Palladium-catalyzed regio- and chemoselective direct desulfitative arylation of anilides with arylsulfonyl chlorides

Article abstract of DOI:10.1016/j.tet.2017.07.022

A straightforward and practical palladium-catalyzed regioselective arylation of anilides is described. This method provides a new approach to prepare 2-aminobiaryls, which are valuable precursors for the synthesis of various N-containing heterocycles, using arylsulfonyl chlorides as readily available arylating agents.

Full text of DOI:10.1016/j.tet.2017.07.022

Accepted Manuscript
Palladium-catalyzed regio- and chemoselective direct desulfitative arylation of anilides
with arylsulfonyl chlorides
Ebrahim Kianmehr, Arezoo Tanbakouchian
PII:
S0040-4020(17)30746-9
10.1016/j.tet.2017.07.022
TET 28854
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 1 April 2017
Revised Date: 16 June 2017
Accepted Date: 11 July 2017
Please cite this article as: Kianmehr E, Tanbakouchian A, Palladium-catalyzed regio- and
chemoselective direct desulfitative arylation of anilides with arylsulfonyl chlorides, Tetrahedron (2017),
doi: 10.1016/j.tet.2017.07.022.
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Graphical Abstract
Palladium-catalyzed regio- and chemoselective direct
desulfitative arylation of anilides with arylsulfonyl chlorides
Leave this area blank for abstract info.
Ebrahim Kianmehr* and Arezoo Tanbakouchian
School of Chemistry, College of Science, University of Tehran, Tehran 1417614411, Iran

1
ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Palladium-catalyzed regio- and chemoselective direct desulfitative arylation of
anilides with arylsulfonyl chlorides
Ebrahim Kianmehr* and Arezoo Tanbakouchian
School of Chemistry, College of Science, University of Tehran, Tehran 1417614411, Iran
kianmehr@khayam.ut.ac.ir
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A straightforward and practical palladium-catalyzed regioselective arylation of anilides is
described. This method provides a new approach to prepare 2-aminobiaryls, which are valuable
precursors for the synthesis of various N-containing heterocyles, using arylsulfonyl chlorides as
readily available arylating agents.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
C-H bond activation
Arylation
Cross-coupling
Palladium
Arylsulfonyl chlorides
workers in 2014 (eq 2.).12b Ortho-arylation of pivanilide
derivatives with aryl iodides as coupling reagents was reported
by Cheng et al. in 2015 (eq. 3).12c A ruthenium catalyzed
arylation of acetanilides using bronic acid derivatives as coupling
partners was reported independently by Jeganmohan’s and
Ackermann’s groups in 2014 and 2015, respectively (eq 4.).12d,e
1. Introduction
The prevalence of biaryl moiety in natural and biologically
active compounds as well as advanced organic materials is
motive for finding efficient methods for the construction of this
structural
motif.1
Direct
transition
metal-catalyzed
functionalization of unreactive C-H bonds serves as a powerful
tool in organic synthesis.2 Direct C-H bond arylation through
transition metal-catalyzed reactions using various coupling
reagents such as arylboronic acids,3 organometallic reagents,4
aryl halides, aryl tosylates,5 (di)aryliodonium salts,6 benzoic
acids7 and arenes8 have been reported. In most cases, the
presence of a directing group to activate the target C-H bond
selectively is crucial and choosing the most beneficial directing
group is still the challenging part of a synthetic approach.9
Among the enormous number of directing groups introduced in
the last decades, carbonyl containing groups have received
special consideration. For example, acylamino groups are
beneficial directing groups to activate ortho C-H bonds of arenes
and are easily removed to attain anilines which are omnipresent
structural motifs found in many bioactive compounds.9a
Direct arylation of anilides with arenes has also been
reported.12f-i Yu and coworkers described Pd-catalyzed arylation
of pivanilides using arenes as both solvent and coupling reagent
(eq 5.).12h,i As part of our ongoing research program on the
development of efficient methods for direct functionalization of
C-H bonds, we turned our attention to the synthesis of 2-
arylanilides via a palladium catalyzed C-H bond activation
reaction. In comparison with the above-mentioned methods, an
appropriate economically favorable coupling partner is obviously
required. Among the coupling candidates, arylsulfonyl chlorides
could be the best choice because of their indisputable advantages.
Palladium-catalyzed C-H bond functionalization with
arylsulfonyl chlorides has been reported, recently.13 To the best
of our knowledge palladium-catalyzed desulfitative direct
arylation of arenes using arylsulfonyl chlorides as the coupling
partners has not received more attention. Towards addressing
these reports and in continuation of our interest in this area,14 we
wish to report the palladium-catalyzed regioselective direct
arylation of anilides with arylsulfonyl chlorides as the arylation
agent through C-H bond activation for the first time (Scheme 1).
2-Aminobiaryls have received particular attention due to their
applications in organic synthesis. They can be used as precursors
for synthetically important heterocycles such as carbazoles.10 In
addition to well-known coupling reactions such as Suzuki-
Miyaura,11a,b Kumada11c-e and Negishi reactions,11f the direct
regioselective coupling of anilides with various coupling partners
have been reported for the synthesis of this structural motif.12 As
shown in Scheme 1, in 2007, Shi and co-workers described direct
palladium catalyzed arylation of acetanilides with silyl reagents
(eq 1.).12a Palladium-catalyzed decarboxylative arylation of
anilides with acylperoxides was reported by Wang and co-

2
Tetrahedron
entry 17) and control experiments showed that no reaction
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occurred in the absence of catalyst (Table 1, entry 18). The effect
of ligand was also investigated and no improvement in yields was
observed in the presence of Ph3P, bipyridine, phenanthroline or
Et3N (Table S1, entries 1-4). Finally, upon decreasing the
reaction temperature from 140 to 120 °C, the yield of the reaction
decreased from 81 to 36 % (Table 1, entry 19).
