behavior of Imides
Han Zhang, Chaowei Dai, Lice Liu, Hongfei Ma, Hongzhong Bu, Yufeng Li
School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, PR China

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Nickel (II)-catalyzed efficient aminocarbonylation of unreactive alkanes with
formanilides—exploiting the deformylation behavior of imides
Han Zhang, Chaowei Dai, Lice Liu, Hongfei Ma, Hongzhong Bu, Yufeng Li
School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, PR China
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Challenging functionalization of C(sp3)-H has recently attracted much attention of organic
chemists. In this paper, we developed a Ni(acac)2-catalyzed activation of unreactive alkanes with
formanilides in the presence of carbon monoxide to furnish moderate to excellent yields of
amides. This is the first example of aminocarbonylation of inert alkanes using nickel-based
catalyst, and formanilides is disclosed to be an interesting amine source owing to the peculiar
deformylation nature of imide intermediates.
Available online
Keywords:
Nickel-catalyst
Aminocarbonylation
Alkanes
2009 Elsevier Ltd. All rights reserved
.
C(sp3)-H bond activation
Formanilide
1. Introduction
2. Results and discussion
A tremendous growth in transition-metal-catalyzed C-H
activation has been witnessed over recent decades.1
Functionalization of C-H bonds represents a powerful, valuable,
straightforward strategy for the construction of complex organic
frameworks relative to pharmaceuticals and natural products,
etc.2 In comparison with the well-developed C(sp2)-H activation,
synthetically useful C(sp3)-H activation started rather late
because of the inert nature of alkanes and the selectivity issue in
the reaction.3 Group-assisting methodology has been exploited to
improve the reactivity and selectivity of alkanes in order to
achieve the controllable functionalization.4 In spite of the most
We initiated the activation reaction with cyclohexane (1a, also
as the solvent) and aniline as the model substrates for
catalyst-screening (Table 1). Most reactions gave N,
N/-diphenylurea as the main product, wherein, Cu-catalytic
procedures just leaded to inseparable mixtures (Table 1, Entries
1-15). To our pleasure, Co(acac)2 and Ni(acac)2 also exhibited
certain activation on the transformation even without assistance
of auxiliary ligands (Table 1, Entries 11-15). Replacing aniline
with its hydrochloride, urea formation was partly controlled, but
the yield of 3aa was still unsatisfactory (Table 1, Entry 16).
Without the catalyst, the activation of cyclohexane didn’t take
place but urea was generated by the interaction between aniline
and CO in the presence of DTBP (Table 1, Entry 17).
recent
progress
in
straight-functionalization
of
directing-group-free alkanes, C(sp3)-H activation has still been a
challenging issue pursued by synthetic chemists.5 On the other
hand, the first-row transition metals have acted as positive
alternatives to the second- and third-row metals in many organic
reactions. In the case of VIII elements, different valence of Fe,
Co, Ni, have presented comparable performance in some
reactions6 that catalyzed by Ru, Rh, Pd, Ir, and Pt.7 And lately,
nickel-based catalyst has been reported for the activation of some
inert sp3 carbon-hydrogen bonds.8
Table 1. The initial exploration into activation of cyclohexane
with aniline for catalyst-screeninga
Promoted by those pioneering progress in sp3 C-H activation,
we have developed a Ni-catalyzed carbonylation of unreactive
alkanes with formanilides in carbon monoxide to acquire high
yields of amide products. Herein, we wish to describe the results
of this study.
Entry
Metal
CoCl2
CoCl2
NiCl2
NiCl2
Ligand
1,10-phen
PPh3
3aa Yield(%)b
trace
1
2
3
4
5
trace
1,10-phen
PPh3
Trace
Trace
Co(OAc)2 1,10-phen
Trace

2
pressure and the charging amounts of catalyst but leading to no
6
CuCl
CuI
1,10-phen
1,10-phen
Trace
Trace
Trace
0
ACCEPTED MANUSCRIPT
better results (Table 2, Entries 3 and 4). Benzene was checked as
an auxiliary solvent giving a comparably satisfactory result
(Table 2, Entry 5), from which it can also be seen that sp2 C-H
bond be steady enough to the catalytic conditions. Acetonitrile
was an unfavorable solvent for this conversion (Table 2, Entry 6).
To confirm the effect in this transformation, control experiments
were carried out as shown in Entries 7-9 (Table 2). Without the
catalyst and additional solvents, DTBP was also able to generate
a little quantity of urea in no more than 10% yield but with no
3aa observed (Table 2, Entry 7). Dichloroethane, which was
reported by Lei and coworkers as a facilitating solvent for
metal-free carbonylation of cyclohexane,9 was confirmed to be
some helpful to the reaction in the absence of metal catalyst, but
the yield of 3aa was very low and no imide was obtained (Table
2, Entry 8). Compared with cyclohexane and benzene,
dichloroethane in the presence of Ni(acac)2 cannot exerted
distinct facilitation on the transformation under such conditions
(Table 2, Entry 9).
7
8
Cu(OAc)2 1,10-phen
9
FeCl3
1,10-phen
10
11
12
13
14
15
16c
17
Fe(acac)2
Co(acac)2
Co(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
–
1,10-phen
13
1,10-phen
31
PPh3
34
1,10-phen
39
PPh3
40
–
–
–
42
47
0
acac= acetylacetonate. DTBP= di-tert-butylperoxide. 1,10- phen= 1,10-
phenanthroline.
a Reaction conditions unless otherwise stated: 1a (20 mL), 2a (10 mmol),
metal (10% mol), ligand (20% mol), DTBP (12 mmol), CO (20 bar), time 24
h.
b Isolated yields, Urea was obtained as the main product.
c Aniline hydrochloride was utilized instead of 2a.
