Cp?CoIII-Catalyzed syn-Selective C-H Hydroarylation of Alkynes Using Benzamides: An Approach Toward Highly Conjugated Organic Frameworks

Article abstract of DOI:10.1021/acs.joc.6b02516

Hydroarylation of internal alkynes by cost-effective Co^III-catalysis, directed by N-tert-butyl amides, is achieved to avail mono- or dihydroarylated amide products selectively in an atom and step economic way. Several important functional groups were tolerated under the reaction conditions, and syn-hydroarylation products were exclusively isolated. Notably, a 4-fold C-H hydroarylation provided a highly conjugated organic framework in one step. Kinetic study with extensive deuterium labeling experiments were performed to support the proposed mechanism.

Full text of DOI:10.1021/acs.joc.6b02516

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Article
Cp*CoIII-Catalyzed syn-Selective C-H Hydroarylation of Alkynes Using
Benzamides: An Approach Towards Highly Conjugated Organic Frameworks
Sourav Sekhar Bera, Suvankar Debbarma, Avick Kumar Ghosh, Santanu Chand, and Modhu Sudan Maji
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02516 • Publication Date (Web): 05 Dec 2016
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Cp*CoIII-Catalyzed syn-Selective C-H Hydroarylation of Alkynes Us-
ing Benzamides: An Approach Towards Highly Conjugated Organic
Frameworks
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Sourav Sekhar Bera, Suvankar Debbarma, Avick Kumar Ghosh, Santanu Chand, Modhu Sudan
Maji*
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, W. B., India.
ABSTRACT: Hydroarylation of internal alkynes by cost effective CoIII-catalysis, directed by N-tert-butyl amides, is
achieved to avail mono- or di-hydroarylated am-
ide products selectively in an atom and step eco-
nomic way. Several important functional groups
were tolerated the reaction conditions, and syn-
hydroarylation products were exclusively isolat-
ed. Notably, a fourfold C-H hydroarylation pro-
vided a highly conjugated organic framework in
one step. Kinetic study with extensive deuterium
labelling experiments were performed to support
the
proposed
mechanism.
INTRODUCTION
as this need to use the corresponding pre-functionalized
aryl dihalides which requires tedious synthetic efforts.11
Transition metal catalyzed C-H activation has emerged as
a powerful atom and step economic method to function-
alize inert C-H bonds to install desired functional groups
of great synthetic interest.1 Compared to noble metals, C-
H bond functionalization based on the corresponding
first row transition metal catalysts are much under devel-
oped and recently gained considerable attention due to
their low cost and ready availability. In this line low va-
lent cobalt catalysts have played a crucial role for directed
C-H bond functionalization.2,3 However in many cases,
reactive Grignard reagents used to generate active low
valent cobalt catalyst restrict its application for many sub-
strates having reactive functionalities. In this direction,
recently high valent cationic CoIII-catalyzed C-H bond
functionalization has gained significant attention. Kanai,
Matsunaga and co-workers have first reported the cation-
ic CoIII-catalyzed insertion reaction of C-H bond to al-
kynes (Scheme 1), imines and enones.4 Later on Glorius,
Ackermann and Chang groups reported CoIII-catalyzed
cyanation, halogenation and allylation reactions.5 Ellman
and co-workers has applied this Cp*CoIII-catalyst for the
synthesis of indazole and furan by C-H functionalization
strategy.6 Since then this catalyst has been an attractive
choice to achieve some remarkable transformations by
site selective functionalization of unactivated C-H
bonds.7-10
Scheme 1. Amide Directed C-H Hydroarylations
Alkenylated aryls are very important molecules as they
are key starting precursors for the synthesis of conjugated
LED materials.12,13 Hydroarylation of alkynes by C-H bond
activation is a highly efficient, atom and step economic
method to synthesize alkenylated arenes.14 More im-
portantly, manifold C-H hydroarylation is a highly prom-
ising method to generate highly conjugated organic
frameworks in just one step. Amide directed rhodium and
ruthenium catalyzed hydroarylation was previously re-
Installation of alkenyl moieties on the aryl unit by clas-
sical cross-coupling methods faces some limitations, such
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ported by Tanaka14c and Miura et al. (Scheme 1).14e Previ-
(entry 5). Interestingly, on decreasing the Cu(OAc)2·H2O
ously, Kisch and Yoshikai groups15a-d reported a low valent
cobalt catalyzed hydroarylation reaction on azobenzene
and aromatic imines system, but limited scope and sensi-
tive catalytic system with complex reaction conditions
restrict its broad application. Although Petit et al. report-
ed an anti-selective hydroarylation reaction, but catalytic
system involves highly combustible and air sensitive
Co(PMe3)4 catalyst.15e-f Later on using internal alkyne,
Kanai et al.4c introduced stable high valent CoIII-catalyzed
carbamoyl directed hydroarylation on indole system, and
here we have revealed our results on amide directed cost
effective CoIII-catalyzed syn-hydroarylation on arene sys-
tem using internal alkynes under robust reaction condi-
tions. We advanced the scope of hydroarytion by synthe-
sizing mono- and di-hydroarylated products selectively,
and extended our methodology to four-fold C-H activa-
tion strategy.
additive, although the yield of 3a decreased, it favored the
formation of 4a (entries 6 to 7). Gratifyingly, on using 2.5
equiv of 2a, all 3a was converted to 4a and isolated as sole
product in 82% yield (entry 8). Even without
Cu(OAc)2·H2O additive, 4a was isolated in 70% yield (en-
try 9). Further optimization by decreasing the catalyst
loading to 5.0 mol % provided 3a selectively (entry 7 vs.
10). Finally, the yield of 3a was further improved on in-
creasing the amount of 2a to 1.3 equiv (entry 11). Screening
of different benzamides revealed that free N-H-functional
group is necessary for this hydroarylation reaction.
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With optimized conditions in hand, the scope of the
mono-hydroarylation reaction was studied first by varying
several amides 1. The reaction proceeds with good to ex-
cellent yields for several amides having wide range of
functional groups (Scheme 2). 4-Fluoro and 4-chloro ben-
zamide reacted smoothly to provide mono-alkenylated
product 3b and 3c in 60% and 63% yields, respectively. In
both cases, di-alkenylated products were also isolated in
low yields as shown in the parenthesis (5% and 19% re-
spectively).
RESULT AND DISCUSSION
We optimized the reaction conditions by using N-(tert-
butyl)benzamide 1a and diphenylacetylene 2a (Table 1).
The Cp*Co(CO)I2 catalyst was employed in combination
with Ag(I)-salt and hydrated Cu(OAc)2 additives.
Scheme 2. Scope of mono-hydroarylation reactiona,b
Table 1. Optimization of the reaction conditionsa
entry catalyst Ag(I)-
[mol %] additive
Cu(OAc)2·H2O yield [%]b
[equiv]
3a
4a
1
10
0
AgSbF6
AgSbF6
no
1.05
1.05
1.05
1.05
2.1
52
0
8
2
0
3
10
10
10
10
10
10
10
5
0
0
4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
AgBF4
56
35
45
38
0
8
5
4
6
0.50
0.15
0.15
0
15
27
82
70
17
19
7
8c
9c
10d
11d,e
4
0.15
0.15
58
63
aReaction Conditions:
1 (0.25 mmol), 2 (0.33 mmol),
5
Cp*Co(CO)I2 (0.0125 mmol), AgBF4 (0.0375 mmol),
Cu(OAc)2·H2O (0.0375 mmol), DCE (1.0 mL), 12 h. bIn paren-
thesis isolated yields of the corresponding di-alkenylated
products 4 were given. c10 mol % catalyst and 30 mol %
AgBF4 used.
aReaction conditions: 1a (0.25 mmol), 2a (0.25 mmol), 12-16
h. bIsolated yields. c2.5 equiv of 2a was used. d15 mol % AgBF4
used and reaction temp. 100 oC. e1.3 equiv of 2a was used.
For this reaction 1,2-dichloroethane was found to be the
best solvent (entry 1). Cp*CoIII-catalyst and AgSbF6 addi-
tive were mandatory for our reaction (entries 2 and 3). On
changing the additive to AgBF4, the yield of 3a slightly
improved to 56% (entry 4). On increasing the amount of
Cu(OAc)2·H2O additive, the yield of 3a and 4a decreased
Amides having electron withdrawing trifluoromethyl,
cyanide, and nitro groups at the para position also reacted
selectively to provide mono-alkenylated products 3d-3f in
62-68% yields. For meta substituted benzamides, less ste-
rically hindered ortho-C-H-bond underwent reaction
which was confirmed by 1H NMR analysis. Amides having
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electron donating methoxy and methyl substitutions at
Finally, we explored the scope of this reaction with
various internal symmetrical and unsymmetrival alkynes
(Scheme 4). Unsymmetrical arylalkyne, 1-
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3
4
5
6
7
8
the meta position provided products 3g and 3h in 51% and
61% yields, respectively. Several electron withdrawing
functional groups at the meta position of amides also re-
acted smoothly to provide products 3i-3l in 36 to 80%
yields. 2-Fluoro and sterically hindered 2-bromo ben-
zamides also provided desired product 3m and 3n in
moderate yields. 1-Naphthamide was also a suitable sub-
strate for our reaction and product 3o was isolated in 53%
yield. On changing the amine part of the amide to cyclo-
hexyl, product 3p was isolated in 55% yield along with 11%
of di-alkenylated product.
(phenylethynyl)naphthalene, reacted with 1a selectively
to provide 3q in 61% yield as a 4.7:1 regioisomeric mixture.
Two other unsymmetrical aryl alkylalkynes, methyl phe-
nylpropiolate and 1-phenyl-1-propyne, have also taken
part in the reaction and products 3r and 3s were isolated
in moderate yields and regioselectivities. Electron
donating methyl and fluoro substituted alkynes reacted
smoothly to provide di-alkenylated products 4m and 4n
in good yields. Symmetrical 4-chloro and 4-bromo
substituted diarylalkynes were also suitable substrates for
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Scheme 3. Scope of di-hydroarylation reactiona,b
the
reaction.