Once the optimized conditions for the desired arylation
reaction were established, the scope of the reaction was
investigated (Scheme 2). Anilides with halo substituents (F, Cl,
Br) smoothly led to the corresponding arylated products in good
yields.
Table 1. Optimization of the Reaction Conditions[a]
Catalyst
(mol %)
additive
(equiv)
Yielda
(%)
entry
Solvent
1
2
PdCl2 (10)
PdCl2 (10)
Li2CO3 (2)
Li2CO3 (2)
1,4-dioxane
DCE
51
59b
3
4
5
PdCl2 (10)
PdCl2 (10)
PdCl2 (10)
Li2CO3 (2)
Li2CO3 (2)
Li2CO3 (2)
DME
DMF
CH3CN
43
-
-
6
PdCl2 (10)
PdCl2 (10)
Li2CO3 (2)
Li2CO3 (2)
Na2CO3(2)
K2CO3 (2)
Cs2CO3 (2)
LiCl (2)
PhCl
63
81
7
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
8
PdCl2 (10)
35
9
PdCl2 (10)
trace
trace
80
10
11
12
13
14
15
16
17
18
19
PdCl2 (10)
PdCl2 (10)
Scheme 1. Examples of anilide arylation
PdCl2 (10)
-
-
-
Li2CO3 (2)
LiCl (2)
-
PdCl2(MeCN)2 (10)
Pd(OAc)2 (10)
PdCl2(COD)2 (10)
PdCl2(PPh3)2(10)
PdCl2 (5)
43
2. Results and discussion
LiCl (2)
47
Our initial attempt toward this aim was started by an
investigation of the reaction between 4-methyl pivanilide (1a)
and p-toluenesulfonyl chloride (2a) as the model reaction (Table
1). To optimize the reaction parameters, the effects of different
catalysts, additives, solvents and temperature were examined. To
begin our initial trial the reaction between 1a and 2a in the
present of 10 mol% of PdCl2 as catalyst and 2 equivalents of
Li2CO3 as additive in 1,4-dioxane was considered and to our
delight, the desired product 3a was formed in 51% yield (Table
1, entry 1). Various solvents were screened to optimize the
reaction conditions (Table 1, entries 2-7, see also Table S1,
entries 8-10 in the Supporting Information). When the reaction
was carried out in DCE the yield slightly increased but the best
result was obtained in toluene with 81% yield (Table 1, entry 7).
The reaction was performed in the presence of different additives
and it was revealed that the role of the additive is crucial for this
transformation, and the formation of the desired product 3 is
strongly depended on the presence of lithium salts. As shown in
Table 1, the best results were obtained with Li2CO3 and LiCl
whereas Na2CO3, K2CO3 and Cs2CO3 were found to be inferior
(entries 7-11, see also Table S1, entries 6 and 7 in the Supporting
Information), and finally, no desired product was obtained in the
absence of additive (Table 1, entry 12). Other common palladium
catalysts such as Pd(OAc)2, PdCl2(CH3CN)2, PdCl2(COD)2 and
PdCl2(PPh3)2 were examined and no improvement in yields was
observed (Table 1, entries 13-16). Decreasing the amount of
catalyst from 10 to 5 mol% led to insufficient outcomes (Table 1,
LiCl (2)
54
LiCl (2)
31
LiCl (2)
69
36c
PdCl2 (10)
LiCl (2)
[a]
Reaction conditions: 1a (0.5 mmol), 2a (1.5 eq), additive (2 eq.) in
solvent (2.0 mL) were stirred at 140 °C for 48 h. b The ortho chlorinated
pivanilide was detected in 29% yield as the side product. The reaction
was carried out at 120 °C.
c
Given that these halogen substituents remained intact during
the reaction, they can enable additional functionalization at these
positions (3e, 3f, 3g and 3m). No remarkable electronic effect of
substituents at para or meta position of pivanilides was observed
but in general the presence of alkyl groups slightly enhanced the
yields. The presence of CF3 group on meta or para position of
anilide ring resulted in lower yields (3h and 3n). It is worth
noting that with pivanalides bearing strong electron-donating
groups, such as OMe, the corresponding chlorinated products
were obtained as the side products. Using meta-substituted
pivanilides, arylation occurred exclusively at the C-6 position of
the substrate with less steric hindrance (3j-3m). Unfortunately, 2-
substituted pivanalides did not afford the corresponding products
(3t). A series of functional groups on the phenyl ring of
arylsulfonyl chlorides, such as bromo, chloro, nitro, methyl were
compatible under this procedure, and the products were isolated
in good to high yields (3p-3s). High yields of 3 were obtained
from benzenesulfonyl chloride and arylsulfonyl chlorides

3
containing electron-withdrawing groups such as NO2 and Br. In
ACCEPTED MANUSCRIPT
O
addition to the acetamido group, other directing amido moieties
were tested in this ortho-arylation reaction. Phenyl moieties gave
slightly lower yield while other amido derivatives substituted
with Me, n-pentyl or CF3 had disappointing yields.
R1 NH
H
R1
HN
X
C-H
Activation
O
Scheme 2. Substrate Scopea
PdII
O
SO2Cl
2
PdIIX2
R1
NH
A
NHPiv
SO2Cl
NHPiv
PdCl2 (10 mol%)
Li2CO3 (2 eq.)
H
R1
R1
+
R2
Toluene, 140°C, 48h
R2
1
2
3
Ox. Ad.
NHPiv
NHPiv
NHPiv
NHPiv
Red. E.
