Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbismuth reagents

Article abstract of DOI:10.1016/j.tetlet.2019.150971

Various Pd-catalyzed protocols have been developed for the atom-efficient cross-coupling of chloroarenes with triarylbismuth reagents. Using the developed protocols, an efficient synthesis of unsymmetrical biaryls in good to excellent yields was achieved by employing electron-deficient chloroarenes and a range of triarylbismuth reagents.

Full text of DOI:10.1016/j.tetlet.2019.150971

Accepted Manuscript
Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbis-
muth reagents
Maddali L.N. Rao, Suresh Meka
PII:
S0040-4039(19)30722-1
https://doi.org/10.1016/j.tetlet.2019.150971
150971
DOI:
Article Number:
Reference:
TETL 150971
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
7 June 2019
17 July 2019
22 July 2019
Please cite this article as: Rao, M.L.N., Meka, S., Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with
triarylbismuth reagents, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.2019.150971
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Graphical Abstract
Atom-efficient Pd-catalyzed cross-couplings of
chloroarenes with triarylbismuth reagents
Leave this area blank for abstract info.
Maddali L. N. Rao*, Suresh Meka
[Pd]
Bi
Cl
3
R'
R'
R
R
35-86%
R = 4-NO2, 2-NO2, 4-CHO, 4-CN, 2,4-NO2
R' = H, 4-Me, 4-OMe, OEt, OiPr, OnBu, OiBu, 4-F, 4-Cl, vinyl

1
Tetrahedron Letters
journal homepage: www.elsevier.com
Atom-efficient Pd-catalyzed cross-couplings of chloroarenes with triarylbismuth
reagents
Maddali L. N. Rao*, Suresh Meka
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur-208016, India
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Various Pd-catalyzed protocols have been developed for the atom-efficient cross-coupling of
chloroarenes with triarylbismuth reagents. Using the developed protocols, an efficient synthesis
of unsymmetrical biaryls in good to excellent yields was achieved by employing electron-
deficient chloroarenes and a range of triarylbismuth reagents.
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
Aryl chlorides
Triarylbismuth reagents
Cross-coupling
Palladium
The metal-catalyzed cross-coupling of aryl electrophiles with
various organometallic reagents serves as a major tool for C-C
bond formation.1-4 The Suzuki, Stille, Negishi, Hiyama, and
Kumada cross-couplings involving a variety of organometallic
reagents have significantly enriched this methodology.5 Among
the organometallic reagents used in coupling reactions,
triarylbismuth reagents are embedded with a threefold coupling
advantage as they deliver three aryl groups during the coupling
process.6,7 We have been involved in expanding the scope of
triarylbismuth reagents as atom-efficient coupling partners with
various organic electrophiles under Pd-catalyzed conditions. In
particular, we have developed a number of efficient protocols for
the couplings of aryl bromides, iodides and triflates with
triarylbismuth reagents to synthesize functionalized biaryls.7 This
field of research was recently reviewed by Gagnon and co-
workers.8a Various research groups have also reported reactions
involving chloro heteroarenes,8b arenes8c,d and arenes containing
more than one halide.8e-h Generally, in these cross-coupling
reactions, oxidative addition is the rate determining step.8i
Notably, the diversified biaryl scaffold is a privileged structure
with importance in pharmaceuticals, materials and natural
products.9 Boscalid is an important fungicide with a biaryl
system, marketed by BASF, which is used for the protection of
plants and trees against gray and blue molds.10 In the industrial
synthesis of Boscalid, 2-amino-4-chlorobiphenyl is accessed via
the cross-coupling of electron-deficient 1-chloro-2-nitrobenzene
and aryl organo-metallic reagents.11-12 The reactivity of these
substrates is consequently significant in terms of their industrial
applications.
Therefore, it is of interest to investigate the scope of atom-
efficient triarylbismuth couplings with aryl chlorides. Herein, we
report that aryl chlorides can be effectively engaged in couplings
with triarylbismuth reagents under Pd-catalyzed reaction
conditions.