Electron
deficient
1,2-bis(4-
(trifluoromethyl)phenyl) ethyne reacted under our
reaction conditions to provide di-alkenylated product 4q
in 45% yield. 1-phenyl-1-propyne also readily reacted
under dihydroarylation conditions, and all three isomers
4r, 4rʹand 4rʹʹ were isolated in a combined yield of 84% as
an inseparable mixture. Single crystal X-ray analysis of
products 3m and 4a confirmed that hydroarylation
occurred in syn-fashion (Figure S7).20 The alkene
geometry of products 3a-l, 3n-p and 4b-q are assigned in
analogy to 3m and 4a, respectively.
Scheme 4. Scope of alkyne for hydroarylation reac-
tion
aReaction Conditions:
1 (0.25 mmol), 2 (0.63 mmol),
Cp*Co(CO)I2 (0.025 mmol), AgBF4 (0.075 mmol),
Cu(OAc)2·H2O (0.0375 mmol), DCE (1.0 mL), 16 h. bIn paren-
thesis the isolated yields of 3 were given.
After successfully studying the scope of the mono-
hydroarylation method, we investigated the scope of the
dihydroarylation method (Scheme 3). It will provide many
important 1,3-di-alkenylated benzamides, a key building
block presents in important conjugated PPVs polymers.
In general, the reaction was highly efficient and in most of
the cases clean formation of di-alkenylated product 4 was
observed. Amides having fluoro, chloro, and bromo func-
tionalities at the para position reacted smoothly to pro-
vide products 4b-4d in moderate to excellent yields (61-
83%). Electron withdrawing trifluoromethyl, cyanide,
nitro, and ester substitutions at the para position of the
benzamide also reacted smoothly to provide 4e-4h in 60-
80% yields. 4-Methoxy and 4-methyl substituted ben-
zamide also provided di-alkenylated products 4i and 4j in
70% and 71% yields, respectively. Finally, 3-
methoxybenzamide also provided desired product 4k in
excellent yield. On changing the amide functional groups
from tert-butyl to cyclohexyl, product 4l was obtained in
decent yield.
b
aReaction Conditions: As described under Scheme 2. In the
parenthesis regioselectivities are given. cReaction Conditions:
As described under Scheme 3. dIn parenthesis the isolated
yields of 3 provided.
Organic frameworks containing arenes with conjugated
π-systems show potential utility as organic electronic ma-
terials.16 Synthesizing them directly from simple starting
materials is highly demanding area of research. Besides
the cross-coupling reactions, C-H activation has already
been introduced to prepare them in highly efficient way.17
To show the efficiency of our method, bi-phenyl based
diamide 1w was subjected under the optimized reaction
conditions to achieve fourfold C-H hydroarylations in a
single step. To our delight, the desired highly conjugated
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poly aromatic tetra-alkenylated framework 5 was ob- To gain insight in to the catalyst’s mode of action we
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4
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tained albeit in relatively low yield from 1w (24%, Scheme
5a). Due to extended π-conjugation, compound 5 was
found to be fluorescence active. It absorbs UV (in metha-
nol) at λmax 288 nm and fluoresces at λmax 390 nm (Figure
S8).20 In presence of sulphuric acid, hydroarylated prod-
uct 3a leads to the formation of isoindolinone structure 6
with N-substituted quaternary center which is a privi-
leged structural motif present in many natural products
and biologically active molecules (Scheme 5b).18
performed intermolecular competition experiment using
electronically different benzamides, and we found
electron rich benzamides are converted more efficiently
with almost 3.4:1 ratio (4i/4h, Scheme 6a).20 This result
can be explained by a base assisted intermolecular
electrophilic
substitution
reaction
(BIES)
type
mechanism.1c,19a-d Deuterium exchange experiments using
CD3OD co-solvent under the same reaction conditions
did not show a significant amount of H/D scrambling at
the ortho-positions, suggesting an irreversible C-H-
activation step. Further mechanistic investigation with
alkyne also reveals that the alkene proton is deuterated
partially (~34%) by the external deuterium source
(Scheme 6c). Parallel experiment, intermolecular and
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Scheme 5. Four-fold C-H activation and hydroamina-
tion of hydroarylated product
intramolecular competition experiments
have been
performed to study kinetic isotopic effect. A KIE value of
4.0 and a KH/KD value of 2.8 were obsearved form the
intermolecular competition
experiment and parallel
experiment, respectively (Scheme 6d). Finally, an
intramolecular competition experiment has also been
conducted and it showed a KIE value of 2.6 (Scheme 6e).
All these results indicate that C-H activation probably
occurs in the rate determining step (RDS) of the
reaction.19b
Scheme 6. Intermolecular competition experiment,
deuterium labelling study, and kinetic isotopic effect
study.
Scheme 7. Proposed mechanism for hydroarylation
reaction
Based on the above experiments and previous reports,
we propose that cobalt(III)-catalyzed C−H hydroarylation
proceeds via a facile BIES-type C−H cobaltation step
(Scheme 7).1c,19 In the presence of copper acetate additive,
in situ prepared Cp*Co(III)-complex
A
generates
metallacycle through the acetate assisted C-H
B
activation.1c Thereafter subsequent alkyne co-ordination
to the cyclometallated intermediate B delivers C followed
by the migratory insertion to produce intermediate D.
Finally in the presence of acid, proto-demetallation takes
place to provide hydroarylated product 3 along with the
regenerated active catalyst A, completing the catalytic
cycle.
CONCLUSION
In conclusion, we have developed an elegant method to
synthesize several mono- and di-alkenylated benzamides
selectively using readily available tert-butylbenzamides
derivatives and internal alkyne as starting precursors. An
inexpensive cobalt(III)-catalyst was employed to achieve
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rified by silica gel column chromatography using petroleum
the goal. Several important functional groups such as
1
2
3
4
5
6
ether/ ethylacetate eluent.
chloride, bromide, cyanide, ester and nitro were tolerated
the reaction conditions. The reaction showed excellent
scope as several amides and alkynes were suitable
substrates for our reaction. This method is highly
effective to build structurally defined extended π-
conjugated frameworks in a single step.
General Procedure for mono C-H hydroarylation with
N-(tert-butyl)benzamide (GP IIB). Similar to GP IIA, ex-
cept catalyst Cp*Co(CO)I2 (11.9 mg, 0.025 mmol, 10.0 mol %)
and additive AgBF4 (14.6 mg, 0.075 mmol, 30.0 mol %)
amounts were changed.
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8
9
General Procedure for di C-H hydroarylation with N-
(tert-butyl)benzamide (GP III). N-(tert-butyl)benzamide 1
(0.25 mmol, 1.0 equiv) was taken in a 12.0 mL screw capped
reaction tube, and 1.0 mL of anhydrous 1,2-dichloroethane
was added. Then alkyne 2 (0.63 mmol, 2.5 equiv), catalyst
Cp*Co(CO)I2 (11.9 mg, 0.025 mmol, 10.0 mol %), additive
AgBF4 (14.6 mg, 0.075 mmol, 30.0 mol %) and Cu(OAc)2·H2O
(7.5 mg, 0.0375 mmol, 15.0 mol %) were added to the reaction
mixture. The resultant reaction mixture was allowed to stir at
120 °C for 16 h. After completion of the reaction as indicated
by TLC, the crude product was directly purified by silica gel
column chromatography using petroleum ether/ethylacetate
eluent.
EXPERIMENTAL SECTION
General Information. All reactions were carried out in an
oven dried sealed tube. Unless otherwise stated, all solvents
were dried by following standard procedure. Analytical thin
layer chromatography (TLC) was performed on pre-coated
silica gel 60 F254 plates. Column chromatography was per-
formed through silica gel (100-200 mesh) using a proper sol-
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1
vent system. H NMR and 13C NMR were recorded on a (400
MHz) and (600 MHz) spectrometer in CDCl3. Data are re-
ported in the following order: chemical shift (δ) in ppm; mul-
tiplicities are indicated as br (broad), s (singlet), d (doublet),
t (triplet), q (quartet), m (multiplet); coupling constants (J)
1
are given in Hertz (Hz). Chemical shift for H NMR spectra
N-(tert-butyl)benzamide (1a). The title compound 1a was
synthesized according to the GP I and isolated as white solid
(1.50 g, 85%). 1H NMR (400 MHz, CDCl3): δ (ppm) 7.72 (d, J =
6.5 Hz, 2H), 7.47-7.41 (m, 3H), 5.95 (br s, 1H), 1.47 (s, 9H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 167.1, 136.0, 131.2, 128.6,
126.8, 51.8, 29.0.
were reported with respect to the residual signal of CHCl3 at
7.26 ppm present in CDCl3. Chemical shifts for 13C NMR spec-
tra were mentioned in ppm with respect to the center of a
triplet at 77.16 ppm of chloroform-d. High resolution mass
spectra (HRMS) were recorded in TOF, ESI (+ Ve) method.
Other chemicals were obtained from commercial sources
and used without further purification. Single crystal X-ray
data of the crystal was collected at 293 K on a CCD diffrac-
tometer. Infrared (IR) spectra were recorded by FTIR spec-
trometer and reported in cm−1.
N-(tert-butyl)-4-fluorobenzamide (1b). The title compound
1b was synthesized according to the GP I and isolated as
white solid (1.52 g, 78%). 1H NMR (400 MHz, CDCl3): δ (ppm)
7.73-7.69 (m, 2H), 7.08-7.04 (m, 2H), 5.93 (br s, 1H), 1.45 (s,
9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 166.0, 164.6 (d, J =
251.2 Hz), 132.2, 129.1 (d, J = 8.8 Hz), 115.5 (d, J = 21.7 Hz), 51.9,
29.0.
General Procedure for the Preparation of Aromatic Am-
ides: (GP I). The benzamides 1a-w were prepared according
to the literature procedure from the corresponding acid chlo-
ride or acid.10d For the preparation of acid chloride, the car-
boxylic acid (10.0 mmol) and thionyl chloride (5.0 mL) were
mixed and refluxed for 2 h. After completion of the reaction,
volatiles were removed in vacuo to obtain crude acid chloride
which was directly used for the next step without further
purification. For the synthesis of aryl amides, to a solution of
the corresponding benzoyl chloride (10.0 mmol) in diethyl
ether (0.5 mmol/mL), triethylamine (2.0 equiv) was added
and the reaction mixture was allowed to cool at 0 °C for 15
min. To this cooled reaction mixture amine was added slowly
and then stirring was continued at room temperature for 3 h.
The reaction mixture was quenched using 1.0 N HCl and ex-
tracted with ethyl acetate (30 mL x 2). The combined organic
layers were washed with brine, dried over Na2SO4 and con-
centrated in vacuo. The crude product was further purified
by silica gel column chromatography using hex-
ane/ethylacetate eluent.