O
O
S
R1
O
OMe
3d, 79%b
L
3a, 81%b
3b, 87%
3c, 86%
PdIV
HN
B
R1
O
X
L
NHPiv
NHPiv
NHPiv
NHPiv
PdIV
Cl
HN
X
Cl
SO2
C
F
Cl
Br
CF3
3e
3f
3g
, 84%
3h
, 71%
, 74%
, 77%
NHPiv
NHPiv
NHPiv
NHPiv
Scheme 3. Plausible mechanisms
MeO
NO2
3. Conclusion
3i, 79%
3j,85%
3k, 89%
3l, 75%b
In conclusion, we have developed the palladium-catalyzed
ortho arylation of anilide derivatives with arylsulfonyl chlorides
as the arylating source for the synthesis of 2-arylanilides. The
reaction is chemoselective and no over arylation was detected.
This method is well tolerated with both EDGs and EWGs
substituents on the both coupling partners. Moreover, the
directing group can easily removed16 and provides a simple and
practical route for producing the titled products, which could be
used as precursors in synthesis of valuable hetrocycles found in
pharmaceuticals, electronics industries and bioactive compounds.
NHPiv
NHPiv
NHPiv
NHPiv
F3C
MeO
OMe
b
3m, 67%
3n, 78%
3o
, 71%
3p
, 96%
Cl
Br
NO2
NHPiv
NHPiv
NHPiv
NHPiv
3t
, 0%
3s
, 93%
3q
3r
, 89%
, 86%
O
4. Experimental section
4.1. General
NHPiv
Cl
R
NH
4a: R1=Me, R2=H, 29%
5: R=Ph, 59%;
1
2
6
4d
: R= Me<5%
: R =OMe, R =H, 17%
R2
1
2
7: R=CF3, trace;
4l
: R =H, R =OMe, 15%
R1
8
1
2
: R=n-pentyl<5%
4o
: R , R =OMe, 21%
Solvents, palladium chloride (98%), aniline derivatives were
purchased from Merck. Other reagents were purchased from
commercial distributors and used without further purification.
Anilide derivatives were synthesized according to literature
procedures.11a Analytical thin layer chromatography (TLC) was
performed on precoated silica gel 60 F254 plates. The products
were purified by preparative column chromatography on silica
aReaction conditions: Pivanilide (0.5 mmol), p-toluenesulfonyl chloride
(1.5 equiv), Li2CO3 (2 equiv) in toluene (2.0 mL) were stirred at 140 °C for
48 h.bThe ortho-chlorinated product 4 was obtained as the side product.
Although the mechanism of this reaction has not been
established experimentally, on the basis of previous chemistry13,15
the catalytic cycle shown on Scheme 3 is proposed. Initially,
palladation occurs preferentially at the ortho position of the
anilide, likely via a concerted metallation-deprotonation step
which leads to the formation of palladacycle A. In the next step,
the oxidative addition of arenesulfonyl chloride to the
1
gel (0.063-0.200 mm; Merck). H and 13C-NMR Spectra: were
recorded on Bruker DRX 500 and 400 Advance instruments in
CDCl3 and DMSO-d6; δ in ppm, J in Hz. Mass spectrometry was
obtained on Agilent 5975C VL MSD (Ion source: EI+, 70eV, 230
°C).
intermediate
A
forms the Pd(IV) intermediate B. The
4.2. General Procedure for the Synthesis of 2-aryl anilides
intermediate B produces intermediate C with concomitant loss of
SO2 at a higher temperature, and in the next step, the reductive
elimination from the Pd(IV) complex affords the 2-aryl anilide
and regenerates Pd(II).
A 10 mL microwave vial was charged with the anilide
derivatives (1 equiv, 0.5 mmol), the arenesulfonyl chloride (1.5
equiv), PdCl2 (10 mol%), Li2CO3 (2 equiv) and toluene (2 mL).
The vial was then sealed and immersed in an oil bath, which was
preheated at 140 °C, for 48 h. After this time the reaction mixture
was cooled to room temperature and then diluted with DCM and
filtered. The residue was purified by using column
chromatography (n-hexane) to yield the desired products.

4
Tetrahedron
4.2.1. 1- N-(4',5-dimethyl-[1,1'-biphenyl] -2-yl)
198 (57), 168 (15), 57 (34). Anal. Calcd for C19H23NO2: C, 76.74;
ACCEPTED MANUSCRIPT
1 2 h
pivalamide (3a)1 1 a ,
H, 7.80; N, 4.71; found: C, 76.97; H, 7.85; N, 4.74.
The general procedure was followed using 4-methyl pivanilide
4.2.4. 2- N-(5-fluoro-4'-methyl-[1,1'-biphenyl] -
(95 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3a (114 mg, 81% yield) as white needle
(m.p.= 101–103 ºC, n-hexane). δH (400 MHz, CDCl3) 8.25 (1H,
d, J 8.5 Hz, =CH), 7.49 (1H, br, CONH), 7.33–7.26 (4H, m,
=CH), 7.19 (1H, dd, J 8.5, 2.0 Hz, =CH), 7.08 (1H, d, J 2.0 Hz,
=CH), 2.46 (3H, s, Me), 2.37 (3H, s, Me), 1.15 (9H, s, 3Me); δC
(100 MHz, CDCl3) 176.2, 137.7, 135.2, 133.4, 132.6, 132.2,
130.4, 129.6, 129.1, 128.7, 121, 39.7, 27.4, 21.2, 20.8; MS (IE)
m/z (relative intensity %) 281 (M+, 29), 233 (57), 197 (30), 119
(17), 105 (100), 57 (43). Anal. Calcd for C19H23NO: C, 81.10; H,
8.24; N, 4.98; found: C, 81.27; H, 8.29; N, 4.95.