To explore this reactivity, the model coupling reaction of 4-
chloronitrobenzene 1a with triphenylbismuth was screened under
different Pd-catalyzed conditions as summarized in Table 1.
Table 1. Screening with 4-chloronitrobenzene 1a.a-c
Ph
Ph
[Pd]
Bi
O2N
O2N
Cl
ligand
base
solvent
Ph
1a
(3.5 equiv.)
2a
(3 equiv.)
Entry Base
(equiv.)
Ligand
(0.4
Solvent
Temp
Time
(h)
Yield
2a (%)
(oC)
equiv.)
PPh3
1
2
K3PO4 (6)
K3PO4 (6)
Cs2CO3 (3)
Cs2CO3 (3)
K3PO4 (3)
DMF
NMP
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
DMF
110
110
110
110
110
90
4
4
4
4
4
6
4
6
6
6
6
20
26
34
73
64
79
64
52
48
--
PPh3
PPh3
3
4
P(p-tolyl)3
P(p-tolyl)3
5
6
Cs2CO3 (3) P(p-tolyl)3
7
Cs2CO3 (3)
Cs2CO3 (2)
Cs2CO3 (4)
--
P(p-tolyl)3
P(p-tolyl)3
P(p-tolyl)3
P(p-tolyl)3
--
90
8
90
9
90
10
11
90
______
Cs2CO3 (3)
90
--
a Reagents and conditions: 1a (0.875 mmol, 3.5 equiv.), BiPh3 (0.25 mmol, 1
 Corresponding author. E-mail address: maddali@iitk.ac.in

2
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), ligand (0.1 mmol, 0.4 equiv.),
base, temp, time, solvent (3 mL).
c Homo-coupled biaryl from BiAr3 was obtained in minor amounts.
b Isolated yield.
The coupling reactions of 4-chloronitrobenzene 1a with
electron-rich triarylbismuth reagents furnished the corresponding
biaryls (2a-2j) in 57−86% yield (Entries 1-10, Table 2). The
cross-coupling of electron-deficient triarylbismuth reagents
containing 4-fluoro and 4-vinyl groups gave the corresponding
biaryls (2k and 2l) in moderate yields (Entries 11 and 12, Table
2). Further reactivity tested with trinaphthalen-2-ylbismuthine
afforded biaryl 2m in 40% yield (Entry 13, Table 2). The
coupling of other aryl chlorides with different triarylbismuth
reagents did not afford the desired products (Entries 14-17, Table
2).
c Homo-coupled biphenyl from BiPh3 was obtained in minor amounts.
Our initial attempts of cross-coupling were carried out with
Pd(OAc)2, PPh3 and inorganic bases in DMF or NMP; however,
these reactions gave poor yields (Table 1, entries 1-3). Therefore,
the reaction was further investigated with P(p-tolyl)3 in DMF
(Entries 4-6, Table 1). This resulted in the formation of biaryl 2a
in 79% yield (Entry 6, Table 1)13 after chromatographic
purification. Further screening with different loadings of base,
time and controls (Entries 7-11, Table 1) revealed that the Pd-
coupling protocol conducted with P(p-tolyl)3, Cs2CO3 (3 equiv.),
o
in DMF at 90 C for 6 h were the most efficient to deliver the
We next investigated the coupling of sterically demanding 1-
chloro-2-nitrobenzene 1b with various triarylbismuth reagents
under the above optimized conditions. However, under these
conditions the coupling afforded the corresponding 2-nitro-1,1'-
biphenyl 3a in 44% yield. This prompted us to explore the
reactivity with an electron-rich P(p-anisyl)3 ligand (Table 3). This
change afforded the desired 3a in 55% yield (Entry 1, Table 3).
Further cross-coupling results obtained with 1-chloro-2-
nitrobenzene 1b and other triarylbismuth reagents under these
conditions are shown in Table 3.
corresponding biaryl 2a in high yield (Entry 6, Table 1).
Encouraged by this, the optimized protocol was employed in
testing the reactivity of different aryl chlorides with
triarylbismuth reagents. These results are shown in Table 2.