N-(tert-butyl)-4-chlorobenzamide (1c). The title compound
1c was synthesized according to the GP I and isolated as
1
white solid (1.69 g, 80%). H NMR (400 MHz, CDCl3): δ
(ppm) 7.64 (d, J = 7.2 Hz, 2H), 7.36 (d, J = 7.2 Hz, 2H), 5.92
(br s, 1H), 1.46 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm)
166.0, 137.4, 134.4, 128.8, 128.3, 51.9, 29.0.
4-Bromo-N-(tert-butyl)benzamide (1d). The title compound
1d was synthesized according to the GP I and isolated as
white solid (2.18 g, 85%). 1H NMR (400 MHz, CDCl3): δ (ppm)
7.58 (d, J = 8.4 Hz, 1H), 7.52 (d, J = 8.3 Hz, 1H), 5.92 (br s, 1H),
1.45 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm) 166.0, 134.9,
131.8, 128.5, 125.8, 51.9, 29.0.
N-(tert-butyl)-4-(trifluoromethyl)benzamide (1e). The title
compound 1e was synthesized according to the GP I and iso-
lated as white solid (1.59 g, 65%). 1H NMR (400 MHz, CDCl3):
δ (ppm) 7.82 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 5.98
(br s, 1H), 1.48 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm)
165.8, 139.4, 133.0 (q, J = 32.5 Hz), 127.3, 125.7 (q, J = 3.8 Hz),
123.9 (q, J = 272.2 Hz), 52.1, 28.9.
General Procedure for mono C-H hydroarylation with
N-(tert-butyl)benzamide
(GP
IIA).
N-(tert-
butyl)benzamide 1 (0.25 mmol, 1.0 equiv) was taken in a 12.0
mL screw capped reaction tube, and 1.0 mL of anhydrous 1,2-
dichloroethane was added. Then alkyne 2 (0.33 mmol, 1.3
equiv), catalyst Cp*Co(CO)I2 (6.0 mg, 0.0125 mmol, 5.0 mol
%), AgBF4 (7.3 mg, 0.0375 mmol, 15.0 mol %) and
Cu(OAc)2·H2O (7.5 mg, 0.0375 mmol, 15.0 mol %) were added
to the reaction mixture. The resultant reaction mixture was
allowed to stir at 100 °C for 12 h. After completion of the reac-
tion as indicated by TLC, the crude product was directly pu-
N-(tert-butyl)-4-cyanobenzamide (1f). The title compound
1f was synthesized according to the GP I and isolated as white
1
solid (1.37 g, 68%). H NMR (600 MHz, CDCl3): δ (ppm) 7.80
(d, J = 8.3 Hz, 2H), 7.70 (d, J = 8.3 Hz, 2H), 5.98 (br s, 1H), 1.47
(s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 165.2, 140.0,
132.5, 127.6, 118.2, 114.8, 52.3, 28.9.
N-(tert-butyl)-4-nitrobenzamide (1g). The title compound
1g was synthesized according to the GP I and isolated as
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white solid (1.73 g, 78%). 1H NMR (400 MHz, CDCl3): δ (ppm)
8.24 (d, J = 8.5 Hz, 2H), 7.86 (d, J = 8.5 Hz, 2H), 6.02 (br s,
1H), 1.48 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm) 165.0,
149.4, 141.7, 128.1, 123.9, 52.4, 28.9.
isolated as white solid (1.93 g, 82 %). IR (KBr): 3277, 2983,
1
2955, 1723, 1635, 1536 cm-1. H NMR (400 MHz, CDCl3): δ
1
2
3
4
5
6
(ppm) 8.28 (s, 1H), 8.10 (d, J = 7.6 Hz, 1H), 7.97 (d, J = 7.5 Hz,
1H), 7.48 (t, J = 7.6 Hz, 1H), 6.07 (br s, 1H), 3.92 (s, 3H), 1.47
(s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm) 166.6, 166.0,
136.4, 132.1, 131.8, 130.4, 128.9, 127.4, 52.5, 52.0, 29.0. LCMS
(ESI): calculated for C13H18NO3 ([M+H]+): 236.1; found 236.3.
Methyl 4-(tert-butylcarbamoyl)benzoate (1h). The title
compound 1h was synthesized according to the GP I and
1
isolated as white solid (1.98 g, 84 %). H NMR (400 MHz,
7
8
9
CDCl3): δ (ppm) 8.03 (d, J = 7.8 Hz, 2H), 7.75 (d, J = 8.2 Hz,
2H), 6.06 (s, 1H), 3.91 (s, 3H), 1.46 (s, 9H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 166.5, 166.2, 140.0, 132.4, 129.8, 126.9, 52.4,
52.0, 28.9.
N-(tert-butyl)-3-(trifluoromethyl)benzamide (1q). The title
compound 1q was synthesized according to the GP I and
isolated as white solid (1.76 g, 72%). H NMR (600 MHz,
CDCl3): δ (ppm) 7.97 (s, 1H), 7.89 (d, J = 7.8 Hz, 1H), 7.72 (d, J
= 7.7 Hz, 1H), 7.54 (t, J = 7.8 Hz, 1H), 5.98 (s, 1H), 1.48 (s, 9H).
13C NMR (150 MHz, CDCl3): δ (ppm) 165.61, 136.85, 131.15 (q, J
= 33 Hz), 130.17, 129.25, 127.83 (q, J = 3.6 Hz), 123.894 (q, J =
270.9 Hz), 123.894 (q, J = 3.8 Hz), 52.17, 28.93.
1
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-(tert-butyl)-4-methoxybenzamide (1i). The title com-
pound 1i was synthesized according to the GP I and isolated
1
as white solid (1.76 g, 85%). H NMR (400 MHz, CDCl3): δ
(ppm) 7.68 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 8.4 Hz, 2H), 5.88
(br s, 1H), 3.83 (s, 3H), 1.46 (s, 9H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 166.7, 162.0, 128.6, 128.3, 113.8, 55.5, 51.6, 29.1.
N-(tert-butyl)-2-fluorobenzamide: (1r). The title compound
1r was synthesized according to the GP I and isolated as
white solid (1.6 g, 82%). 1H NMR (600 MHz, CDCl3): δ (ppm)
8.05-8.02 (m 1H), 7.43-7.40 (m, 1H), 7.24-721 (m, 1H), 7.09-
7.05 (m, 1H), 6.58 (d, J = 10.4 Hz, 1H), 1.46 (s, 9H). 13C NMR
(150 MHz, CDCl3): δ (ppm) 162.42 (d, J = 3.3 Hz), 160.51 (d, J =
244.5 Hz), 132.94 (d, J = 9.3 Hz), 131.91, 124.84 (d, J = 3.0 Hz),
122.44 (d, J = 11.7 Hz), 116.0 (d, J = 25.5 Hz), 51.88, 28.99.
N-(tert-butyl)-4-methylbenzamide (1j). The title compound
1j was synthesized according to the GP I and isolated as
white solid (1.43 g, 75%). 1H NMR (400 MHz, CDCl3): δ (ppm)
7.61 (d, J = 7.7 Hz, 2H), 7.19 (d, J = 7.6 Hz, 2H), 5.94 (br s, 1H),
2.37 (s, 3H), 1.46 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm)
166.9, 141.5, 133.1, 129.2, 126.8, 51.6, 29.0, 21.5.
2-Bromo-N-(tert-butyl)benzamide (1s). The title compound
1s was synthesized according to the GP I and isolated as
N-(tert-butyl)-3,4-dimethoxybenzamide (1k). The title com-
pound 1k was synthesized according to the GP I and isolated
1
1
white solid (2.05 g, 80%). H NMR (600 MHz, CDCl3): δ
as white solid (1.52 g, 64%). H NMR (400 MHz, CDCl3): δ
(ppm) 7.55 (d, J = 8.0 Hz, 1H), 7.48 (dd, J = 7.6, 1.1 Hz, 1H),
7.34-7.31 (m, 1H), 7.24-7.22 (m, 1H), 5.73 (br s, 1H), 1.47 (s,
9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 167.1, 139.2, 133.3,
131.0, 129.4, 127.6, 119.3, 52.4, 28.9.
(ppm) 7.38 (s, 1H), 7.17 (d, J = 8.1 Hz, 1H), 6.78 (d, J = 8.1 Hz,
1H), 5.98 (br s, 1H), 3.87 (s, 3H), 3.865 (s, 3H), 1.43 (s, 9H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 166.5, 151.4, 148.9, 128.5,
118.9, 110.5, 110.1, 56.00, 55.98, 51.6, 28.9.
N-(tert-butyl)-1-naphthamide (1t). The title compound 1t
N-(tert-butyl)-3-methoxybenzamide (1l). The title com-
pound 1l was synthesized according to the GP I and isolated
was synthesized according to the GP I and isolated as white
1
1
solid (1.84 g, 81%). H NMR (400 MHz, CDCl3): δ (ppm) 8.26
as white solid (1.68 g, 81%). H NMR (400 MHz, CDCl3): δ
(d, J = 7.9 Hz, 1H), 7.86 (t, J = 8.1 Hz, 2H), 7.56-7.21 (m, 3H),
7.43 (t, J = 7.4 Hz, 1H), 5.83 (br s, 1H), 1.53 (s, 9H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 169.3, 136.1, 133.8, 130.2, 130.1,
128.4, 127.1, 126.4, 125.4, 124.9, 124.5, 52.2, 29.0.
(ppm) 7.32-7.27 (m, 2H), 7.20 (d, J = 7.3 Hz, 1H), 7.00 (d, J =
7.8 Hz, 1H), 5.95 (br s, 1H), 3.84 (s, 3H), 1.46 (s, 9H). 13C NMR
(100 MHz, CDCl3) δ (ppm) 166.8, 159.9, 137.5, 129.5, 118.5, 117.5,
112.3, 55.6, 51.8, 29.0.