2-yl) pivalamide (3e)
The general procedure was followed using 4-fluoro pivanilide
(97 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3e (105 mg, 74% yield) as colorless prism
(m.p.= 75–77 ºC, n-hexane). δH (400 MHz, CDCl3) 8.30 (1H, dd,
J 9.0, 5.5 Hz, =CH), 7.44 (1H, br, CONH), 7.32–7.34 (2H, m,
=CH), 7.28–7.25 (2H, m, =CH), 7.10–7.04 (1H, m, =CH), 6.98
(1H, dd, J 9.0, 3.0 Hz, =CH), 2.46 (3H, s, Me), 1.14 (9H, s,
3Me); δF (375 MHz, CDCl3) -118.71; δC (100 MHz, CDCl3)
176.3, 158.9 (d, J 244.0 Hz), 138.3, 134.2 (d, J 7.5 Hz), 134,
131.2 (d, J 2.0 Hz), 129.8, 128.9, 122.8 (d, J 8.5 Hz), 116.4 (d, J
22.5 Hz), 114.6 (d, J 22.0 Hz), 39.7, 27.4, 21.2; MS (IE) m/z
(relative intensity %) 285 (M+, 27), 201 (26), 167 (31), 149 (72),
71 (22), 57 (100), 43 (32), 41 (54). Anal. Calcd for C18H20FNO:
C, 75.76; H, 7.06; N, 4.91; found: C, 75.57; H, 7.10; N, 4.88.
4.2.2. N-(4'-methyl-[1,1'-biphenyl] -2-yl)
pivalamide (3b)1 2 c
The general procedure was followed using phenyl pivanilide
(88 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3b (116 mg, 87% yield) as a yellow oil; δH
(400 MHz, CDCl3) 8.42 (1H, dd, J 8.0, 1.0 Hz, =CH), 7.57 (1H,
br, CONH), 7.40–7.25 (6H, m, =CH), 7.18 (1H, td, J 7.5, 1.0 Hz,
=CH), 2.47 (3H, s, Me), 1.16 (9H, s, 3Me); δC (100 MHz, CDCl3)
176.3, 137.8, 135.2, 135, 132, 129.8, 129.7, 129.2, 128.3, 123.8,
120.79, 39.8, 27.4, 21.2; MS (IE) m/z (relative intensity %) 268
(M+1, 92), 267 (M+, 93), 183 (49), 167 (23), 149 (20), 57 (100),
41 (37). Anal. Calcd for C18H21NO: C, 80.86; H, 7.92; N, 5.24;
found: C, 80.65; H, 7.88; N, 5.28.
4.2.5. N-(5-chloro-4'-methyl-[1,1'-biphenyl] -2-
yl) pivalamide (3f)1 2 h
The general procedure was followed using 4-chloro pivanilide
(106 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3f (116 mg, 77% yield) as off-white needle
(m.p.= 102–104 ºC, n-hexane). δH (400 MHz, CDCl3) 8.36 (1H,
d, J 9.0 Hz, =CH), 7.53 (1H, br, CONH), 7.37–7.28 (3H, m,
=CH), 7.25–7.22 (3H, m, =CH), 2.45 (3H, s, Me), 1.13 (9H, s,
3Me); δC (125 MHz, CDCl3) 176.2, 138.4, 133.8, 133.7, 133.5,
129.8, 129.5, 128.9, 128.6, 128, 121.9, 39.7, 27.3, 21.1; MS (IE)
m/z (relative intensity %) 303 (M+2, 45), 301 (M+, 100), 217
(81), 180 (26), 57 (72). Anal. Calcd for C18H20ClNO: C, 71.63;
H, 6.68; N, 4.64; found: C, 71.91; H, 6.63; N, 4.61.
N-(5-ethyl-4'-methyl-[1,1'-biphenyl] -2-yl)
pivalamide (3c)
The general procedure was followed using 4-ethyl pivanilide
(102 mg , 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3c (127 mg, 86% yield) as off-white
needle (m.p.= 77–79 ºC, n-hexane). δH (400 MHz, CDCl3) δ 8.28
(1H, d, J 8.5 Hz, =CH), 7.50 (1H, br, CONH), 7.34–7.28 (4H, m,
=CH), 7.23 (1H, dd, J 8.5, 2.0 Hz, =CH), 7.11 (1H, d, J = 2.0 Hz,
=CH), 2.68 (2H, q, J = 7.5 Hz, CH2Me), 2.46 (3H, s, Me), 1.28
(3H, t, J = 7.5 Hz, CH2Me), 1.15 (9H, s, 3Me); δC (100 MHz,
CDCl3) 176.1, 139.9, 137.7, 135.3, 132.8, 132.2, 129.67, 129.2,
129.2, 127.6, 121, 39.7, 28.3, 27.4, 21.2, 15.7; MS (IE) m/z
(relative intensity %) 296 (M+, 17), 295 (55), 238 (16), 211 (24),
196 (41), 180 (15), 167 (19), 149 (34), 57 (100), 41 (54). Anal.
Calcd for C20H25NO: C, 81.31; H, 8.53; N, 4.74; found: C, 81.44;
H, 8.50; N, 4.72.
4.2.6. N-(5-bromo-4'-methyl-[1,1'-biphenyl] -2-
yl) pivalamide (3g)1 2 h
The general procedure was followed using 4-bromo pivanilide
(128 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3g (145 mg, 84% yield) as yellow needle
(m.p.= 98–100 ºC, n-hexane). δH (400 MHz, CDCl3) 8.33 (1H, d,
J 9.0 Hz, =CH), 7.51 (1H, br, CONH), 7.48 (1H, dd, J 9.0, 2.5
Hz, =CH), 7.39 (1H, d, J 2.5 Hz, =CH), 7.33 (2H, d, J 8.0 Hz,
=CH), 7.27–7.23 (2H, m, =CH), 2.46 (3H, s, Me), 1.13 (9H, s,
3Me); δC (100 MHz, CDCl3) 176.3, 138.5, 134.4, 133.8, 133.6,
132.4, 131, 129.9, 129, 122.2, 116.3, 39.8, 27.3, 21.2; MS (IE)
m/z (relative intensity %) 347 (M+2, 61), 345 (M+, 62), 263 (38),
261 (43), 180 (33), 167 (29), 149 (32), 57 (100), 41 (22). Anal.