Table 2. Cross-couplings of 1a and other chloroarenes with
BiAr3.a-c
Pd(OAc)2 (0.1 equiv.)
Ar
Ar
P(p-tolyl)3 (0.4 equiv.)
Cs2CO3 (3 equiv.)
DMF, 90 oC, 6 h
Bi
Cl
(3.5 equiv.)
Substrate
Ar
R
Ar
R
2a-2m
Table 3.
(3 equiv.)
Cross-couplings with 1-chloro-2-nitrobenzene 1b.a-c
Yield (%)b
79
Entry
1
Product
BiAr3
O2N
Cl
Bi
Bi
Bi
O2N
NO2
Ar
NO2
Cl
Pd(OAc)2 (0.1 equiv.)
P(p-anisyl)3 (0.4 equiv.)
Cs2CO3 (3 equiv.)
3
2a
2b
2c
2d
2e
2f
1a
1a
Ar
Ar
Bi
O2N
O2N
Me
73
80
2
3
Me
Ar
DMF, 90 oC, 6 h
3a-3f
(3 equiv.)
1b
3
(3.5 equiv.)
1a
OMe
OEt
OMe
OEt
OiPr
Entry
BiAr3
Yield (%)
Product
NO2
3
Bi
Bi
Bi
O2N
O2N
O2N
79
76
58
55
78
4
5
1a
1a
1
2
Bi
Bi
3
3
3a
NO2
OiPr
3
Me
Me
F
3
3b
6
1a
3
3
NO2
Me
Me
3
4
Bi
F
35
72
7
8
1a
1a
57
86
Bi
Bi
O2N
O2N
3
3c
2g
OMe
OMe
OiBu
NO2
OiBu
Bi
Bi
Bi
OnBu
OiBu
OEt
OnBu
OiBu
OEt
3
2h
2i
3
3d
NO2
9
1a
1a
Bi
Bi
OnBu
OMe
O2N
O2N
OnBu
OMe
81
83
3
3
5
6
70
82
3
10
3e
NO2
2j
OMe
OMe
11
1a
60
Bi
F
O2N
F
3
3f
3
2k
a Reagents and conditions: 1b (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), P(p-anisyl)3 (0.1 mmol, 0.4
equiv.), Cs2CO3 (0.75 mmol, 3 equiv.), DMF (3 mL), 90 oC, 6 h.
12
13
1a
1a
Bi
Bi
O2N
O2N
55
40
3
3
2l
b Isolated yield.
2m
--
--
Bi
Bi
OMe
OMe
Cl
14
15
c Homo-coupled biaryl from BiAr3 was obtained in minor amounts.
3
The reactions using electron-rich bismuth reagents proceeded
efficiently to afford the corresponding biaryls (3b, 3d-3f) in high
yields (Entries 2, 4-6, Table 3).14 The coupling of electron-
deficient triarylbismuth reagents with fluoro substitution afforded
biaryl 3c in poor yield (Entry 3, Table 3).
Ac
Ac
Cl
3
3
Ac
Ac
--
--
Bi
Bi
16
17
Cl
Cl
F3C
OMe
F3C
OMe
3
a Reagents and conditions: 1a (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), P(p-tolyl)3 (0.1 mmol, 0.4
equiv.), Cs2CO3 (0.75 mmol, 3 equiv.), DMF (3 mL), 90 oC, 6 h.
We then investigated the coupling of 4-chlorobenzaldehyde 1c
(Table 4) under the conditions used in Table 3; unfortunately this
coupling afforded biaryl 4a in only 6% yield (Entry 1, Table 4).
To improve the cross-coupling, we performed additional
screening under different conditions. The cross-coupling carried
b Isolated yield.

3
out with PCy3 gave poor yields (Entries 2 and 3, Table 4).
However, the coupling efficiency improved with the addition of
TBAB or TBAI additives (Entries 4-6, Table 4). The highest
coupling yield (68%) was obtained under the conditions using
Pd(OAc)2 (0.1 equiv.), PCy3 (40 mol%), Cs2CO3 (3 equiv.),
Table 5.