N-Cyclohexylbenzamide (1u). The title compound 1u was
synthesized according to the GP I and isolated as white solid
(1.75 g, 86%). 1H NMR (400 MHz, CDCl3): δ (ppm) 7.75 (d, J =
7.7 Hz, 2H), 7.49-7.45 (m, 1H), 7.42-7.39 (m, 2H), 6.06 (s, 1H),
4.02-3.92 (m, 1H), 2.04-2.01 (m, 2H), 1.77-1.73 (m, 2H), 1.66-
1.63 (m, 1H), 1.47-1.37 (m, 2H), 1.28-1.18 (m, 3H). 13C NMR (100
MHz, CDCl3): δ (ppm) 166.8, 135.1, 131.2, 128.5, 127.0, 48.8,
33.2, 25.6, 25.0.
N-(tert-butyl)-3-methylbenzamide (1m). The title com-
pound 1m was synthesized according to the GP I and isolated
1
as white solid (1.36 g, 71%). H NMR (400 MHz, CDCl3): δ
(ppm) 7.54 (s, 1H), 7.49-7.47 (m, 1H), 7.31-7.27 (m, 2H), 5.94
(br s, 1H), 2.38 (s, 3H), 1.47 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 167.4, 138.4, 136.0, 131.9, 128.5, 127.6, 123.8,
51.7, 29.00, 21.5.
N-(tert-butyl)-3-chlorobenzamide (1n). The title compound
1n was synthesized according to the GP I and isolated as
white solid (1.6 g, 76%). 1H NMR (400 MHz, CDCl3): δ (ppm)
7.68 (s, 1H), 7.57 (d, J = 7.6 Hz, 1H), 7.42 (d, J = 7.5 Hz, 1H),
7.34-7.31 (m, 1H), 5.95 (s, 1H), 1.46 (s, 9H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 165.7, 137.8, 134.7, 131.2, 129.9, 127.2, 125.0,
52.0, 28.9.
N4,N4'-di-tert-butyl-[1,1'-biphenyl]-4,4'-dicarboxamide (1w).
The title compound 1w was synthesized according to the GP
I and isolated as white solid (0.5 mmol scale, 68 mg, 56%). IR
1
(KBr): 3283, 2965, 1610, 1640, 1543, 1492 cm-1. H NMR (600
MHz, CDCl3): δ (ppm) 7.80 (d, J = 8.1 Hz, 4H), 7.64 (d, J = 8.1
Hz, 4H), 5.98 (s, 2H), 1.49 (s, 18H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 166.6, 142.9, 135.3, 127.5, 127.4, 51.9, 29.1.
HRMS (ESI): calculated for C22H29N2O2 ([M+H]+): 353.2224;
found 353.2237.
N-(tert-butyl)-3-nitrobenzamide (1o). The title compound
1o was synthesized according to the GP I and isolated as
white solid (1.55 g, 70%). 1H NMR (400 MHz, CDCl3): δ (ppm)
8.50 (s, 1H), 8.29 (d, J = 8.1 Hz, 1H), 8.09 (d, J = 7.7 Hz, 1H),
7.59 (t, J = 7.9 Hz, 1H), 6.14 (br s, 1H), 1.48 (s, 9H). 13C NMR
(100 MHz, CDCl3): δ (ppm) 164.6, 148.2, 137.6, 133.2, 129.8,
125.8, 121.7, 52.4, 28.9.
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)benzamide (3a). The
title compound 3a was synthesized according to the GP IIA
and the crude product was purified by using 10:90 ethylacte-
tate/hexane eluent. The product 3a was isolated as white
solid (56 mg, 63%) and in a second fraction the product 4a
was also isolated as white solid (25 mg, 19%). mp 124-126 °C.
Methyl 3-(tert-butylcarbamoyl)benzoate (1p). The title
compound 1p was synthesized according to the GP I and
1
IR (KBr): 3292, 2965, 1629, 1535, 1452, 1261 cm-1. H NMR (400
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The Journal of Organic Chemistry
MHz, CDCl3): δ (ppm) 7.58-7.55 (m, 1H), 7.36-7.32 (m, 2H),
132.6, 130.9, 130.4, 129.5, 129.2, 128.8, 128.3, 128.2, 127.7, 118.2,
7.24-7.10 (m, 11H), 6.75 (s, 1H), 5.72 (br s, 1H), 1.21 (s, 9H). 13C
NMR (100 MHz, CDCl3): δ (ppm) 168.8, 142.2, 141.4, 139.8,
137.6, 137.3, 131.1, 131.0, 130.5, 129.6, 129.5, 128.5, 128.4, 128.2,
127.7, 127.6, 127.1, 51.6, 28.7. HRMS (ESI): calculated for
C25H26NO ([M+H]+): 356.2009; found 356.2008.
113.4, 52.2, 28.6. HRMS (ESI): calculated for C26H25N2O
([M+H]+): 381.1961; found 381.1975.
1
2
3
4
5
6
7
8
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-4-nitrobenzamide
(3f). The title compound 3f was synthesized according to the
GP IIA and the crude product was purified by using 10:90
ethylactetate/hexane eluent. The product 3f was isolated as
light yellow solid (68 mg, 68%) and in a second fraction the
product 4g was also isolated as yellow solid (33.5 mg, 23%).
mp 128-130 °C. IR (KBr): 3274, 3060, 2969, 1633, 1523, 1349 cm-
1. 1H NMR (600 MHz, CDCl3): δ (ppm) 8.16 (dd, J = 8.4, 1.7 Hz,
1H), 8.09 (d, J = 1.6 Hz, 1H), 7.69 (d, J = 8.4 Hz, 1H), 7.27-7.26
(m, 3H), 7.18 (s, 5H), 7.11-7.10 (m, 2H), 6.80 (s, 1H), 5.68 (br s,
1H), 1.22 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 166.9,
148.3, 144.0, 143.1, 139.3, 138.7, 136.4, 132.7, 130.4, 129.6, 128.8,
128.3, 128.3, 127.8, 125.9, 122.4, 52.3, 28.6. HRMS (ESI): calcu-
lated for C25H25N2O3 ([M+H]+): 401.1860; found 401.1862.
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-4-fluorobenzamide
(3b). The title compound 3b was synthesized according to
the GP IIA. The crude product was purified by using 10:90
ethylactetate/hexane eluent. The product 3b was isolated as
white solid (54.4 mg, 60%) and in a second fraction the
product 4b was also isolated as white solid (7 mg, 5%). mp
146-148 °C. IR (KBr): 2924, 2854, 1737, 1634, 1539, 1456 cm-1. 1H
NMR (600 MHz, CDCl3): δ (ppm) 7.57 (dd, J = 8.3, 6.0 Hz,
1H), 7.24-7.23 (m, 3H), 7.17-7.16 (m, 5H), 7.10-7.09 (m, 2H),
7.02 (td, J = 8.3, 2.1 Hz, 1H), 6.92 (dd, J = 9.5, 2.0 Hz, 1H), 6.76
(s, 1H), 5.70 (s, 1H), 1.20 (s, 9H). 13C NMR (150 MHz, CDCl3): δ
(ppm) 167.9, 163.0 (d, J = 249.9 Hz), 144.8 (d, J = 7.8 Hz), 140.3
(d, J = 1.1 Hz), 139.2, 136.8, 133.8 (d, J = 3.2 Hz), 131.70, 130.68
(d, J = 8.6 Hz), 130.4, 129.5, 128.6, 128.3, 128.0, 127.5, 117.8 (d, J
= 21.7 Hz), 114.6 (d, J = 21.3 Hz), 51.7, 28.7. HRMS (ESI): calcu-
lated for C25H25FNO ([M+H]+): 374.1915; found 374.1935.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-4,5-
dimethoxybenzamide (3g). The title compound 3g was syn-
thesized according to the GP III. The crude product was puri-
fied by using 20:80 ethylactetate/hexane eluent and isolated
as white solid (52.8 mg, 51%). mp 156-158 °C. IR (KBr): 3385,
2970, 1663, 1594, 1498, 1451 cm-1. 1H NMR (600 MHz, CDCl3): δ
(ppm) 7.23-7.22 (m, 3H), 7.19-7.16 (m, 6H), 7.14-7.13 (m, 2H),
6.75 (s, 1H), 6.65 (s, 1H), 6.00 (s, 1H), 3.94 (s, 3H), 3.81 (s, 3H),
1.20 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 167.9, 149.8,
148.4, 141.2, 139.4, 137.1, 135.0, 131.2, 130.3, 129.5, 129.4, 128.5,
128.3, 127.9, 127.3, 113.7, 112.1, 56.3, 56.2, 51.6, 28.6. HRMS (ESI):
calculated for C27H30NO3 ([M+H]+): 416.2220; found 416.2221.
(E)-N-(tert-butyl)-5-chloro-2-(1,2-diphenylvinyl)benzamide
(3c). The title compound 3c was synthesized according to the
GP IIA and the crude product was purified by using 10:90
ethylactetate/hexane eluent. The product 3c was isolated as
white solid (61.5 mg, 63%) and in a second fraction the prod-
uct 4c was also isolated as white solid (27 mg, 19%). mp 186-
1
190 °C. IR (KBr): 2966, 3286, 1632, 1591, 1541, 1446 cm-1. H
NMR (600 MHz, CDCl3): δ (ppm) 7.52 (d, J = 8.3 Hz, 1H), 7.31
(dd, J = 8.3, 1.7 Hz, 1H), 7.24-7.22 (m, 4H), 7.17-7.16 (m, 5H),
7.10-7.09 (m, 2H), 6.75 (s, 1H), 5.70 (br s, 1H), 1.19 (s, 9H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 167.7, 144.0, 140.3, 139.1,
136.8, 136.0, 135.5, 131.8, 130.9, 130.4, 130.0, 129.5, 128.6, 128.3,
128.0, 127.8, 127.5, 51.8, 28.7. HRMS (ESI): calculated for
C25H25ClNO ([M+H]+): 390.1619; found 390.1618.