Calcd for C18H20BrNO: C, 62.44; H, 5.82; N, 4.05; found: C,
62.68; H, 5.78; N, 4.09.
4.2.3. N-(5-methoxy-4'-methyl-[1,1'-biphenyl] -
2-yl) pivalamide (3d)
The general procedure was followed using 4-methoxy
pivanilide (103 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3d (117 mg, 79% yield) as off-
white needle (m.p.= 109-111 ºC, n-hexane). δH (400 MHz,
CDCl3) 8.18 (1H, d, J 9.0 Hz, =CH), 7.36 (1H, br, CONH), 7.33–
7.26 (4H, m, =CH), 6.92 (1H, dd, J 9.0, 3.0 Hz, =CH), 6.82 (1H,
d, J 3.0 Hz, =CH), 3.82 (3H s, OMe), 2.45 (3H, s, Me), 1.14 (9H,
s, 3Me); δC (125 MHz, CDCl3) 176, 155.9, 137.8, 135.1, 134.1,
129.5, 129, 128.3, 122.9, 115.3, 113.1, 55.4, 39.5, 27.3, 21.1; MS
(IE) m/z (relative intensity %) 297 (M+, 100), 240 (18), 213 (59),
4.2.7. N-(4'-methyl-5-(trifluoromethyl)-[1,1'-
biphenyl] -2-yl) pivalamide (3h)1 2 h
The general procedure was followed using 4- trifluoromethyl
pivanilide (122.5 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3h (119 mg, 71% yield) as off-
white needle (m.p.= 83–85 ºC, n-hexane). δH (400 MHz, CDCl3)
8.61 (1H, d, J 8.5 Hz, =CH), 7.71 (1H, br, CONH), 7.63 (1H, dd,

5
J 8.5, 2.0 Hz, =CH), 7.50 (1H, d, J 2.0 Hz, =CH), 7.40–7.27 (4H,
m, =CH), 2.48 (3H, s, Me), 1.14 (9H, s, 3Me); δF (375 MHz,
CDCl3) δ -62.01; δC (100 MHz, CDCl3) 176.5, 138.7, 138.4,
133.5, 131.8, 130, 129, 126.7 (q, J 4.0 Hz), 125.4 (q, J 32.5 Hz),
125.4 (q, J 4.0 Hz), 123.4 (q, J 269.5 Hz), 120.1, 40, 27.3, 21.2;
MS (IE) m/z (relative intensity %) 335 (M+, 63), 251 (68), 248
(25), 235 (14), 85 (24), 57 (100), 41 (37). Anal. Calcd for
C19H20F3NO: C, 68.05; H, 6.01; N, 4.18; found: C, 67.88; H,
6.05; N, 4.16.
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
ACCEPTED MANUSCRIPT
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3l (123 mg, 75% yield) as off-
white needle (m.p.= 101–103 ºC, n-hexane) δH (400 MHz,
CDCl3) 8.19 (1H, d, J 2.5 Hz, =CH), 7.64 (1H, br, CONH), 7.32–
7.25 (4H, m, =CH), 7.15 (1H, d, J 8.5 Hz, =CH), 6.74 (1H, dd, J
8.5, 2.5 Hz, =CH), 3.89 (3H, s, OMe), 2.45 (3H, s, Me), 1.15
(9H, s, 3Me); δC (100 MHz, CDCl3) 176.4, 159.5, 137.5, 136.2,
134.8, 130.4, 129.7, 129.4, 124.1, 110.5, 105, 55.4, 39.9, 27.4,
21.2; MS (IE) m/z (relative intensity %) 297 (M+, 100), 240
(22), 213 (63), 57 (85), 41 (24). Anal. Calcd for C19H23NO2: C,
76.74; H, 7.80; N, 4.71; found: C, 76.50; H, 7.83; N, 4.73.
4.2.8. N-(4'-methyl-5-nitro-[1,1'-biphenyl] -2-yl)
pivalamide (3i)
The general procedure was followed using 4-nitro pivanilide
(111 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3i (123 mg, 79% yield) as light brown
needle (m.p.= 82–84 ºC, n-hexane). δH (400 MHz, CDCl3) 8.69
(1H, d, J 9 Hz, =CH), 8.22 (1H, dd, J 9, 2.5 Hz, =CH), 8.12 (1H,
d, J 2.5 Hz, =CH), 7.86 (1H, br, CONH), 7.39 (2H, d, J 8.0 Hz,
=CH), 7.28 (2H, d, J 8.0 Hz, =CH), 2.47 (3H, s, Me), 1.13 (9H, s,
3Me); δC (125 MHz, CDCl3) 176.6, 142.9, 141.2, 139.2, 132.5,
131.9, 130.2, 129, 125.1, 124, 119.5, 40.1, 27.1, 21.2; MS (IE)
m/z (relative intensity %) 312 (M+, 64), 228 (18), 211 (26), 180
(24), 85 (35), 57 (100), 41 (61). Anal. Calcd for C18H20N2O3: C,
69.21; H, 6.45; N, 8.97; found: C, 69.39; H, 6.49; N, 8.92.