Table 3. Ni-catalyzed carbonylation of alkanes with
formanilidesa
Table 2. Condition optimization for the Ni-catalyzed reaction
O
O
O
O
decomposition
-CO
CO, Ni(acac)
of 1a and 2a in COa
2
R2
R1
N
H
R1 NHR2
R1-H
+
H
N
DTBP, 110oC
16 h
R2
H
O
3
1
2
unstableimide
Ph
O
CO, Ni(acac)2
N
3, yieldb
H
DTBP, 110oC, 16 h
H
NHPh
3aa
1a
2a
Entry
Catalyst
loading
Auxiliary
solvent
Pressure
3aa
Yield(%)b
1
2
3
4
5
6
7
8d
9
10 mol%
10 mol%
10 mol%
5 mol%
10 mol%
10 mol%
–
–
20 bar N2
20 bar CO
10 bar CO
20 bar CO
20 bar CO
20 bar CO
20 bar CO
60 bar CO
20 bar CO
trace
90
–
–
85
O
N
–
80
benzene c
acetonitrile c
–
ClCH2CH2Cl c
ClCH2CH2Cl c
87
Et
H
3ai, 81%
44
F
O
O
0
N
H
N
H
–
˂10%
88
COOEt
F
3ak, 85%
3aj, 86%
10 mol%
OCH3
O
a Reaction conditions (unless otherwise stated): 1a (20 mL), 2a (10 mmol),
CO, catalyst (10 mol%,), DTBP (12 mmol), 110 oC, 16 h.
b Isolated yield.
O
N
H
N
H
3bf, 85%
3bc, 88%
c solvent (20 mL), 1a (10 mmol)
The reaction was conducted under the conditions according to the
d
F
H
N
O
literature.9
N
H
O
Cl
3cd, 68%c
F
3bj, 81%
Hindered by the serious urea formation between aniline and
CO, we had to turn to other amine sources to improve the
selectivity. Formanilide, which can be looked as the integrity of
CO and aniline, seemed a desirable substrate due to its weakened
nucleophilicity. Hence a new round of probe into the reaction of
formanilide (2a) was started using Ni(acac)2 as the catalyst.
H
N
Br
O
3dp, 66%
The first reaction between 1a and 2a was conducted under 20
o
bar nitrogen pressure at 110 C only giving trace of 3aa without
urea generation (Table 2, Entry 1). Surprisingly, an excellent
yield of 3aa (90%) was obtained while the reaction underwent
under 20 bar of carbon monoxide (Table 2, Entry 2). Noteworthy,
the requirement of carbon monoxide disclosed clearly that a
deformylation behavior should be involved in the process. Then,
condition-optimization was performed concerning mainly the
O
H
N
Ph
N
H
O
3cr, 53%
a
Reaction conditions (unless specially illustrated): 1 (20 mL), 2 (10
mmol), CO, Ni(acac)2 (10 mol%), DTBP (12 mmol), 110 oC, 16 h.

3
b Isolated yield.
O
ACCEPTED MANUSCRIPT
cadamantane (3c, 10 mmol), dichloroethane solvent (20 mL).
O
N
5
3ab(28)
NH
4e
O
5e
(42)
With the optimized conditions, a range of formanilides were
inspected, and all worked well with cyclohexane to give the
corresponding amides with good yields (Table 3, 3aa– 3al).
N-pyridylformamide was also tolerated in the reaction to furnish
amide 3am, though the yield was some lowered (Table 3, 3am).
Under the same conditions, Cylcopentane activations with
several formanilides in the presence of carbon monoxide
provided comparably high yields of carbonylation products
(Table 3, 3bc– 3bn). It can be seen that substituents of
formanilides (2) with different electronic effect were well
tolerated with this transformation. When adamantane (2c) was
tried using dichloroethane as the sole solvent, 3cd were obtained
in a lowered yield (68%). The reaction can be also applicable to
toluene and ethylbenzene expressing an obvious benzylic
selectivity, though the yields were just moderate (Table 3, 3da–
3ef). Utilizing N/-formylbenzohydrazide in the place of 2, the
reactions under the optimal conditions gave the corresponding
diacylhydrazines in moderate yields (Table 3, 3ar– 3cr).
O
O
N
6
3aa(trace)
NH
O
Ph
4f
5f
(57)
a Reaction conditions: 1a (20 mL), 4 (10 mmol), CO, catalyst (10 mol%,),
DTBP (12 mmol), 110 oC, 20 h.
b Isolated yield.
Based on the above experimental results and previous
reports,5d, 10 a plausible mechanism of this carbonylation was
proposed as depicted in Scheme 1. Initially, homolytic cleavage
of DTBP with the assistance of Ni(II) catalyst generates Ni(III)
species and the tert-butyloxy radical, which subsequently
abstracts hydrogen from 1a to generate cyclohexyl radical and
tert-butyl alcohol. Oxidative addition of Ni(III) species with
cyclohexyl radical leads to Nickel (IV) species (A). The reaction
between complex A with 2a gives the intermediate B with
releasing tert-butyl alcohol through an H-transfer process.
Following CO insertion allows the generation of C or D species,
which transforms to unstable E through reductive elimination and
regenerates the Ni(II) catalyst. Finally, Thermal decomposition of
E completes immediately under the reaction conditions leading to
the formation of 3aa.
Then, attention of us was shifted to acetanilide substrates,
since from which the formation of imides was expectable under
similar conditions to ours except for using a Cu catalyst
according to Wu’s work.5d When 4a was reacted with
cyclohexane in CO for 20 h, both amide (3aa) and imide (5a)
were obtained by flash chromatography (Table 4, Entry 1).