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-5 methylbenzamide
(3h). The title compound 3h was synthesized according to
the GP III. The crude product was purified by using 10:90
ethylactetate/hexane eluent and the product 3h was isolated
as white solid (56.5 mg, 61%). In a second fraction the corre-
sponding dialkenylated product was also isolated as white
solid (10 mg, 7%). mp 116-118 °C. IR (KBr): 3249, 3056, 2966,
1
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-4-
1630, 1545, 1447 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
(trifluoromethyl)benzamide (3d). The title compound 3d was
synthesized according to the GP IIA and the crude product
was purified by using 10:90 ethylactetate/hexane eluent. The
product 3d was isolated as white solid (65.4 mg, 62%) and in
a second fraction the product 4e was also isolated as white
solid (9 mg, 6%). mp 160-164 °C. IR (KBr): 3296, 2927, 2968,
7.49 (d, J = 7.8 Hz, 1H), 7.22-7.21 (m, 3H), 7.19-7.17 (m, 2H),
7.16-7.13 (m, 4H), 7.11-7.10 (m, 2H), 7.04 (s, 1H), 6.73 (s, 1H),
5.76 (br s, 1H), 2.33 (s, 3H), 1.20 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 168.7, 142.2, 141.7, 139.8, 139.7, 137.3, 134.8,
131.7, 130.8, 130.5, 129.5, 128.7, 128.4, 128.4, 128.2, 127.7, 127.1,
51.5, 28.7, 21.4. HRMS (ESI): calculated for C26H28NO
([M+H]+): 370.2165; found 370.2176.
1
1637, 1542, 1327 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
7.66 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.50 (s, 1H),
7.24-7.23 (m, 3H), 7.17 (s, 5H), 7.11-7.10 (m, 2H), 6.77 (s, 1H),
5.67 (s, 1H), 1.20 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm)
167.5, 143.0, 140.8, 140.2, 139.0, 136.8, 132.1, 131.65 (q, J = 32.4
Hz), 130.5, 129.6, 129.0, 128.6, 128.3, 128.1, 127.9, 127.9 (q, J = 3.7
Hz), 127.6, 124.5 (q, J = 3.7 Hz), 52.0, 28.6. HRMS (ESI): calcu-
lated for C26H25F3NO ([M+H]+): 424.1883; found 424.1885.
(E)-N-(tert-butyl)-5-chloro-2-(1,2-diphenylvinyl)benzamide
(3i). The title compound 3i was synthesized according to the
GP III. The crude product was purified by using 10:90
ethylactetate/hexane eluent and the product 3i was isolated
as white solid (73 mg, 75%). In a second fraction the corre-
sponding dialkenylated product was also isolated as white
solid (15.5 mg, 11%). mp 162-164 °C. IR (KBr): 3279, 3054, 2970,
1628, 1541, 1454 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.53
(d, J = 2.0 Hz, 1H), 7.32 (dd, J = 8.3, 2.1 Hz, 1H), 7.23-7.22 (m,
3H), 7.17-7.15 (m, 6H), 7.10-7.08 (m, 2H), 6.73 (s, 1H), 5.67 (br
s, 1H), 1.20 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 167.4,
140.7, 140.2, 139.5, 139.0, 137.0, 133.6, 132.5, 131.4, 130.5, 129.6,
129.6, 129.5, 128.5, 128.2, 127.9, 127.4, 51.9, 28.6. HRMS (ESI):
calculated for C25H25ClNO ([M+H]+): 390.1619; found
390.1634.
(E)-N-(tert-butyl)-4-cyano-2-(1,2-diphenylvinyl)benzamide
(3e). The title compound 3e was synthesized according to the
GP IIA and the crude product was purified by using 10:90
ethylactetate/hexane eluent. The product 3e was isolated as
white solid (62.0 mg, 65%) and in a second fraction the
product 4f was also isolated as white solid (5.8 mg, 4%). mp
106-108 °C. IR (KBr): 3285, 2967, 2927, 2230, 1633, 1544 cm-1.
1H NMR (600 MHz, CDCl3): δ (ppm) 7.63-7.58 (m, 2H), 7.50
(s, 1H), 7.27-7.24 (m, 3H), 7.17-7.14 (m, 5H), 7.10-7.08 (m, 2H),
6.76 (s, 1H), 5.70 (br s, 1H), 1.21 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 167.1, 143.4, 141.5, 139.1, 138.8, 136.5, 134.6,
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-5-nitrobenzamide
(3j). The title compound 3j was synthesized according to the
GP III. The crude product was purified by using 15:85 ethylac-
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tetate/hexane eluent and isolated as light yellow solid (68
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-1-naphthamide (3o).
The title compound 3o was synthesized according to the GP
1
mg, 68%). IR (KBr): 3406, 3272, 2924, 1631, 1521, 1343 cm-1. H
1
2
3
4
5
6
7
8
9
NMR (600 MHz, CDCl3): δ (ppm) 8.37 (d, J = 2.4 Hz, 1H), 8.18
(dd, J = 8.5, 2.4 Hz, 1H), 7.40 (d, J = 8.5 Hz, 1H), 7.27-7.24 (m,
3H), 7.18-7.15 (m, 5H), 7.11-7.09 (m, 2H), 6.81 (s, 1H), 5.69 (br
s, 1H), 1.23 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 166.6,
149.0, 146.8, 139.6, 138.9, 138.8, 136.4, 132.9, 132.2, 130.5, 129.6,
128.8, 128.3, 128.3, 127.9, 124.2, 123.6, 52.2, 28.6. HRMS (ESI):
calculated for C25H25N2O3 ([M+H]+): 401.1860; found 401.1875.
III. The crude product was purified by using 10:90 ethylacte-
tate/hexane eluent and isolated as white solid (54 mg, 53%).
IR (KBr): 3419, 2959, 2922, 1666, 1509, 1452 cm-1. 1H NMR (600
MHz, CDCl3): δ (ppm) 8.08 (d, J = 8.4 Hz, 1H), 7.81 (d, J = 8.1
Hz, 1H), 7.72 (d, J = 8.6 Hz, 1H), 7.57-7.55 (m, 1H), 7.51-7.49
(m, 1H), 7.26-7.23 (m, 6H), 7.16-7.10 (m, 5H), 6.98 (s, 1H), 5.73
(br s, 1H), 1.35 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm)
168.7, 140.5, 140.3, 138.6, 137.2, 135.0, 132.6, 132.1, 130.6, 130.4,
129.8, 128.7, 128.5, 128.1, 127.7, 127.6, 127.6, 127.3, 127.1, 126.4,
125.7, 52.3, 28.9. HRMS (ESI): calculated for C29H28NO
([M+H]+): 406.2165; found 406.2165.
(E)-Methyl
3-(tert-butylcarbamoyl)-4-(1,2-diphenylvinyl)
benzoate (3k). The title compound 3k was synthesized ac-
cording to the GP III. The crude product was purified by us-
ing 15:85 ethylactetate/hexane eluent and isolated as white
solid (82.5 mg, 80%). mp 190-194 °C. IR (KBr): 3273, 3055,
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(E)-N-Cyclohexyl-2-(1,2-diphenylvinyl)benzamide (3p). The
title compound 3p was synthesized according to the GP IIA
and the crude product was purified by using 10:90 ethylacte-
tate/hexane eluent. The product 3p was isolated as white
solid (52.4 mg, 55%) and in a second fraction the correspond-
ing dihydroarylated product was also isolated as white solid
(15.5 mg, 11%). IR (KBr): 2929, 2372, 2342, 1738, 1526, 1442 cm-
1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.53 (d, J = 7.5 Hz, 1H),
7.37 (t, J = 7.0 Hz, 1H), 7.33 (t, J = 7.4 Hz, 1H), 7.28 (d, J = 7.5
Hz, 1H), 7.22-7.21 (m, 3H), 7.18-7.12 (m, 5H), 7.09 (d, J = 6.6
Hz, 2H), 6.75 (s, 1H), 5.65 (d, J = 7.4 Hz, 1H), 3.66-3.62 (m,
1H), 1.75-1.73 (m, 2H), 1.64-1.51 (m, 4H), 1.11-1.07 (m, 1H), 0.99-
0.93 (m, 2H), 0.89-0.84 (m, 1H). 13C NMR (150 MHz, CDCl3): δ
(ppm) 168.6, 142.4, 141.5, 139.8, 137.2, 137.0, 133.1, 131.8, 131.0,
130.9, 130.6, 129.7, 129.6, 128.3, 128.2, 127.7, 127.2, 48.7, 33.0,
25.6, 24.8. HRMS (ESI): calculated for C27H28NO ([M+H]+):
382.2165; found 382.2165.
1
2961, 1724, 1624, 1543 cm-1. H NMR (600 MHz, CDCl3): δ
(ppm) 8.17 (d, J = 1.6 Hz, 1H), 7.99 (dd, J = 8.0, 1.6 Hz, 1H),
7.31 (d, J = 8.0 Hz, 1H), 7.23-7.21 (m, 3H), 7.17-7.15 (m, 5H),
7.10-7.09(m, 2H), 6.78 (s, 1H), 5.68 (br s, 1H), 3.93 (s, 3H), 1.21
(s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 168.0, 166.5,
147.1, 140.7, 139.4, 138.0, 136.9, 131.7, 131.3, 130.5, 130.4, 129.6,
129.4, 129.2, 128.5, 128.2, 127.9, 127.4, 52.4, 51.9, 28.7. HRMS
(ESI): calculated for C27H28NO3 ([M+H]+): 414.2064; found
414.2063.
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-5-(trifluoromethyl)
benzamide (3l). The title compound 3l was synthesized ac-
cording to the GP III. The crude product was purified by us-
ing 10:90 ethylactetate/hexane eluent and isolated as white
solid (37 mg, 36%). mp 192-196 °C. IR (KBr): 3286, 1720, 1629,
1542, 1494, 1457 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.81
(s, 1H), 7.59 (d, J = 7.9 Hz, 1H), 7.35 (d, J = 8.0 Hz, 1H), 7.25-
7.22 (m, 3H), 7.17 (s, 5H), 7.12-7.10 (m, 2H), 6.78 (s, 1H), 5.72
(s, 1H), 1.22 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm)
167.4, 145.8, 140.1, 139.2, 138.2, 136.7, 132.1, 131.6, 130.4, 129.79
(q, J = 33.0 Hz), 129.6, 128.7, 128.3, 128.1, 127.6, 126.2 (q, J = 3.6
Hz), 125.5 (q, J = 3.8 Hz), 123.9 (q, J = 272.2 Hz), 52.0, 28.7.
HRMS (ESI): calculated for C26H25F3NO ([M+H]+): 424.1883;
found 424.1882.