4.2.12. N-(4'-methyl-4-(trifluoromethyl)-[1,1'-
biphenyl]-2-yl) pivalamide (3m)1 2 h
The general procedure was followed using 3-trifluoromethyl
pivanilide (122.5 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3m (112 mg, 67% yield) as
colorless needle (m.p.= 117–119 ºC, n-hexane). δH (400 MHz,
CDCl3) 8.82 (1H, d, J 1.0 Hz, =CH), 7.66 (1H, br, CONH), 7.43-
7.41 (1H, m, =CH), 7.38–7.34 (3H, m, =CH), 7.31–7.26 (2H, m,
=CH), 2.48 (3H, s, Me), 1.15 (9H, s, 3Me); δF (375 MHz,
CDCl3) δ -62.57; δC (100 MHz, CDCl3) 176.5, 138.7, 135.8,
134.9, 133.7, 130.5 (q, J 32.0 Hz), 130.1, 130, 128.9, 124 (q, J
270.5 Hz), 120.2 (q, J 4.0 Hz), 117.4 (q, J 4.0 Hz), 39.9, 27.3,
21.2; MS (IE) m/z (relative intensity %) 335 (M+, 67), 278 (11),
251 (83), 250 (36), 248 (26), 235 (17), 18 (13), 85 (19), 57 (100),
41 (33). Anal. Calcd for C19H20F3NO: C, 68.05; H, 6.01; N, 4.18;
found: C, 68.26; H, 6.05; N, 4.20.
4.2.9. N-(4,4'-dimethyl-[1,1'-biphenyl] -2-yl)
h
pivalamide (3j)1 2 b ,
The general procedure was followed using 3-methyl pivanilide
(95 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3j (119 mg, 85% yield) as a yellow oil; δH
(400 MHz, CDCl3) 8.28 (1H, d, J 1.0 Hz, =CH), 7.55 (1H, br,
CONH), 7.33-7.26 (4H, m, =CH), 7.15 (1H, d, J 7.5 Hz, =CH),
7.00 (1H, ddd, J 8.0, 1.5, 0.5 Hz, =CH), 2.46 (3H, s, Me), 2.43
(3H, s, Me), 1.16 (9H, s, 3Me); δC (100 MHz, CDCl3) 176.3,
138.2, 137.6, 135, 134.9, 129.7, 129.6, 129.3, 124.6, 121.3, 39.8,
27.4, 21.5, 21.2; MS (IE) m/z (relative intensity %) 281 (M+,
53), 224 (16), 197 (42), 180 (15), 167 (15), 149 (26), 57 (100), 41
(50). Anal. Calcd for C19H23NO: C, 81.10; H, 8.24; N, 4.98;
found: C, 81.41; H, 8.28; N, 4.95.
4.2.13. N-(4,4',5-trimethyl-[1,1'-biphenyl]-2-yl)
pivalamide (3n)
The general procedure was followed using 3, 4-dimethyl
pivanilide (102 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3n (115 mg, 78% yield) as a
yellow oil; δH (400 MHz, CDCl3) 8.20 (1H, s, =CH), 7.49 (1H,
br, CONH), 7.35–7.25 (4H, m, =CH), 7.05 (1H, s, =CH), 2.46
(3H, s, Me), 2.35 (3H, s, Me), 2.29 (3H, s, Me), 1.17 (9H, s,
3Me); δC (100 MHz, CDCl3) 176.2, 137.5, 136.6, 135.2, 132.7,
132.2, 130.9, 129.8, 129.6, 129.2, 122.2, 39.7, 27.4, 21.2, 19.8,
19.2; MS (IE) m/z (relative intensity %) 295 (M, 67), 238 (27),
212 (21), 211 (66), 194 (18), 57 (100), 41 (39). Anal. Calcd for
C20H25NO: C, 81.31; H, 8.53; N, 4.74; found: C, 81.42; H, 8.50;
N, 4.72.
4.2.10. N-(4-ethyl-4'-methyl-[1,1'-biphenyl] -2-
yl) pivalamide (3k)
The general procedure was followed using 3-ethyl pivanilide
(102 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3k (131 mg, 89% yield) as pale yellow
needle (m.p.= 75–77, n-hexane). δH (400 MHz, CDCl3) 8.35 (1H,
d, J 1.5 Hz, =CH), 7.60 (1H, br, CONH), 7.33-7.27 (4H, m,
=CH), 7.19 (1H, d, J 7.5 Hz, =CH), 7.03 (1H, dd, J 8.0, 1.5 Hz,
=CH), 2.74 (2H, q, J 7.5 Hz, CH2Me), 2.46 (3H, s, Me), 1.34
(4H, t, J 7.5 Hz, CH2Me), 1.17 (9H, s, 3Me); δC (100 MHz,
CDCl3) 176.3, 144.6, 137.6, 135.1, 129.7, 129.7, 129.5, 129.3,
123.4, 120.2, 39.8, 28.9, 27.4, 21.2, 15.6; MS (IE) m/z (relative
intensity %) 295 (M+, 100), 238 (48), 211 (75), 196 (24), 180
(23), 57 (57). Anal. Calcd for C20H25NO: C, 81.31; H, 8.53; N,
4.74; found: C, 81.18; H, 8.49; N, 4.76.
4.2.14. N-(4,5-dimethoxy-4'-methyl-[1,1'-
biphenyl]-2-yl) pivalamide (3o)
The general procedure was followed using 3,4-dimethoxy
pivanilide (118.5 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the final product 3o (116 mg, 71% yield) as a
brown oil; δH (400 MHz, CDCl3) 8.12 (1H, s, =CH), 7.48 (1H, br,
CONH), 7.32–7.25 (4H, m, =CH), 6.77 (1H, s, =CH), 3.97 (3H,
s, OMe), 3.88 (3H, s, OMe), 2.44 (3H, s, Me), 1.15 (9H, s, 3Me);
δC (100 MHz, CDCl3) 176.2, 148.3, 145.1, 137.6, 134.9, 129.7,
129.3, 128.7, 127.1, 112.8, 105, 56.1, 56, 39.7, 27.4, 21.2; MS
(IE) m/z (relative intensity %) 327 (M+, 100), 228 (35), 211
(20), 196 (19), 57 (55). Anal. Calcd for C20H25NO3: C, 73.37; H,
7.70; N, 4.28; found: C, 73.60; H, 7.76; N, 4.32.