Cross-couplings
of
4-chlorobenzaldehyde
(1c),
4-
chlorobenzonitrile (1d) and other chloroarenes.a-e
Pd(OAc)2 (0.1 equiv.)
Ar
Ar
PCy3 (0.4 equiv.)
Cs2CO3 (3 equiv.)
TBAI (5 equiv.)
R
Cl
Bi
R
Ar
o
TBAI (5 equiv.), DMF (3 mL) at 110 C for 4 h (Entry 6, Table
4).
Ar
1c-1d
(3.5 equiv.)
4a-4i
(3 equiv.)
DMF, 110 oC, 4 h
Entry
1
Arylchloride
BiAr3
Product
Yield (%)
Table 4.
Screening with 4-chlorobenzaldehyde 1c.a-c
68
OHC
Cl
Bi
OMe
OHC
OMe
3
4a
1c
1c
Bi
Bi
OEt
OHC
OHC
OEt
69
67
2
3
Pd(OAc)2
3
3
OHC
Cl
OHC
OMe
Bi
OMe
4b
4c
ligand, additive
Cs2CO3 (3 equiv.)
DMF, heat
3
4a
OiBu
OiBu
1c
1c
(3 equiv.)
(3.5 equiv.)
Entry
Ligand
(0.4 equiv.)
P(p-anisyl)3
Additive
(equiv.)
--
Temp (oC)
Yield (%)
NC
Cl
Bi
Bi
OMe
4
5
NC
NC
OMe
Me
69
45
3
1d
1d
4d
4e
1
2
3
4
5
90
6
Me
3
PCy3
PCy3
PCy3
PCy3
PCy3
--
110
130
110
110
110
24
32
42
65
68
--
6
7
8
1d
1d
Bi
Bi
Bi
OEt
NC
NC
NC
OEt
65
61
57
3
3
3
TBAB (3.5)
TBAI (3.5)
TBAI (5.0)
4f
OiPr
OnBu
OiPr
OnBu
4g
6
1d
1d
a
Reagents and conditions: 4-cholorobenzaldehyde (0.875 mmol, 3.5 equiv.),
Bi(p-anisyl)3 (0.25 mmol, 1 equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.),
ligand (0.1 mmol, 0.4 equiv.), temp, DMF (3 mL), 4 h.
4h
4i
9
Bi
OiBu
NC
OiBu
65
--
3
b Isolated yield.
10
11
Ac
Ac
Cl
Cl
Bi
Bi
OMe
OMe
Ac
Ac
OMe
OMe
c Homo-coupled biaryl from BiAr3 was obtained in minor amounts.
3
3
--d
The cross-coupling reactivity of 4-chlorobenzaldehyde 1c was
also tested with different triarylbismuth reagents under the above
optimized conditions (Entries 1-3, Table 5). These couplings
afforded the corresponding functionalized biaryls (4a-4c) in good
yields. The coupling of 4-chlorobenzonitrile with different
triarylbismuth reagents gave biaryls (4d-4i) in good yields
(Entries 4-9, Table 5). Furthermore, we examined the reactivity
Ac
Ac
--
12
13
Cl
Cl
Bi
Bi
OMe
OMe
OMe
OMe
3
3
--e
Me
Me
Me
Me
14
--
Bi
Cl
with
4-chloroacetophenone,
3-chloroacetophenone,
4-
3
chlorotoluene and 3-chlorotoluene using different conditions.
However, these efforts did not result in cross-couplings with
triarylbismuth reagents (Entries 10-14, Table 5).
a
Reagents and conditions: 1c or 1d (0.875 mmol, 3.5 equiv.), BiAr3 (0.25
mmol, 1 equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), PCy3 (0.1 mmol, 0.4
equiv.), Cs2CO3 (0.75 mmol, 3 equiv.), TBAI (1.25 mmol, 5 equiv.), DMF (3
mL), 110 o C, 4 h.