(E)-N-(tert-butyl)-2-(2-(naphthalen-2-yl)-1-
phenylvinyl)benzamide (3q). The title compound 3q was
synthesized according to the GP IIA and the crude product
was purified by using 10:90 ethylactetate/hexane eluent. The
product 3q was isolated as white solid (61.6 mg, 61%) and in a
second fraction the corresponding dihydroarylated product
was also isolated as white solid (11.3 mg, 7%). IR (KBr): 3056,
1
2966, 1656, 1506, 1446, 1364 cm-1. H NMR (600 MHz, CDCl3):
(E)-N-(tert-butyl)-2-(1,2-diphenylvinyl)-6-fluorobenzamide
(3m). The title compound 3m was synthesized according to
the GP IIB. The crude product was purified by using 10:90
ethylactetate/hexane eluent and isolated as white solid (57
mg, 61%). IR (KBr): 3291, 3056, 2966, 1640, 1542, 1450 cm-1. 1H
NMR (400 MHz, CDCl3): δ (ppm) 7.22-7.20 (m, 6H), 7.12 (s,
3H), 7.07-7.05 (m, 2H), 7.02-7.00 (m, 2H), 6.79 (s, 1H), 5.49
(br s, 1H), 1.22 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm)
163.8, 159.4 (d, J = 247.0 Hz), 144.9 (d, J = 3.4 Hz), 140.1 (d, J =
2.1 Hz), 140.0, 137.1, 131.3, 130.6, 130.0 (d, J = 8.9 Hz), 129.6,
128.5, 128.1, 127.6, 127.1, 126.5 (d, J = 2.9 Hz), 126.3 (d, J = 17.9
Hz), 114.7 (d, J = 22.5 Hz), 52.1, 28.8. HRMS (ESI): calculated
for C25H25FNO ([M+H]+): 374.1915; found 374.1927.
δ (ppm) 8.13 (d, J = 8.4 Hz, 1H), 7.85-7.84 (m, 2H), 7.49 (d, J =
7.3 Hz, 1H), 7.45-7.40 (m, 3H), 7.34 (t, J = 7.5 Hz, 1H), 7.24 (d,
J = 7.7 Hz, 1H), 7.21-7.17 (m, 1H), 7.13 (s, 1H), 7.07 (d, J = 7.9
Hz, 1H), 6.99-6.95 (m, 3H), 6.86 (d, J = 7.0 Hz, 2H), 5.79 (s,
1H), 1.31 (s, 9H). (major isomer). 13C NMR (150 MHz, CDCl3):
δ (ppm) 170.0, 142.2, 138.4, 138.0, 137.4, 136.9, 134.1, 133.8, 131.7,
130.5, 129.8, 129.3, 129.2, 128.7, 128.3, 128.2, 128.00, 127.98, 127.2,
127.1, 126.5, 126.0, 125.9, 51.8, 28.8 (major isomer). HRMS
(ESI): calculated for C29H27NNaO ([M+Na]+): 428.1985; found
428.1989. The regioselectivity was determined by cleaving the
alkene moiety of 3q.
(E)-methyl
3-(2-(tert-butylcarbamoyl)phenyl)-3-
phenylacrylate (3r). The title compound 3r was synthesized
according to the GP IIA and the crude product was purified
by using 20:80 ethylactetate/hexane eluent. The product 3r
was isolated as white solid (57 mg, 68%) and in a second
fraction the corresponding dihydroarylated product was also
isolated as white solid (5 mg, 4%). IR (KBr): 2964, 1710, 1662,
(E)-2-Bromo-N-(tert-butyl)-6-(1,2-diphenylvinyl)benzamide
(3n). The title compound 3n was synthesized according to
the GP IIB. The crude product was purified by using 10:90
ethylactetate/hexane eluent and isolated as white solid (54.4
mg, 50%). IR (KBr): 3293, 3054, 2965, 1639, 1537, 1445 cm-1. 1H
NMR (600 MHz, CDCl3): δ (ppm) 7.48 (dd, J = 7.7, 1.1 Hz, 1H),
7.25-7.24 (m, 3H), 7.22-7.20 (m, 2H), 7.14-7.11 (m, 4H), 7.10-
7.08 (m, 1H), 7.07-7.05 (m, 2H), 6.82 (s, 1H), 5.42 (br s, 1H),
1.27 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 166.7, 144.1,
140.2, 139.7, 139.0, 136.9, 131.8, 131.7, 130.4, 129.6, 129.6, 129.5,
128.6, 128.1, 127.7, 127.2, 120.4, 52.3, 28.7. HRMS (ESI): calcu-
lated for C25H25BrNO ([M+H]+): 434.1114; found 434.1111.
1
1528, 1450, 1362 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
7.64-7.62 (m, 1H), 7.44-7.42 (m, 2H), 7.36-7.30 (m, 5H), 7.10-
7.08 (m, 1H), 6.55 (s, 1H), 6.23 (s, 1H), 3.64 (s, 3H), 1.20 (s, 9H)
(major isomer). 13C NMR (150 MHz, CDCl3): δ (ppm) 168.1,
167.4, 139.0, 137.5, 136.8, 130.1, 129.8, 129.2, 128.8, 128.6, 128.5,
128.0, 127.9, 116.6, 51.7, 51.5, 28.5. (major isomer). HRMS (ESI):
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1
calculated for C21H23NNaO3 ([M+Na]+): 360.1570; found
360.1544.
(E)-N-(tert-butyl)-2-(1-phenylprop-1-en-2-yl)benzamide
1672, 1560, 1445 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
7.30-7.27 (m, 10H), 7.21 (s, 2H), 7.15-7.12 (m, 6H), 7.08-7.06
(m, 4H), 6.82 (s, 2H), 5.40 (br s, 1H), 1.01 (s, 9H). 13C NMR
(150 MHz, CDCl3): δ (ppm) 167.4, 144.3, 139.8, 139.5, 136.9,
136.5, 132.1, 131.9, 130.4, 129.6, 128.7, 128.1, 127.8, 127.2, 122.0,
51.9, 28.7. HRMS (ESI): calculated for C39H35BrNO ([M+H]+):
612.1897; found 612.1909.
1
2
3
4
5
6
7
8
(3s): The title compound 3s was synthesized according to the
GP IIA and the crude product was purified by using 10:90
ethylactetate/hexane eluent. The product 3s was isolated as
white solid (42.7 mg, 58%) and in a second fraction the cor-
responding dihydroarylated product was also isolated as
white solid (12.1 mg, 12%). IR (KBr): 2928, 2856, 1656, 1528,
1444, 1384 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.69 (dd,
J = 7.6, 1.2 Hz, 1H), 7.42-7.33 (m, 6H), 7.29-7.27 (m, 2H), 6.58
(s, 1H), 6.04 (s, 1H), 2.24 (d, J = 1.4 Hz, 3H), 1.36 (s, 9H) (ma-
jor isomer). 13C NMR (150 MHz, CDCl3): δ (ppm) 168.4, 143.6,
139.6, 137.5, 135.6, 130.2, 130.0, 129.1, 129.0, 128.9, 128.5, 127.6,
127.1, 51.6, 28.8, 20.7. (major isomer). HRMS (ESI): calculated
for C20H23NNaO ([M+Na]+): 316.1672; found 316.1678.
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-4-
(trifluoromethyl)benzamide (4e). The title compound 4e was
synthesized according to the GP III and the crude product
was purified by using 5:95 ethylactetate/hexane eluent. The
product 4e was isolated as white solid (100 mg, 66%) and in a
second fraction the product 3d was also isolated as white
solid (4.5 mg, 4%). IR (KBr): 3428, 2961, 2925, 1669, 1508, 1445
cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.33-7.27 (m, 12H),
7.17-7.13 (m, 6H), 7.09-7.08 (m, 4H), 6.84 (s, 2H), 5.41 (br s,
1H), 1.03 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) δ 167.1,
143.4, 140.4, 139.7, 139.6, 136.9, 132.2, 130.4 (q, J = 32.4), 130.3,
129.6, 128.8, 128.2, 127.9, 127.3, 126.1 (q, J = 3.7 Hz), 123.7 (q, J =
272.6 Hz), 52.1, 28.7. HRMS (ESI): calculated for C40H35F3NO
([M+H]+): 602.2665; found 602.2687.
9
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14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)benzamide (4a).
The title compound 4a was synthesized according to the GP
III. The crude product was purified by using 5:95 ethylacte-
tate/hexane eluent and isolated as white solid (109.0 mg,
82%). mp 168-172 °C. IR (KBr): 3410, 3057, 2968, 1669, 1506,
1
1449 cm-1. H NMR (600 MHz, CDCl3): δ (ppm) 7.31-7.28 (m,
N-(tert-butyl)-4-cyano-2,6-bis((E)-1,2-
4H), 7.27-7.25 (m, 5H), 7.20-7.17 (m, 2H), 7.15-7.06 (m, 12H),
6.84 (s, 2H), 5.47 (br s, 1H), 1.04 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 168.25, 142.36, 140.77, 140.61, 137.45, 137.35,
131.09, 130.41, 129.64, 129.41, 128.54, 128.06, 127.92, 127.50,
126.91, 51.76, 28.69. HRMS (ESI): calculated for C39H36NO
([M+H]+): 534.2791; found 534.2791.
diphenylvinyl)benzamide (4f). The title compound 4f was
synthesized according to the GP III and the crude product
was purified by using 5:95 ethylactetate/hexane eluent. The
product 4f was isolated as white solid (84 mg, 60%) and in a
second fraction the product 3e was also isolated as white
solid (20 mg, 21%). mp 226-228 °C. IR (KBr): 3357, 2960, 2233,
1
1672, 1520, 1447 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-4-
7.31-7.26 (m, 12H), 7.15-7.14 (m, 6H), 7.09-7.07 (m, 4H), 6.86
(s, 2H), 5.55 (br s, 1H), 1.05 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 166.6, 143.7, 141.1, 139.6, 138.7, 136.6, 132.6,
132.5, 130.3, 129.6, 128.9, 128.2, 128.1, 127.5, 118.2, 112.1, 52.3,
28.6. HRMS (ESI): calculated for C40H35N2O ([M+H]+):
559.2744; found 559.2736.
fluorobenzamide (4b). The title compound 4b was synthe-
sized according to GP III and the crude product was purified
by using 5:95 ethylactetate/hexane eluent. The product 4b
was isolated as white solid (98.0 mg, 71%) and in a second
fraction the product 3b was also isolated as white solid (3.5
1
mg, 3%). IR (KBr): 3430, 2964, 2921, 1666, 1585, 1495 cm-1. H
NMR (600 MHz, CDCl3): δ (ppm) 7.30-7.27 (m, 10H), 7.15-7.12
(m, 6H), 7.08-7.07 (m, 4H), 6.85 (s, 2H), 6.76 (d, J = 9.2 Hz,
2H), 5.44 (br s, 1H), 1.03 (s, 9H). 13C NMR (150 MHz, CDCl3): δ
(ppm) 167.6, 161.6 (d, J = 248.9 Hz), 144.8 (d, J = 7.9 Hz),
140.0, 139.8 (d, J = 1.4 Hz), 137.0, 131.6, 130.3, 129.7, 129.4 (d, J =
4.9 Hz), 128.7, 128.1, 127.8, 127.2, 116.2 (d, J = 21.5 Hz), 51.9,
28.7. HRMS (ESI): calculated for C39H35FNO ([M+H]+):
552.2697; found 552.2699.