4.2.11. N-(4-methoxy-4'-methyl-[1,1'-biphenyl] -
2-yl) pivalamide (3l)
The general procedure was followed using 3-methoxy
pivanilide (103 mg, 0.5 mmol), p-toluenesulfonyl chloride (143

6
Tetrahedron
4.2.15. N-(5-methyl-[1,1'-biphenyl]-2-yl)
20.8; MS (IE) m/z (relative intensity %) 312 (M+, 100), 262
ACCEPTED MANUSCRIPT
pivalamide (3p)1 1 a , 1 2 b , c
(31), 228 (72), 211 (33), 180 (40), 57 (83). Anal. Calcd for
C18H20N2O3: C, 69.21; H, 6.45; N, 8.97; found: C, 69.07; H, 6.48;
N, 8.94.
The general procedure was followed using 4-methyl pivanilide
(95 mg, 0.5 mmol), benzenesulfonyl chloride (133 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3ab (128 mg, 96% yield) as white needle
(m.p.= 94–96 ºC, n-hexane). δH (400 MHz, CDCl3) 8.24 (1H, d, J
8.5 Hz, =CH), 7.54–7.49 (2H, m, =CH), 7.47–7.37 (4H, m,
=CH), 7.21 (1H, dd, J 8.5, 2 Hz, =CH), 7.11–7.09 (1H, m, =CH),
2.38 (3H, s, Me), 1.13 (9H, s, 3Me); δC (125 MHz, CDCl3) 176.1,
138.2, 133.4, 132.5, 132.3, 130.2, 129.2, 128.9, 127.8, 121.1,
121, 39.6, 27.3, 20.7; MS (IE) m/z (relative intensity %) 267
(M+, 67), 210 (16), 183 (77), 182 (37), 57 (100), 41 (28). Anal.
Calcd for C18H21NO: C, 80.86; H, 7.92; N, 5.24; found: C, 80.62;
H, 7.96; N, 5.21.
4.2.19. N-(2-chloro-4-
methylphenyl)pivalamide(4a)1 7
The general procedure was followed using 4-methyl pivanilide
(95 mg, 0.5 mmol), p-toluenesulfonyl chloride (143 mg, 0.75
mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the side product 4a (32 mg, 29% yield) as white needle
(m.p.= 65–67 ºC, n-hexane); δH (500 MHz, CDCl3) 8.25 (1H, d, J
8.5 Hz, =CH), 7.91 (1H, br, CONH), 7.17 (1H, s, =CH), 7.06
(1H, d, J 8.5 Hz, =CH), 2.28 (3H, s, Me), 1.33 (9H, s, 3Me); δC
(125 MHz, CDCl3) 176.4, 134.4, 132.1, 129.1, 128.2, 122.8,
121.3, 40.0, 28.4, 20.5; MS (IE) m/z (relative intensity %) 227
(M+2, 3) 225 (M+, 11), 190 (20), 141 (73), 106 (13), 57 (100).
Anal. Calcd for C12H16ClNO: C, 63.85; H, 7.14; N, 6.21; found:
C, 63.63; H, 7.17; N, 6.24.
4.2.16. N-(4'-chloro-5-methyl-[1,1'-biphenyl]-2-
yl) pivalamide (3q)
The general procedure was followed using 4-methyl pivanilide
(95 mg, 0.5 mmol), 4-chloro benzenesulfonyl chloride (158 mg,
0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3q (129 mg, 86% yield) as off-white
needle (m.p.= 105–107 ºC, n-hexane). δH (400 MHz, CDCl3) 8.11
(1H, d, J 8.5 Hz, =CH), 7.47–7.44 (2H, m, =CH), 7.32–7.29 (3H,
m, =CH), 7.20 (1H, d, J 8.5 Hz, =CH), 7.05 (1H, d, J 2.0 Hz,
=CH), 2.37 (3H, s, Me), 1.15 (9H, s, 3Me); δC (100 MHz, CDCl3)
176.3, 136.9, 134, 133.9, 132.3, 131.7, 130.6, 129.3, 129, 122.2,
120.2, 39.6, 27.4, 20.8; MS (IE) m/z (relative intensity %) 301
(M+, 5), 225 (28), 190 (85), 141 (66), 106 (28), 77 (24), 57
(100), 41 (25). Anal. Calcd for C18H20ClNO: C, 71.63; H, 6.68;
4.2.20. N-(2-chloro-4-methoxyphenyl)pivalamide
(4d)
The general procedure was followed using 4-methoxy
pivanilide (103 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (42 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the side product 4d (20 mg, 17% yield) as yellow
oil; δH (400 MHz, CDCl3) 8.25 (1H, d, J 9.0 Hz, =CH), 7.81 (1H,
br, CONH), 6.96 (1H, d, J 3.0 Hz, =CH), 6.85 (1H, dd, J 9.0, 3.0
Hz, =CH), 3.81 (3H s, OMe), 1.37 (9H, s, 3Me); δC (100 MHz,
CDCl3) 176.4, 156.0, 128.1, 124.1, 122.8, 114.4, 113.1, 55.7,
39.9, 27.6; MS (IE) m/z (relative intensity %) 243 (M+2, 9), 241
(M+, 28), 206 (74), 157 (40), 142 (48) 57 (100). Anal. Calcd for
C12H16ClNO2: C, 59.63; H, 6.67; N, 5.79; found: C, 59.79; H,
6.62; N, 5.82.
N, 4.64; found: C, 71.91; H, 6.71; N, 4.66
.