Several other amides were then reacted with 1a to afford imides
and amides with different distribution, among of which
benzanilide reaction gave the corresponding imide 5e besides
trace of 3aa (Table 4, Entries 2-6). Different extent of
decomposition of these imides was also observed even after
several hours of storage at room temperature in line with the
literature.5d, 10
CO
O
O
H
N
3aa
DTBP
Ph
t-BuO
E (unstable)
Ni(II)
Ni(III)
OBu-t
(IV)
Ni
Table 4. Ni-catalyzed aminocarbonylation of alkanes with
O
other amidesa
O
C
O
OBu-t
(IV)
Ni
A
N
H
or
Ni
N
H
(IV)
D
O
O
O
O
Ph
H
N
Ph
C
O
H
decomposition
CO, Ni(acac)
2
N
R2
NHR2
Ph
R2
+
2a
N
DTBP, 110oC
20 h
O
H
3
1
4
5
Ni(IV)
t-BuOH
CO
H
N
3 (yield%)b
5 (yield%) b
Ph
Entry
4
B
O
O
N
Scheme 1. Proposed reaction mechanism
1
2
3aa (50)
O
5a (25)
3. Conclusion
O
N
O
O
In conclusion, activation of alkanes bearing no assisting group
were realized by using Ni(acac)2 catalyst without auxiliary
ligands. The inexpensive nickel-based catalyst and the high
yields of the reaction enable this protocol synthetically useful for
straight functionalization of alkanes to provide amides. Further
efforts will be made to expand the applicable scope of
nickel-based catalysts in the direction of C(sp3)-H activation.
3ab(48)
3ac(45)
3aa(32)
H3C
NH
4b
5b
(37)
OMe
O
N
3
4
O
5c
(40)
O
4. Experimental section
O
N
NH
4.1. General Information
O
4d
5d
(37)
Commercially available materials were used as received.
Carbon monoxide (99.99%) was used as the carbon source.
Solvents were not further purified unless stated. Melting points

4
were measured with an Electrothermal-9200 melting points
apparatus. Proton nuclear magnetic resonance (1H NMR) spectra
were recorded on a Bruker (400 MHz) spectrometer. Chemical
shifts were recorded in parts per million (ppm, δ ) relative to
tetramethylsilane (δ = 0.00 ppm). Carbon nuclear magnetic
resonance (13C NMR) spectra were recorded on a Bruker (400
MHz) (101 MHz) spectrometer. Thin-layer chromatography
(TLC) was carried out on WFH-203 F254 silica gel plate.
High-resolution mass spectra (HRMS) were reported on a
Bruker APEX IV 7T FT-ICR instrument. YT-r50 autoclave was
used as the reactor (Nanjing Yantu Experimental Instrument co.
LTD, China).
White solid, 88% yield, mp 148-150 oC; 1H NMR (400 MHz,
ACCEPTED MANUSCRIPT
CDCl3) δ 7.44 (d, J= 8.5 Hz, 2H), 7.21 (br, 1H NH), 6.86 (d, J=
8.5 Hz, 2H), 3.80 (s, 3H), 2.22 (t, J= 11.6 Hz, 1H), 1.97 (d, J=
12.3 Hz, 2H), 1.85 (d, J= 9.6 Hz, 2H), 1.71 (s, 2H), 1.55 (d, J=
10.8 Hz, 2H), 1.29 (d, J= 8.4 Hz, 2H); 13C NMR (101 MHz,
CDCl3) δ 175.01, 157.63, 121.61, 114.10, 77.35, 77.04, 76.72,
55.50, 46.43, 29.72, 25.71; HRMS (ESI): calcd for C14H19NO2
[M+H]+ 234.1416, found 234.1417.
N-(4-Chlorophenyl)-cyclohexanecarboxamide 3ad
o
1
White solid, 87% yield, mp 182-186 C; H NMR (400 MHz,
CDCl3) δ 7.48 (d, J= 8.6 Hz, 2H), 7.30 (br, 1H NH), 7.26 (d, J=
8.6 Hz, 2H), 2.23 (t, J= 12.8 Hz, 1H), 1.94 (d, J= 12.6 Hz, 2H),
1.83 (d, J= 11.4 Hz, 2H), 1.71 (s, 1H), 1.61– 1.45 (m, 2H), 1.37–
1.17 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 174.46, 136.66,
129.12, 128.95, 121.02, 46.50, 29.62, 25.63; HRMS (ESI): calcd
for C13H17ClNO [M+H]+ 238.0920, found 238.0922.
4.2. Experimental procedures
(1) Typical procedure for the reaction of alkanes (1) and
formanilides (2) without auxiliary solvent
To a 50 mL of autoclave, was added cyclohexane (1a, 20 mL),
formanilide (2a, 10 mmol), Ni(acac)2 (1 mmol, 0.26 g) and
DTBP (12 mmol, 1.76 g). After replaced with argon twice, the
autoclave was rinsed three times with CO and then heated to 110
°C under 20 bar CO for 16 h. The autoclave is then cooled to
room temperature and carefully relieved of pressure. The solid
catalyst was filtered off. The excess alkane was removed under
reduced pressure and the residue was separated by silica gel
column chromatography (Petroleum ether/ ethyl acetate) to give
the product 3aa.
N-(4-Bromophenyl)-cyclohexanecarboxamide 3ae
1
White solid, 87% yield, mp 188-190 oC; H NMR (400 MHz,
CDCl3) δ 7.42 (s, 4H), 7.26 (br, 1H NH), 2.22 (t, J= 12.8 Hz, 1H),
1.94 (d, J= 10.8 Hz, 2H), 1.82 (s, 2H), 1.71 (s, 1H), 1.53 (d, J=
11.1 Hz, 2H), 1.27 (d, J= 8.1 Hz, 3H); 13C NMR (101 MHz,
CDCl3) δ 174.48, 136.94, 128.91, 121.32, 46.54, 29.62, 25.63;
HRMS (ESI): calcd for C13H16BrNO [M+H]+ 282.0415, found
282.0410.