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-4-
nitrobenzamide (4g). The title compound 4g was synthesized
according to the GP III and the crude product was purified
by using 5:95 ethylactetate/hexane eluent. The product 4g
was isolated as yellow solid (103 mg, 71%) and in a second
fraction the product 3f was also isolated as light yellow solid
(13 mg, 13%). IR (KBr): 3401, 3055, 2964, 1667, 1516, 1346 cm-1.
1H NMR (600 MHz, CDCl3): δ (ppm) 7.91 (s, 2H), 7.33-7.31 (m,
10H), 7.17-7.16 (m, 6H), 7.11-7.10 (m, 4H), 6.88 (s, 2H), 5.49 (br
s, 1H), 1.06 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 166.5,
147.2, 144.3, 142.6, 139.3, 138.7, 136.5, 132.6, 130.3, 129.6, 128.9,
128.2, 128.2, 127.5, 124.0, 52.3, 28.6. HRMS (ESI): calculated for
C39H35N2O3 ([M+H]+): 579.2642; found 579.2637.
N-(tert-butyl)-4-chloro-2,6-bis((E)-1,2-
diphenylvinyl)benzamide (4c). The title compound 4c was
synthesized according to the GP III and the crude product
was purified by using 5:95 ethylactetate/hexane eluent. The
product 4c was isolated as white solid (86.5 mg, 61%) and in
a second fraction the product 3c was also isolated as white
solid (6 mg, 6%). mp 152-156 °C. IR (KBr): 3411, 3055, 2966,
Methyl
4-(tert-butylcarbamoyl)-3,5-bis((E)-1,2-
diphenylvinyl)benzoate (4h). The title compound 4h was syn-
thesized according to the GP III. The crude product was puri-
fied by using 10:90 ethylactetate/hexane eluent and isolated
as white solid (121 mg, 82%). IR (KBr): 3391, 2970, 1717, 1665,
1
1668, 1567, 1505 cm-1. H NMR (600 MHz, CDCl3): δ (ppm)
7.30-7.27 (m, 10H), 7.16-7.13 (m, 6H), 7.09-7.07 (m, 6H), 6.84
(s, 2H), 5.43 (br s, 1H), 1.03 (s, 9H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 167.4, 144.2, 139.9, 139.6, 136.9, 136.0, 133.8,
131.8, 130.3, 129.6, 129.2, 128.7, 128.1, 127.8, 127.2, 51.9, 28.6.
HRMS (ESI): calculated for C39H35ClNO ([M+H]+): 568.2402;
found 568.2418.
1
1517, 1237 cm-1. H NMR (400 MHz, CDCl3): δ (ppm) 7.73 (s,
2H), 7.26-7.24 (m, 10H), 7.11-7.06 (m, 10H), 6.79 (s, 2H), 5.38
(br s, 1H), 3.80 (s, 3H), 1.01 (s, 9H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 167.4, 166.5, 142.8, 141.2, 140.0, 139.9, 137.1,
131.7, 130.4, 130.4, 129.8, 129.6, 128.6, 128.1, 127.8, 127.1, 52.4,
52.0, 28.7. HRMS (ESI): calculated for C41H38NO3 ([M+H]+):
592.2846; found 592.2864.
4-Bromo-N-(tert-butyl)-2,6-bis((E)-1,2-
diphenylvinyl)benzamide (4d). The title compound 4d was
synthesized according to the GP III. The crude product was
purified by using 5:95 ethylactetate/hexane eluent and isolat-
ed as white solid (125 mg, 82%). IR (KBr): 3420, 3022, 2971,
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-4-
methoxybenzamide (4i). The title compound 4i was synthe-
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Page 10 of 12
sized according to the GP III. The crude product was purified
127.8, 127.1, 51.7, 28.7, 21.43, 21.37. HRMS (ESI): calculated for
C43H44NO ([M+H]+): 590.3417; found 590.3431.
1
2
3
4
5
6
7
8
by using 10:90 ethylactetate/hexane eluent and isolated as
white solid (98 mg, 70%). IR (KBr): 3424, 2963, 1657, 1588,
1507, 1447 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.29-7.26
(m, 9H), 7.12-7.07 (m, 11H), 6.82 (s, 2H), 6.60 (s, 2H), 5.41 (br
s, 1H), 3.66 (s, 3H), 1.00 (s, 9H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 168.2, 158.7, 144.1, 140.8, 140.3, 137.3, 130.9, 130.9, 130.4,
129.6, 128.5, 128.1, 127.5, 126.9, 114.9, 55.4, 51.6, 28.7. HRMS
(ESI): calculated for C40H38NO2 ([M+H]+): 564.2897; found
564.2898.
2,6-Bis((E)-1,2-bis(4-fluorophenyl)vinyl)-N-(tert-
butyl)benzamide (4n). The title compound 4n was synthe-
sized according to the GP III and the crude product was puri-
fied by using 5:95 ethylactetate/hexane eluent. The product
4n was isolated as white solid (106 mg, 70%) and in a second
fraction the corresponding mono-hydroarylated product was
also isolated as white solid (11 mg, 11%). IR (KBr): 3433, 3058,
1
2967, 1665, 1599, 1506 cm-1. H NMR (600 MHz, CDCl3): δ
9
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-4-
(ppm) 7.25-7.20 (m, 4H), 7.05-7.03 (m, 7H), 6.97 (t, J = 8.6
Hz, 4H), 6.85 (t, J = 8.6 Hz, 4H), 6.76 (s, 2H), 5.46 (s, 1H), 1.05
(s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 168.2, 162.3 (d, J
= 246 Hz), 161.8 (d, J = 246 Hz), 142.0, 139.7 (d, J = 0.9 Hz),
137.4, 136.2 (d, J = 3.5 Hz), 133.2 (d, J = 3.3 Hz), 132.1 (d, J = 8.0
Hz), 131.2 (d, J = 7.9 Hz), 130.0, 129.5, 128.2, 115.7 (d, J = 21.3
Hz), 115.2 (d, J = 21.4 Hz), 51.9, 28.7. HRMS (ESI): calculated
for C39H32F4NO ([M+H]+): 606.2415; found 606.2429.
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methylbenzamide (4j). The title compound 4j was synthe-
sized according to the GP III. The crude product was purified
by using 5:95 ethylactetate/hexane eluent and isolated as
white solid (97 mg, 71%). IR (KBr): 3428, 2963, 1663, 1596,
1496, 1444 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.32-7.25
(m, 10H), 7.15-7.12 (m, 5H), 7.11-7.08 (m, 5H), 6.89 (s, 2H),
6.81 (s, 2H), 5.46 (br s, 1H), 2.21 (s, 3H), 1.03 (s, 9H). 13C NMR
(150 MHz, CDCl3): δ 168.4, 142.4, 141.0, 140.6, 137.7, 137.4,
135.0, 130.9, 130.4, 130.0, 129.6, 128.5, 128.0, 127.5, 126.8, 51.6,
28.7, 21.2. HRMS (ESI): calculated for C40H38NO ([M+H]+):
548.2948; found 548.2971.
2,6-Bis((E)-1,2-bis(4-chlorophenyl)vinyl)-N-(tert-
butyl)benzamide (4o). The title compound 4o was synthe-
sized according to the GP III and the crude product was puri-
fied by using 5:95 ethylactetate/hexane eluent. The product
4o was isolated as white solid (114 mg, 68%) and in a second
fraction the corresponding mono-hydroarylated product was
also isolated as white solid (13.9 mg, 13%). IR (KBr): 3422,
2963, 1721, 1663, 1586, 1489 cm-1. 1H NMR (600 MHz, CDCl3): δ
(ppm) 7.26-7.24 (m, 3H), 7.20-7.19 (m, 5H), 7.14-7.10 (m, 5H),
7.03-6.99 (m, 6H), 6.76 (s, 2H), 5.44 (s, 1H), 1.04 (s, 9H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 168.0, 141.7, 140.3, 138.5,
137.5, 135.4, 133.8, 133.0, 131.7, 130.8, 130.3, 129.6, 129.0, 128.6,
128.3, 52.0, 28.8. HRMS (ESI): calculated for C39H32Cl4NO
([M+H]+): 670.1233; found 670.1232.
N-(tert-butyl)-2,6-bis((E)-1,2-diphenylvinyl)-3-
methoxybenzamide (4k). The title compound 4k was synthe-
sized according to the GP III. The crude product was purified
by using 10:90 ethylactetate/hexane eluent and isolated as
white solid (113 mg, 80%). mp 192-194 °C. IR (KBr): 3422,
1
2963, 1665, 1494, 1447, 1287 cm-1. H NMR (600 MHz, CDCl3):
δ (ppm) 7.41 (d, J = 7.2 Hz, 2H), 7.28-7.26 (m, 5H), 7.22-7.16
(m, 4H), 7.14-7.09 (m, 7H), 7.07-7.02 (m, 3H), 6.87 (s, 1H),
6.77 (d, J = 8.6 Hz, 1H), 6.67 (s, 1H), 5.44 (br s, 1H), 3.59 (s,
3H), 1.04 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 167.9,
156.6, 141.1, 140.4, 140.3, 139.2, 137.5, 137.4, 134.3, 131.4, 130.89,
130.85, 130.5, 130.4, 130.2, 129.7, 129.6, 128.6, 128.4, 128.01,
127.96, 127.9, 127.4, 126.9, 126.8, 126.7, 111.6, 56.1, 51.7, 28.7.
HRMS (ESI): calculated for C40H38NO2 ([M+H]+): 564.2897;
564.2896.