4.2.17. N-(4'-bromo-5-methyl-[1,1'-biphenyl]-2-yl)
pivalamide (3r)
The general procedure was followed using 4-methyl pivanilide
(95 mg, 0.5 mmol), 4-bromo benzenesulfonyl chloride (192 mg,
0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3r (153 mg, 89% yield) as off-white
needle (m.p.= 122–124 ºC, n-hexane). δH (400 MHz, CDCl3) 8.10
(1H, d, J 8.5 Hz, =CH), 7.62–7.6 (2H, m, =CH), 7.33 (1H, br,
CONH), 7.26–7.23 (2H, m, =CH), 7.20 (1H, dd, J 8.5, 2.0 Hz,
=CH), 7.04 (1H, d, J 2.0 Hz, =CH), 2.36 (3H, s, Me), 1.15 (9H, s,
3Me); δC (100 MHz, CDCl3) 176.3, 137.3, 134.1, 132.2, 132,
131.7, 131, 130.3, 129.3, 122.2, 122.1, 39.6, 27.4, 20.8; MS (IE)
m/z (relative intensity %) 347 (M+2, 34), 345 (M+, 35), 263 (49),
261 (51), 209 (23), 191 (25), 180 (48), 107 (23), 57 (100), 41
(28). Anal. Calcd for C18H20BrNO: C, 62.44; H, 5.82; N, 4.05;
found: C, 62.71; H, 5.87; N, 4.09.
4.2.21. N-(2-chloro-5-methoxyphenyl)pivalamide
(4l)
The general procedure was followed using 3-methoxy
pivanilide (103 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the side product 4l (18 mg, 15% yield) as a
colorless oil; δH (400 MHz, CDCl3) ) 8.19 (1H, d, J 3.0 Hz,
=CH), 8.07 (1H, br, CONH), 7.25 (1H, d, J 9.0 Hz, =CH), 6.62
(1H, dd, J 9.0, 3.0 Hz, =CH), 3.83 (3H s, OMe), 1.38 (9H, s,
3Me); δC (100 MHz, CDCl3) 176.8, 159.0, 135.4, 129.0, 113.8,
111.2, 106.7, 55.6, 40.3, 27.5; MS (IE) m/z (relative intensity %)
243 (M+2, 3), 241 (M+, 11), 206 (100), 157 (28), 57 (88). Anal.
Calcd for C12H16ClNO2: C, 59.63; H, 6.67; N, 5.79; found: C,
59.40; H, 6.64; N, 5.84.
4.2.18. N-(5-methyl-4'-nitro-[1,1'-biphenyl]-2-yl)
pivalamide (3s)
The general procedure was followed using 4-methyl pivanilide
(95 mg, 0.5 mmol), 4-nitro benzenesulfonyl chloride (166 mg,
0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10 mol%).
Purification by column chromatography (silica gel, n-hexane)
gave the final product 3s (145 mg, 93% yield) as yellow powder
(m.p.= 133–135 ºC, n-hexane/EtOAc). δH (400 MHz, CDCl3)
8.34 (d, J = 9.0 Hz, 2H =CH), 7.95 (1H, d, J = 8.5 Hz, =CH),
7.60–7.56 (2H, m, =CH), 7.26 (1H, dd, J 8.5, 2 Hz, =CH), 7.19
(1H, br, CONH), 7.10 (1H, d, J 2 Hz, =CH), 2.40 (3H, s, Me),
1.15 (9H, s, 3Me); δC (100 MHz, CDCl3) 176.5, 147.3, 145.7,
135, 131.9, 131.8, 130.2, 130.2, 130.2, 123.9, 123.7, 39.5, 27.4,
4.2.22. N-(2-chloro-4,5dimethoxyphenyl)
pivalamide (4o)
The general procedure was followed using 3, 4-dimethoxy
pivanilide (118.5 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane) gave the side product 4o (28 mg, 21% yield) as as off-
white powder (m.p.= 107–109 ºC, n-hexane); δH (400 MHz,
CDCl3) 8.11 (1H, s, =CH), 7.48 (1H, br, CONH), 6.73 (1H, s,
=CH), 3.88 (3H, s, OMe), 3.83 (3H, s, OMe), 1.33 (9H, s, 3Me);
δC (100 MHz, CDCl3) 176.5, 148.0, 145.3, 128.3, 113.4, 111.6,

7
K. Isr. J. Chem. 2010, 50, 617–629; (c) Bonesi, S. M.; Fagnoni,
105.2, 56.2, 56.0, 40.0, 27.5; MS (IE) m/z (relative intensity %)
273 (M+2, 17), 271 (M+, 49), 263 (100), 172 (59), 57 (87). Anal.
Calcd for C13H18ClNO3: C, 57.46; H, 6.68; N, 5.15; found: C,
57.59; H, 6.70; N, 5.18.
ACCEPTED MANUSCRIPT
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4.2.23. N-([1,1'-biphenyl] -2-yl)benzamide (5)1 2 a
The general procedure was followed using N-phenyl
benzamide (98.5 mg, 0.5 mmol), p-toluenesulfonyl chloride (143
mg, 0.75 mmol), Li2CO3 (74 mg, 1 mmol), PdCl2 (9 mg, 10
mol%). Purification by column chromatography (silica gel, n-
hexane/EtOAc 10:1), gave the final product 5 (80 mg, 59% yield)
as colorless needle (m.p.= 90–92 ºC, n-hexane/EtOAc); δH (400
MHz, d6-DMSO) 9.84 (1H, br, CONH), 7.81 (2H, d, J 7.5 Hz,
=CH), 7.52 (2H, t, J 8.5, =CH), 7.48–7.37 (9H, m, =CH), 7.30
(1H, t, J 7.5 Hz, =CH). Anal. Calcd for C19H15NO: C, 83.49; H,
5.53; N, 5.12; found: C, 83.59; H, 5.57; N, 5.18.
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Acknowledgements
We gratefully acknowledge the financial support from the
Research Council of the University of Tehran.
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8
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ACCEPTED MANUSCRIPT
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