N-(3-Methylphenyl)-cyclohexanecarboxamide 3af
(2) Special procedure for the reaction of alkanes (1c) and
formanilide (2d) using benzene as the solvent
1
White solid, 88% yield, mp 130-133 oC; H NMR (400 MHz,
CDCl3) δ 7.45 (s, 1H), 7.42 (br, 1H NH), 7.35– 7.28 (m, 1H),
7.20 (dd, J= 9.4, 6.2 Hz, 1H), 6.92 (d, J= 7.5 Hz, 1H), 2.34 (d, J=
4.9 Hz, 3H), 2.25 (tt, J= 11.7, 3.4 Hz, 1H), 1.96 (d, J= 13.3 Hz,
2H), 1.89– 1.76 (m, 2H), 1.71 (d, J= 8.2 Hz, 1H), 1.56 (qd, J=
12.3, 2.9 Hz, 2H), 1.36– 1.23 (m, 3H); 13C NMR (101 MHz,
CDCl3) δ 174.61, 138.86, 138.10, 128.75, 124.85, 120.51, 116.87,
46.51, 29.67, 25.67, 21.48. HRMS (ESI): calcd for C14H19NO
[M+H]+ 218.1467, found 218.1464.
Following the above described procedure, adamantine (1c, 10
mmol) was used in the place of 1a with dichloroethane (20 mL)
as the solvent to perform the reaction to furnish 3cd product.
(3) Typical procedure for the reaction of alkanes (1a) with
amides (4a)
According to the above procedure, acetanilide (4a, 10 mmol)
was used in the place of 2a to react with 1a (20 mL) in the
atmosphere of 20 bar CO for 20 h. After removing the excess 1a,
product 3aa and 5a were obtained by flash chromatography
(Petroleum ether/ ethyl acetate).
N-(2-Fluorophenyl)-cyclohexanecarboxamide 3ag
1
White solid, 86% yield, mp 140-142 oC; H NMR (400 MHz,
CDCl3) δ 9.53 (br, 1H NH), 8.36 (t, J= 7.8 Hz, 1H), 7.43– 6.98
(m, 3H), 2.29 (t, J= 12.8 Hz, 1H), 1.98 (d, J= 13.2 Hz, 2H), 1.90–
1.80 (m, 2H), 1.73 (t, J= 10.8 Hz, 1H), 1.54-1.29 (m, 5H); 13C
NMR (101 MHz, CDCl3) δ 174.36, 161.44, 126.69, 124.61,
123.92, 121.63, 114.74, 46.51, 29.67, 25.68; HRMS (ESI): calcd
for C13H16FNO [M+H]+ 222.1216, found 222.1216.
4.3. Product characterization
N-Phenyl-cyclohexanecarboxamide 3aa
o
1
White solid, 90% yield, mp 136-138 C; H NMR (400 MHz,
CDCl3) δ 7.46 (d, J= 7.8 Hz, 2H), 7.24 (t, J= 7.9 Hz, 2H), 7.14
(br, 1H NH), 7.02 (t, J= 7.4 Hz, 1H), 2.16 (tt, J= 11.8, 3.4 Hz,
1H), 1.89 (d, J= 13.2 Hz, 2H), 1.77 (d, J= 12.2 Hz, 2H), 1.66–
1.41 (m, 4H), 1.24– 1.18 (m, 2H); 13C NMR (101 MHz, CDCl3) δ
174.40, 138.07, 128.99, 124.10, 119.73, 46.60, 29.67, 25.68;
HRMS (ESI): calcd for C13H17NO [M+H]+ 204.1310, found
204.1308.
N-(2-Chlorophenyl)-cyclohexanecarboxamide 3ah
1
White solid, 84% yield, mp 160-162 oC; H NMR (400 MHz,
CDCl3) δ 8.33 (d, J= 7.8 Hz, 1H), 7.65 (s, 1H NH), 7.28 (dd, J=
8.0, 1.4 Hz, 1H), 7.23– 7.14 (m, 1H), 6.95 (td, J= 7.8, 1.5 Hz,
1H), 2.24 (tt, J= 11.7, 3.5 Hz, 1H), 1.94 (dd, J= 13.3, 1.9 Hz, 2H),
1.84– 1.73 (m, 2H), 1.65 (dd, J= 10.0, 4.0 Hz, 1H), 1.47 (qd, J=
12.2, 3.0 Hz, 2H), 1.29– 1.17 (m, 3H); 13C NMR (101 MHz,
CDCl3) δ 174.30, 134.72, 128.91, 127.74, 124.38, 122.65, 121.55,
46.66, 29.67, 25.66; HRMS (ESI): calcd for C13H17ClNO [M+H]+
238.0920, found 238.0925.
N-(4-Methylphenyl)-cyclohexanecarboxamide 3ab
1
White solid, 89% yield, mp 158-160 oC; H NMR (400 MHz,
CDCl3) δ 7.33 (d, J= 8.4 Hz, 2H), 7.13 (br, 1H NH), 7.03 (d, J=
8.2 Hz, 2H), 2.23 (s, 3H), 2.14 (t, J= 11.6 Hz , 1H), 1.87 (d, J=
12.8 Hz, 2H), 1.76 (d, J= 12.0 Hz, 2H), 1.62 (d, J= 6.6 Hz, 2H),
1.54– 1.40 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 174.36,
135.58, 133.64, 129.42, 119.89, 46.48, 29.68, 25.69, 20.85;
HRMS (ESI): calcd for C14H19NO [M+H]+ 218.1467, found
218.1470.