Finally, we studied the coupling reactivity of 1-chloro-2,4-
dinitrobenzene 1e (Table 6)15 with triphenylbismuth, which gave
biaryl 5a in 65% yield (Entry 1, Table 6). Additional couplings
with triarylbismuth reagents possessing electron-donating groups
gave the corresponding biaryls (5b-5f and 5i-5k) in 71-80% yield
(Entries 2-6 and 9-11, Table 6). Couplings with triarylbismuth
reagents functionalized with electron-deficient halogen groups
such as 4-fluoro, 4-chloro, 3-fluoro and 3-chloro provided biaryls
(5g, 5h, 5l and 5m) in moderate yields (Entries 7, 8, 12 and 13,
Table 6).
b Isolated yield.
c Homo-coupled biaryl from BiAr3 was obtained in minor amounts.
d PtBu3
e XPhos
In summary, we have reported the cross-coupling of electron
deficient chloroarenes with different triarylbismuth reagents
under various Pd-catalyzed conditions. Further study of
couplings with electron-rich chloroarenes requires further
investigation with different ligands and catalysts and will be
addressed in our future efforts.

4
N. Tetrahedron Lett. 2007, 48, 2707-2711; (c) Rao, M. L. N.;
Jadhav, D. N.; Banerjee, D. Tetrahedron 2008, 64, 5762-5772.
Table 6.
Cross-couplings with 1-chloro-2,4-dinitrobenzene 1e.a-c
8.
(a) Gagnon, A.; Dansereau, J.; Le Roch, A. Synthesis 2017, 49,
1707-1745 and references cited therein; (b) Hebert, M.; Petiot, P.;
Benoit, E.; Dansereau, J.; Ahmad, T.; Roch, A. L.; Ottenwaelder,
X.; Gagnon, A. J. Org. Chem. 2016, 81, 5401-5416; (c) Yamazaki,
O.; Tanaka, T.; Shimada, S.; Suzuki, Y.; Tanaka, M. Synlett
2004, 1921-1924; (d) Jadhav, B. D.; Pardeshi, S. K. Appl.
Organometal. Chem. 2017, 31, e3591; (e) Zhou, W.-J.; Wang, K.-
H.; Wang, J.-X.; Huang, D.-F. Eur. J. Org. Chem. 2010, 416-419;
(f) Rao, M. L. N.; Dhanorkar, R. J. RSC Adv. 2014, 4, 13134-
13144; (g) Rao, M. L. N.; Giri, S. RSC Adv. 2012, 2, 12739-12750;
(h) Rao, M. L. N.; Giri, S.; Jadhav, D. N. Tetrahedron Lett. 2009,
50, 6133-6138. (i) Kutudila, P.; Linguerri, R.; Al-Mogren, M. M.;
Pichon, C.; Condon, S.; Hochlaf, M. Theor. Chem. Acc. 2016, 135,
176.
(a) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107,
174-238; (b) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.;
Lemaire, M. Chem. Rev. 2002, 102, 1359-1469; (c) Prieto, M.;
Mayor, S.; Lloyd-Williams, P.; Giralt, E. J. Org. Chem. 2009, 74,
9202-9205; (d) Bringmann, G.; Gulder, T.; Gulder, T. A. M.;
Breuning, M. Chem. Rev. 2011, 111, 563-569; (e) Kozlowski, M.
C.; Morgan, B. J.; Linton, E. C. Chem. Soc. Rev. 2009, 38, 3193-
3207; (f) Yasuda, N. J. Organomet. Chem. 2002, 253, 279-287.
Pd(OAc)2 (0.1 equiv.)
Ar
Ar
PCy3 (0.4 equiv.)
Cs2CO3 (3 equiv.)
TBAI (5 equiv.)
Bi
O2N
Cl
O2N
Ar
Ar
NO2
NO2
5a-5m
(3 equiv.)
DMF, 110 oC, 4 h
1e
(3.5 equiv.)
Entry
BiAr3
Yield (%)
Product
1
Bi
Bi
Bi
O2N
65
3
NO2
NO2
5a
5b
2
3
Me
O2N
O2N
Me
80
72
3
OMe
OiPr
OMe
3
NO2 5c
NO2 5d
9.