2,6-Bis((E)-1,2-bis(4-bromophenyl)vinyl)-N-(tert-
butyl)benzamide (4p). The title compound 4p was synthe-
sized according to the GP III and the crude product was
purified by using 5:95 ethylactetate/hexane eluent. The
product 4p was isolated as white solid (128.4 mg, 60%) and in
a second fraction the corresponding mono-hydroarylated
product was also isolated as white solid (25.5 mg, 22%). IR
N-Cyclohexyl-2,6-bis((E)-1,2-diphenylvinyl)benzamide (4l).
The title compound 4l was synthesized according to the GP
III and the crude product was purified by using 5:95 ethylac-
tetate/hexane eluent. The product 4l was isolated as white
solid (53 mg, 38%) and in a second fraction the product 3p
was also isolated as white solid (20.2 mg, 21%). IR (KBr):
1
(KBr): 3427, 2966, 1659, 1566, 1500, 1446 cm-1. H NMR (600
MHz, CDCl3): δ (ppm) 7.42 (d, J = 8.2 Hz, 4H), 7.31 (d, J = 8.3
Hz, 4H), 7.15 (d, J = 8.3 Hz, 5H), 7.04 (d, J = 7.7 Hz, 2H), 6.96
(d, J = 8.3 Hz, 4H), 6.76 (s, 2H), 5.43 (s, 1H), 1.06 (s, 9H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 168.0, 141.6, 140.4, 138.9,
137.4, 135.8, 132.0, 131.9, 131.5, 131.1, 130.3, 129.6, 128.3, 122.0,
121.3, 52.0, 28.8. HRMS (ESI): calculated for C39H32Br4NO
([M+H]+): 845.9212; found 845.9231.
1
3428, 3053, 2925, 1658, 1494, 1444 cm-1. H NMR (600 MHz,
CDCl3): δ (ppm) 7.27-7.23 (m, 11H), 7.17-7.15 (m, 2H), 7.13-7.09
(m, 6H), 7.05 (d, J = 7.2 Hz, 4H), 6.81 (s, 2H), 5.22 (d, J = 7.1
Hz, 1H), 3.33-3.29 (m, 1H), 1.46-1.43 (m, 2H), 1.39-1.37 (m, 3H),
1.10-1.04 (m, 2H), 0.99-0.95 (m, 1H), 0.76-.071 (m, 2H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 168.0, 142.5, 140.9, 140.4,
137.3, 136.8, 131.1, 130.5, 129.6, 128.4, 128.2, 128.0, 127.5, 126.9,
48.6, 32.6, 25.6, 24.5. HRMS (ESI): calculated for C41H38NO
([M+H]+): 560.2948; found 560.2941.
Spectral data for mono-hydroarylated product (3t). IR
1
(KBr): 3415, 2924, 1720, 1653, 1586, 1511 cm-1. H NMR (600
MHz, CDCl3): δ (ppm) 7.47 (d, J = 7.3 Hz, 1H), 7.37-7.32 (m,
4H), 7.30 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 7.1 Hz, 1H), 7.03 (d, J
= 8.3 Hz, 2H), 6.95 (d, J = 8.3 Hz, 2H), 6.66 (s, 1H), 5.58 (s,
1H), 1.21 (s, 9H). 13C NMR (100 MHz, CDCl3): δ (ppm). δ 168.8,
141.9, 141.5, 138.5, 137.9, 136.0, 132.3, 131.6, 131.5, 131.1, 129.8,
129.7, 128.0, 121.9, 121.2, 51.7, 28.7. HRMS (ESI): calculated for
C25H24Br2NO ([M+H]+): 512.0219; found 512.0235.
N-(tert-butyl)-2,6-bis((E)-1,2-di-p-tolylvinyl)benzamide
(4m). The title compound 4m was synthesized according to
the GP III. The crude product was purified by using 5:95
ethylactetate/hexane eluent and isolated as white solid (105
mg, 71%). IR (KBr): 3428, 2924, 1720, 1661, 1508, 1451 cm-1. 1H
NMR (600 MHz, CDCl3): δ (ppm) 7.18-7.12 (m, 6H), 7.07-7.06
(m, 4H), 7.03-7.02 (m, 2H), 6.99-6.98 (m, 4H), 6.94-6.93 (m,
3H), 6.73 (s, 2H), 5.44 (s, 1H), 2.33 (s, 6H), 2.26 (s, 6H), 1.02 (s,
9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 168.4, 142.7, 139.9,
137.9, 137.5, 137.1, 136.5, 134.7, 130.6, 130.3, 129.5, 129.2, 128.8,
2,6-Bis((E)-1,2-bis(4-(trifluoromethyl)phenyl)vinyl)-N-(tert-
butyl)benzamide (4q). The title compound 4q was synthe-
sized according to the GP III. The crude product was purified
by using 5:95 ethylactetate/hexane eluent and isolated as
white solid (90 mg, 45%). IR (KBr): 3438, 2965, 1740, 1664,
1506, 1411 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.55 (d, J
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The Journal of Organic Chemistry
= 8.1 Hz, 4H), 7.44 (d, J = 8.2 Hz, 5H), 7.39 (d, J = 8.0 Hz, 4H),
2H), 7.10-7.04 (m, 3H), 6.90 (d, J = 7.0 Hz, 2H), 3.65-3.60 (m,
2H), 1.41 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm) 154.9,
147.5, 142.8, 135.0, 132.2, 130.89, 130.86, 128.61, 128.57, 127.8,
127.77, 126.79, 125.5, 123.9, 122.3, 91.8, 53.6, 47.0, 30.5. HRMS
(ESI): calculated for C25H26NO ([M+H]+): 356.2009; found
356.2003.
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7.17 (d, J = 8.1 Hz, 4H), 7.06 (d, J = 7.7 Hz, 2H), 6.94 (s, 2H),
5.49 (s, 1H), 1.04 (s, 9H). 13C NMR (150 MHz, CDCl3): δ (ppm).
167.9, 143.3, 141.6, 141.3, 140.1, 137.4, 131.0, 130.7, 130.1 (q, J = 32.7
Hz), 129.9, 129.7, 129.4 (q, J = 32.5 Hz), 128.6, 125.8 (q, J = 3.6
Hz), 125.4 (q, J = 3.7 Hz), 124.1 (q, J = 272.2 Hz), 52.14, 28.74.
HRMS (ESI): calculated for C43H32F12NO ([M+H]+): 806.2287;
found 806.2286.
ASSOCIATED CONTENT
Supporting Information
N-(tert-butyl)-2,6-bis((E)-1-phenylprop-1-en-1-yl)benzamide
(4r). The title compound 4r was synthesized according to the
GP III. The crude product was purified by using 10:90
ethylactetate/hexane eluent and isolated as mixture of three
possible isomers (combined yields, 86.3 mg, 84%). IR (KBr):
9
The Supporting Information is available free of charge on the
ACS Publications website.
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1
Experimental details, analytical data for all new compounds,
crystallographic data (3m and 4a), and NMR spectra (PDF).
3428, 2964, 1656, 1509, 1445, 1261 cm-1. H NMR (600 MHz,
CDCl3): δ (ppm) 7.37-7.28 (m, 19H), 7.25-7.22 (m, 6H), 7.17
(d, J = 7.6 Hz, 1H), 7.13- 7.11 (m, 0.6 H), 7.06 (d, J = 7.6 Hz,
1H), 6.96 (d, J = 7.7 Hz, 1H), 6.51 (s, 2H), 5.98-5.93 (m, 2H),
5.55 (s, 0.6H minor), 5.33 (s, 1H major), 5.22 (s, 0.45H minor),
2.28 (s, 3H), 2.26 (s, 3H), 1.86-1.83 (m, 6H), 1.28 (s, 6H minor),
1.19 (s, 9H major), 1.18 (s, 4H minor). 13C NMR (150 MHz,
CDCl3): δ (ppm) 168.6, 168.5, 168.4, 144.0, 143.8, 142.4, 142.1,
140.7, 140.4, 140.3, 140.1, 138.7, 138.6, 137.93, 137.88, 137.3, 136.2,
135.4, 130.1, 129.9, 129.6, 129.47, 129.45, 129.1, 129.09, 129.0,
128.7, 128.3, 128.13, 128.06, 127.7, 127.44, 127.35, 127.2, 127.1,
126.88, 126.85, 126.7, 51.6, 51.51, 51.49, 28.8, 28.69, 28.67, 20.6,
20.5, 15.8, 15.8. HRMS (ESI): calculated for C29H32NO
([M+H]+): 410.2478; found 410.2476.
AUTHOR INFORMATION
Corresponding Author
*E-mail: msm@chem.iitkgp.ernet.in
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
M.S.M. gratefully acknowledge SERB, Department of Science
and Technology, New Delhi, India (Sanction No.
EMR/2015/000994) and SRIC, IIT Kharagpur (ISIRD grant)
for funding. S.S.B. sincerely thanks CSIR India and S.D.
thanks IIT Kharagpur for fellowship.
N4,N4'-di-tert-butyl-3,3',5,5'-tetrakis((E)-1,2-diphenylvinyl)-
[1,1'-biphenyl]-4,4'-dicarboxamide (5). N4,N4'-di-tert-butyl-[1,1'-
biphenyl]-4,4'-dicarboxamide 1w (35.5 mg, 0.1 mmol, 1.0
equiv) was taken in a 10.0 mL screw capped reaction tube
and 1.0 mL of anhydrous 1,2-dichloroethane was added. Then
alkyne 2a (0.5 mmol, 5.0 equiv), Cp*Co(CO)I2 (9.5 mg, 0.02
mmol, 20.0 mol %), additive AgBF4 (11.6 mg, 0.06 mmol, 60.0
mol %) and Cu(OAc)2·H2O (6.0 mg, 0.03 mmol, 30.0 mol %)
were added to the reaction mixture. The resultant reaction
mixture was allowed to stir at 120 °C for 36 h. After comple-
tion of the reaction as indicated by TLC, the crude product
was purified by using 15:85 ethylactetate/hexane eluent and
isolated as white solid (25.4 mg, 24%). IR (KBr): 3428, 3054,
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2854, 1723, 1663, 1496 cm-1. H NMR (400 MHz, CDCl3): δ
(ppm) 7.29-7.24 (m, 24H), 7.14-7.07 (m, 20H), 6.80 (s, 4H),
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2H), 7.47-7.45 (m, 2H), 7.34 (t, J = 7.7 Hz, 2H), 7.33-7.27 (m,
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