N-(2-Ethyl-6-methylphenyl)-cyclohexanecarboxamide 3ai
1
White solid, 81% yield, mp 160-163 oC; H NMR (400 MHz,
CDCl3) δ 9.57 (s, 1H NH), 7.24 (t, J= 7.6 Hz, 1H), 7.12 (dd, J=
17.1, 7.5 Hz, 2H), 2.36 (q, J= 7.6 Hz, 3H), 2.06 (m, 3H), 1.81–
1.59 (m, 7H), 1.46– 1.15 (m, 3H), 1.09 (t, J= 7.6 Hz, 3H); 13C
NMR (101 MHz, CDCl3) δ 174.76, 141.13, 136.00, 133.49,
127.39, 126.70, 126.18, 45.95, 30.91, 25.92, 24.77, 18.42, 14.43;
N-(4-Methoxyphenyl)-cyclohexanecarboxamide 3ac

5
HRMS (ESI): calcd for C16H23NO [M+H[+ 246.1780, found
246.1776.
4H), 1.48– 1.36 (m, 2H), 1.09– 0.98 (m, 2H); 13C NMR (101
ACCEPTED MANUSCRIPT
MHz, CDCl3) δ 177.69, 161.44, 159.86, 157.34, 131.39, 112.33,
112.13, 43.44, 29.93, 26.08; HRMS (ESI): calcd for C12H13F2NO
[M+H]+ 226.0965, found 226.0966.
N-(2,6-Difluorophenyl)-cyclohexanecarboxamide 3aj
1
White solid, 86% yield, mp 112-114 oC; H NMR (400 MHz,
N-(3,4-Dichlorophenyl)-cyclopentanecarboxamide 3bn
CDCl3) δ 9.45 (s, 1H), 7.35 (t, J= 8.5 Hz, 1H), 6.97 (d, J= 8.5 Hz,
2H), 2.78– 2.54 (m, 1H), 1.93– 1.71 (m, 3H), 1.72– 1.53 (m, 4H),
1.53– 1.07 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 177.22,
161.30, 159.72, 157.21, 131.3, 112.10, 111.59, 43.19, 28.75,
25.32, 25.22; HRMS (ESI): calcd for C13H15F2NO [M+H]+
240.1122, found 240.1120.
White solid, 84% yield, mp 157-159 oC; H NMR (400 MHz,
1
CDCl3) δ 7.72 (s, 1H), 7.30– 7.23 (m, 2H), 7.19 (br, 1H), 2.60 (t,
J= 8.0 Hz, 1H), 1.82 (d, J= 12.1, Hz, 4H), 1.75– 1.66 (m, 2H),
1.59– 1.50 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 174.87,
137.58, 132.73, 130.44, 127.15, 121.41, 118.89, 46.78, 30.52,
26.02; HRMS (ESI): calcd for C12H13Cl2NO [M+H]+ 258.0374,
found 258.0371.
Ethyl 2-(Cyclohexanecarboxamido)benzoate 3ak
White solid, 85% yield, mp 174-176 oC; 1H NMR (400 MHz,
CDCl3) δ 11.07 (s, 1H), 8.68 (d, J= 8.5 Hz, 1H), 7.97 (d, J= 8.0
Hz, 1H), 7.45 (d, J= 8.7 Hz, 1H), 7.04– 6.86 (m, 1H), 4.31 (q, J=
7.1 Hz, 2H), 2.25 (t, J= 11.8 Hz, 1H), 1.95 (d, J= 13.4 Hz, 2H),
1.82– 1.72 (m, 2H), 1.68– 1.41 (m, 2H), 1.35 (t, J= 7.1 Hz, 3H),
1.29– 1.16 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 175.38,
168.40, 141.90, 134.56, 130.81, 122.17, 120.39, 115.07, 77.38,
77.06, 76.75, 61.36, 47.28, 29.61, 25.75, 14.22; HRMS (ESI):
calcd for C16H21NO3 [M+H[+ 276.1521, found 276.1522.
N-(4-Chlorophenyl)-adamantane-1-carboxamide 3cd
1
White solid, 68% yield, mp 160-163 oC; H NMR (400 MHz,
CDCl3) δ 7.41 (t, J= 5.8 Hz, 2H), 7.25– 7.17 (m, 3H), 2.29 (br,
3H), 2.00– 1.78 (m, 6H), 1.78– 1.56 (m, 6H); 13C NMR (101
MHz, CDCl3) δ 174.61, 138.33, 128.21, 126.65, 121.66, 40.91,
38.22, 36.09, 27.65; HRMS (ESI): calcd for C17H26ClNO [M+H]+
290.1233, found 290.1234.
N-Phenyl-benzeneacetamide 3da
N-(4-(trifluoromethyl)phenyl)cyclohexanecarboxamide 3al
1
White solid, 56% yield, mp 117-119 oC; H NMR (400 MHz,
1
White solid, 68% yield, mp 166-167 oC; H NMR (400 MHz,
CDCl3) δ 7.33 (t, J= 6.7 Hz, 4H), 7.27 (dd, J= 6.7, 4.0 Hz, 3H),
7.23– 7.18 (m, 2H), 7.06 (br, 1H NH), 7.01 (t, J= 7.4 Hz, 1H),
3.67 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 169.10, 137.59,
134.42, 130.54, 129.42, 128.18, 127.72, 124.50, 119.84, 44.83;
HRMS (ESI): calcd for C14H13NO [M+H]+ 212.0997, found
212.1000.
CDCl3) δ 7.66 (d, J = 8.5 Hz, 2H), 7.55 (d, J = 8.6 Hz, 3H), 2.26
(tt, J = 11.7, 3.5 Hz, 1H), 1.95 (d, J = 13.5 Hz, 2H), 1.88 – 1.80
(m, 2H), 1.73 – 1.69 (m, 1H), 1.55 (qd, J = 12.1, 2.9 Hz, 2H),
1.33 – 1.23 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 174.83,
141.16, 126.22 (q, J = 3.7 Hz, 4H), 125.99, 125.67, 125.45,
122.75, 119.33, 46.57, 29.59, 25.58; HRMS (ESI): calcd for
C14H16F3NO [M+H]+ 272.1184, found 272.1185.