OiPr
4
5
Bi
Bi
80
72
O2N
O2N
3
3
Me
NO2
Me
5e
6
O2N
71
Bi
3
10. Xiao, C. L.; Boal, R. J. Plant Dis. 2009, 93, 185-189.
11. (a) Glasnov, T. N.; Kappe, C. O. Adv. Synth. Catal. 2010, 352,
3089-3097; (b) Volovych, I.; Neumann, M.; Schmidt, M.; Buchner,
G.; Yang, J.-Y.; Wolk, J.; Sottmann, T.; Strey, R.; Schomacker, R.;
Schwarze, M. RSC Adv. 2016, 6, 58279-58287.
12. Drageset, A.; Elumalai, V.; Bjorsvik, H.-R. React. Chem. Eng.,
2018, 3, 550-558.
13. Representative procedure for the cross-coupling of 1a with
triarylbismuth reagents: (Table 2). An oven-dried Schlenk tube
NO2 5f OMe
OMe
Bi
Bi
Bi
Bi
F
O2N
O2N
O2N
O2N
F
7
8
60
63
74
72
3
5g
5h
NO2
NO2
NO2
NO2
Cl
Cl
3
9
OEt
OEt
OnBu
3
5i
5j
under
a nitrogen atmosphere was charged with 4-chloro-
nitrobenzene (1a) (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), P(p-tolyl)3 (0.1 mmol,
0.4 equiv.), Cs2CO3 (0.75 mmol, 3 equiv.) and DMF (3 mL). This
mixture was stirred in an oil bath at 90 oC for 6 h. Then the contents
were cooled to rt, quenched with water and extracted with ethyl
acetate (30 mL). The organic extract was treated with brine, dried
over anhydrous MgSO4 and concentrated. The crude product was
purified by silica gel column chromatography (using hexane and
ethyl acetate as eluent) to obtain 2a in 79% yield.
10
OnBu
OiBu
3
3
Bi
Bi
O2N
O2N
OiBu
11
12
78
56
5k
5l
NO2
NO2
3
3
F
F
14. Cross-coupling of 1b with triarylbismuth reagents: (Table 3). The
representative cross-coupling procedure given for Table 2 was
followed with the following reagents and conditions: arylchloride
1b (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1 equiv.),
Pd(OAc)2 (0.025 mmol, 0.1 equiv.), P(p-anisyl)3 (0.1 mmol, 0.4
13
O2N
59
Bi
NO2
Cl
Cl
5m
a Reagents and conditions: 1e (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), PCy3 (0.1 mmol, 0.4 equiv.),
Cs2CO3 (0.75 mmol, 3 equiv.), TBAI (1.25 mmol, 5 equiv.), DMF (3 mL),
110 oC, 4 h.
o
equiv.), Cs2CO3 (0.75 mmol, 3 equiv.) and DMF (3 mL) at 90 C
for 6 h.
15. Cross-coupling of 1c-1e with triarylbismuth reagents: (Table 5 and
Table 6). The representative cross-coupling procedure given for
Table 2 was followed with the following reagents and conditions:
arylchloride 1c-1e (0.875 mmol, 3.5 equiv.), BiAr3 (0.25 mmol, 1
equiv.), Pd(OAc)2 (0.025 mmol, 0.1 equiv.), PCy3 (0.1 mmol, 0.4
equiv.), Cs2CO3 (0.75 mmol, 3 equiv.), TBAI (1.25 mmol, 5 equiv.)
and DMF (3 mL) at 110 oC for 4 h.
b Isolated yield.
c Homo-coupled biaryl from BiAr3 was obtained in minor amounts.
Acknowledgments
We acknowledge the financial support (Project No.
02(0091)/12/EMR-II) received from the Council of Scientific and
Industrial Research (CSIR), New Delhi. S.M also acknowledges
the research fellowship from the CSIR, New Delhi.
Highlights:
 Aryl chloride couplings
 Triarylbismuth Reagents
 Palladium catalysis
References and notes
 Atom-efficient couplings
 Threefold couplings
1.
2.
3.
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