N-(4-Methylphenyl)-benzeneacetamide 3db
1
White solid, 61% yield, mp 140-141 oC; H NMR (400 MHz,
N-(pyridin-2-yl)cyclohexanecarboxamide 3am
CDCl3) δ 7.33 – 7.27 (m, 1H), 7.26 (dt, J = 14.7, 7.8 Hz, 4H),
7.26 – 7.19 (m, 3H), 6.98 (d, J = 8.0 Hz, 1H), 6.98 (d, J = 8.0 Hz,
1H), 3.62 (s, 2H), 2.20 (s, 3H); 13C NMR (101 MHz, CDCl3) δ
169.21, 135.11, 134.62, 134.12, 129.57, 129.43, 129.18, 127.60,
120.05, 44.74, 20.89; HRMS (ESI): calcd for C15H15NO [M+H]+
226.1154, found 226.1151.
1
White solid, 38% yield, mp 180-182 oC; H NMR (400 MHz,
CDCl3) δ 8.72 (s, 1H), 8.31 – 8.21 (m, 2H), 7.75 – 7.67 (m, 1H),
7.07 – 7.00 (m, 1H), 2.26 (tt, J = 11.7, 3.5 Hz, 1H), 1.98 – 1.90
(m, 2H), 1.82 (dd, J = 9.7, 3.1 Hz, 2H), 1.69 (d, J = 5.5 Hz, 1H),
1.60 – 1.48 (m, 2H), 1.31 – 1.20 (m, 3H); 13C NMR (101 MHz,
CDCl3) δ 175.08, 151.86, 147.52, 138.49, 119.58, 114.34, 46.37,
29.46, 25.60, 25.58; HRMS (ESI): calcd for C12H16N2O [M+H]+
205.1263, found 205.1260.
N-(3-Chloro-4-fluorophenyl)-benzeneacetamide 3do
1
White solid, 65% yield, mp 132-134 oC; H NMR (400 MHz,
CDCl3) δ 7.52 (dd, J= 6.5, 2.6 Hz, 1H), 7.40– 7.21 (m, 5H),
7.18– 7.12 (m, 1H), 6.97 (t, J= 8.8 Hz, 2H), 3.67 (s, 2H); 13C
NMR (101 MHz, CDCl3) δ 169.99, 156.07, 153.62, 129.45,
129.20, 127.73, 122.47, 120.95, 120.01, 116.63, 116.52, 116.41,
44.45; HRMS (ESI): calcd for C14H11FNO [M+H]+ 264.0513,
found 264.0511.
N-(4-Methoxyphenyl)-cyclopentanecarboxamide 3bc
1
White solid, 88% yield, mp 149-153 oC; H NMR (400 MHz,
CDCl3) δ 7.39– 7.32 (m, 2H), 7.16 (br, 1H), 6.81– 6.71 (m, 2H),
3.71 (s, 3H), 2.58 (t, J= 8.1 Hz, 1H), 1.87– 1.66 (m, 6H), 1.57–
1.48 (m, 2H); 13C NMR (101 MHz, CDCl3) δ 174.55, 156.19,
131.33, 121.62, 114.06, 55.49, 46.68, 30.58, 26.03; HRMS (ESI):
calcd for C13H17NO2 [M+H]+ 220.1259, found 220.1258.
N-(3-Bromophenyl)-benzeneacetamide 3dp
1
White solid, 66% yield, mp 179-181 oC; H NMR (400 MHz,
N-(3-Methylphenyl)-cyclopentanecarboxamide 3bf
CDCl3) δ 7.60 (d, J = 10.7 Hz, 2H), 7.32 – 7.17 (m, 6H), 7.10 (d,
J = 7.8 Hz, 1H), 7.01 (t, J = 7.8 Hz, 1H), 3.58 (d, J = 12.7 Hz,
2H); 13C NMR (101 MHz, CDCl3) δ 169.78, 138.96, 134.18,
130.25, 129.50, 129.23, 127.73, 127.4, 122.94, 122.52, 118.56,
44.63; HRMS (ESI): calcd for C14H12BrNO [M+H]+ 290.0102,
found 290.0106.
1
White solid, 85% yield, mp 143-145 oC; H NMR (400 MHz,
CDCl3) δ 7.45 (s, 1H), 7.30 (d, J= 9.7 Hz, 2H), 7.20 (t, J= 7.8 Hz,
1H), 6.93 (d, J= 7.4 Hz, 1H), 2.69 (p, J= 8.1 Hz, 1H), 2.34 (s,
3H), 1.92 (dd, J= 13.5, 5.8 Hz, 3H), 1.84– 1.75 (m, 2H), 1.64 (dt,
J= 7.8, 5.7 Hz, 2H), 1.27 (d, J= 4.6 Hz, 1H); 13C NMR (101 MHz,
CDCl3) δ 174.69, 138.91, 138.09, 128.77, 124.84, 120.37, 116.71,
46.89, 30.56, 26.03, 21.50; HRMS (ESI): calcd for C13H17NO
[M+H]+ 204.1310, found 204.1305.
N-(2-Chlorophenyl)-benzeneacetamide 3dq
1
White solid, 61% yield, mp 129-130 oC; H NMR (400 MHz,
CDCl3) δ 7.73 (br, 1H), 7.51 – 7.40 (m, 1H), 7.32 – 7.13 (m, 6H),
7.06 (t, J = 7.7 Hz, 1H), 6.95 (d, J = 7.7 Hz, 1H), 3.58 (s, 2H);
13C NMR (101 MHz, CDCl3) δ 169.82, 138.89, 134.52, 134.25,
129.94, 129.48, 129.19, 127.69, 124.50, 120.15, 118.09, 44.62;
N-(2,6-Difluorophenyl)-cyclopentanecarboxamide 3bj
1
White solid, 81% yield, mp 114-116 oC; H NMR (400 MHz,
CDCl3) δ 9.40 (s, 1H), 7.33 (t, J= 6.3 Hz, 1H), 6.96 (d, J= 7.4 Hz,
2H), 2.22 (dd, J= 11.3, 7.0 Hz, 1H), 1.67 (dd, J= 11.9, 9.2 Hz,

6
HRMS (ESI): calcd for C14H12ClNO [M+H]+ 246.0607, found
246.0611.
N-Acetyl-N-(p-tolyl)cyclohexanecarboxamide 5b
ACCEPTED MANUSCRIPT
1
Colorless solution, 37% yield. H NMR (400 MHz, CDCl3) δ
7.29 – 7.20 (m, 2H), 7.00 (d, J = 8.2 Hz, 2H), 2.68 (ddd, J = 11.5,
7.4, 3.3 Hz, 1H), 2.40 (s, 3H), 2.32 (s, 3H), 1.82 (d, J = 11.7 Hz,
2H), 1.75 – 1.68 (m, 2H), 1.61 (d, J = 11.2 Hz, 1H), 1.52 – 1.41
(m, 2H), 1.15 (tdd, J = 25.3, 17.3, 7.7 Hz, 3H); 13C NMR (101
MHz, CDCl3) δ 179.68, 173.54, 138.67, 136.53, 130.39, 128.34,
44.82, 29.35, 26.92, 25.66, 25.42, 21.21; HRMS (ESI): calcd for
C16H21NO2 [M+H]+ 260.1572, found 260.1569.
N-Phenyl-α-methyl-benzeneacetamide 3ea
1
White solid, 60% yield, mp 160-163 oC; H NMR (400 MHz,
CDCl3) δ 7.34 (d, J= 8.1 Hz, 2H), 7.29– 7.13 (m, 7H), 7.00 (dd,
J= 15.6, 8.2 Hz, 2H), 3.64 (q, J= 7.1 Hz, 1H), 1.52 (d, J= 7.1 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ 174.46, 140.93, 137.84,
129.19, 128.93, 127.67, 124.26, 119.66, 48.15, 18.57; HRMS
(ESI): calcd for C15H15NO [M+H]+ 226.1154, found 226.1150.
N-Acetyl-N-(4-methoxyphenyl)cyclohexanecarboxamide 5c
N-(4-Methoxyphenyl)-α-methyl-benzeneacetamide 3ec
1
Colorless solution, 40% yield. H NMR (400 MHz, CDCl3) δ
1
White solid, 63% yield, mp 160-163 oC; H NMR (400 MHz,
6.98 – 6.91 (m, 2H), 6.90 – 6.82 (m, 2H), 3.74 (s, 3H), 2.67 –
2.57 (m, 1H), 2.22 (s, 3H), 1.74 (dd, J = 13.3, 1.7 Hz, 2H), 1.69 –
1.59 (m, 2H), 1.58 – 1.49 (m, 1H), 1.44 – 1.30 (m, 2H), 1.17 –
0.96 (m, 3H); 13C NMR (101 MHz, CDCl3) δ 179.71, 173.57,
159.49, 131.72, 129.62, 114.86, 55.42, 44.78, 29.33, 28.87, 26.81;
HRMS (ESI): calcd for C16H21NO3 [M+H]+ 276.1521, found
276.1526.
CDCl3) δ 7.41 – 7.34 (m, 4H), 7.33 – 7.27 (m, 3H), 7.07 (br, 1H),
6.83 – 6.76 (m, 2H), 3.75 (s, 3H), 3.70 (q, J = 7.1 Hz, 1H), 1.59
(d, J = 7.2 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 172.24,
156.38, 141.08, 130.95, 129.13, 127.73, 127.53, 121.66, 114.03,
55.48, 47.90, 18.62; HRMS (ESI): calcd for C16H17NO2 [M+H]+
256.1259, found 256.1263.
N-(3-Methylphenyl)-α-methyl-benzeneacetamide 3ef
N-Phenyl-N-propionylcyclohexanecarboxamide 5d
1
White solid, 53% yield, mp 99-101 oC; H NMR (400 MHz,
1
Colorless solution, 37% yield. H NMR (400 MHz, CDCl3) δ
CDCl3) δ 7.37 (d, J= 14.1 Hz, 5H), 7.19– 7.15 (m, 3H), 6.98 (br,
1H NH), 6.91 (d, J= 6.7 Hz, 1H), 3.73 (q, J= 7.2 Hz, 1H, 2.32 (s,
3H), 1.62 (d, J= 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ
174.36, 140.93, 137.84, 133.91, 129.41, 128.93, 127.73, 127.61,
124.26, 119.66, 48.15, 20.70, 18.57; HRMS (ESI): calcd for
C16H17NO [M+H]+ 240.1310, found 240.1306.
7.48 – 7.36 (m, 3H), 7.14 – 7.08 (m, 2H), 2.85 (tt, J = 11.4, 3.3
Hz, 1H), 2.51 (q, J = 7.3 Hz, 2H), 1.92 – 1.82 (m, 2H), 1.78 –
1.69 (m, 2H), 1.63 (dd, J = 5.1, 3.9 Hz, 1H), 1.54 – 1.41 (m, 2H),
1.28 – 1.13 (m, 3H), 1.10 (t, J = 7.3 Hz, 3H); 13C NMR (101
MHz, CDCl3) δ 179.63, 176.85, 139.23, 129.63, 128.83, 128.57,
45.15, 31.93, 29.43, 25.72, 25.50, 9.08; HRMS (ESI): calcd for
C16H21NO2 [M+H]+ 260.1572, found 260.1573.
N'-(Cyclohexanecarbonyl)benzohydrazide 3ar
White solid, 61% yield, mp 200-202 oC; 1H NMR (400 MHz,
CDCl3) δ 9.90 (d, J= 5.5 Hz, 1H), 9.48 (d, J= 5.5 Hz, 1H), 7.84
(d, J= 7.3 Hz, 2H), 7.51 (t, J= 7.4 Hz, 1H), 7.40 (t, J= 7.7 Hz,
2H), 2.35 (tt, J= 11.8, 3.4 Hz, 1H), 1.93– 1.73 (m, 5H), 1.68 (d,
J= 5.6 Hz, 1H), 1.57– 1.46 (m, 2H), 1.37– 1.25 (m, 2H); 13C
NMR (101 MHz, CDCl3) δ 174.69, 164.07, 132.29, 131.40,
128.67, 127.28, 43.22, 29.30, 25.61, 25.54; HRMS (ESI): calcd
for C14H18N2O2 [M+H]+ 247.1368, found 247.1364.
N-(p-Tolyl)-N-propionylcyclohexanecarboxamide 5e
1
Colorless solution, 42% yield. H NMR (400 MHz, CDCl3) δ
7.17 (t, J = 8.8 Hz, 2H), 6.91 (d, J = 8.2 Hz, 2H), 2.79 (tt, J =
11.4, 3.2 Hz, 1H), 2.44 (q, J = 7.3 Hz, 2H), 2.31 (s, 3H), 1.78 (d,
J = 12.4 Hz, 2H), 1.65 (dd, J = 8.8, 2.6 Hz, 2H), 1.58 – 1.51 (m,
1H), 1.45 – 1.32 (m, 2H), 1.20 – 1.05 (m, 3H), 1.02 (t, J = 7.3 Hz,
3H); 13C NMR (101 MHz, CDCl3) δ 179.77, 177.01, 138.53,
136.52, 130.32, 128.49, 45.09, 31.93, 29.43, 25.74, 25.50, 21.19,
9.11; HRMS (ESI): calcd for C17H23NO2 [M+H]+ 274.1729,
found 274.1733.
N'-(Cyclopentanecarbonyl)benzohydrazide 3br
1
White solid, 59% yield, mp 210-212 oC; H NMR (400 MHz,
N-(Cyclohexanecarbonyl)-N-phenylbenzamide 5f
CDCl3) δ 9.26 (d, J= 5.3 Hz, 1H), 8.88 (d, J= 5.3 Hz, 1H), 7.84
(d, J= 7.4 Hz, 2H), 7.56 (t, J= 7.4 Hz, 1H), 7.46 (t, J= 7.6 Hz,
2H), 2.72 (dd, J= 16.2, 8.0 Hz, 1H), 1.96– 1.77 (m, 6H), 1.67 (s,
4H); 13C NMR (101 MHz, CDCl3) δ 174.26, 164.07, 131.40,
128.67, 127.2, 43.22, 29.30, 25.70, 25.50; HRMS (ESI): calcd for
C13H16N2O2 [M+H]+ 233.1212, found 233.1217.
1
Colorless solution, 57% yield. H NMR (400 MHz, CDCl3) δ
7.62 (dd, J = 5.2, 3.3 Hz, 2H), 7.40 – 7.34 (m, 1H), 7.33 – 7.25
(m, 4H), 7.25 – 7.18 (m, 1H), 7.15 – 7.06 (m, 2H), 2.81 (tt, J =
11.5, 3.4 Hz, 1H), 1.99 (dd, J = 11.3, 8.7 Hz, 2H), 1.75 (dd, J =
9.9, 2.7 Hz, 2H), 1.66 – 1.51 (m, 3H), 1.25 – 1.12 (m, 3H); 13C
NMR (101 MHz, CDCl3) δ 180.50, 173.29, 139.49, 135.17,
132.04, 129.45, 129.09, 128.49, 128.42, 127.98, 44.82, 29.66,
25.74, 25.55; HRMS (ESI): calcd for C20H21NO2 [M+H]+
308.1572, found 308.1569.
N'-Benzoyladamantane-1-carbohydrazide 3cr
1
White solid, 53% yield, mp 230-232 oC; H NMR (400 MHz,
CDCl3) δ 9.33 (d, J= 6.0 Hz, 1H), 8.72 (d, J= 5.7 Hz, 1H), 7.82–
7.72 (m, 2H), 7.46 (dd, J= 8.3, 6.4 Hz, 1H), 7.37 (td, J= 7.6, 3.0
Hz, 2H), 2.63– 1.99 (m, 3H), 1.90– 1.74 (m, 6H), 1.71– 1.61 (m,
6H); 13C NMR (101 MHz, CDCl3) δ 174.50, 164.52, 132.24,
131.45, 128.64, 127.28, 48.67, 38.75, 38.72, 36.36; HRMS (ESI):
calcd for C13H16N2O2 [M+H]+ 299.1681, found 299.1676.
Supplementary data
Supplementary data related to this article can be found in the
supporting information.
N-Acetyl-N-phenylcyclohexanecarboxamide 5a
References
1
Colorless solution, 25% yield. H NMR (400 MHz, CDCl3) δ
7.41 – 7.32 (m, 3H), 7.08 – 6.98 (m, 2H), 2.67 – 2.56 (m, 1H),
2.24 (s, 3H), 1.79 – 1.73 (m, 2H), 1.68 – 1.62 (m, 2H), 1.53 (dd,
J = 7.0, 5.3 Hz, 1H), 1.44 – 1.20 (m, 3H), 1.09 – 1.01 (m, 2H);
13C NMR (101 MHz, CDCl3) δ 179.57, 173.37, 139.24, 129.72,
128.68, 119.72, 44.93, 29.35, 26.92, 25.65, 25.43; HRMS (ESI):
calcd for C15H19NO2 [M+H]+ 246.1416, found 246.1410.
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