The Highly Efficient Suzuki–Miyaura Cross-Coupling of (Hetero)aryl Chlorides and (Hetero)arylboronic Acids Catalyzed by “Bulky-yet-Flexible” Palladium–PEPPSI Complexes in Air

Article abstract of DOI:10.1002/cctc.201701076

A series of Pd–PEPPSI complexes were designed and synthesized. The relationship between catalyst structure and properties was systematically investigated. It was revealed that “bulky-yet-flexible” C3 bearing ancenaphthyl backbone was a highly efficient precatalyst and could be successfully employed in Suzuki–Miyaura reactions of (hetero)aryl chlorides with (hetero)arylboronic acids at a low palladium loading in the presence of a weak inorganic base in air.

Full text of DOI:10.1002/cctc.201701076

Accepted Article
Title: The highly efficient Suzuki-Miyaura cross-coupling of (hetero)aryl
chlorides and (hetero)arylboronic acids catalyzed by "bulky-yet-
flexible" Pd-PEPPSI complexes in air
Authors: Jia-Sheng Ouyang, Yan-Fang Li, Fei-Dong Huang, Dong-
Dong Lu, and feng-Shou Liu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201701076
Link to VoR: http://dx.doi.org/10.1002/cctc.201701076
A Journal of
www.chemcatchem.org

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
The highly efficient Suzuki-Miyaura cross-coupling of (hetero)aryl
chlorides and (hetero)arylboronic acids catalyzed by “bulky-yet-
flexible” Pd-PEPPSI complexes in air
Jia-Sheng Ouyang‡,[a] Yan-Fang Li‡,[a] Fei-Dong Huang,[a] Dong-Dong Lu,[a] and Feng-Shou Liu *[a]
Abstract: A series of Pd-PEPPSI complexes were designed and
synthesized. The efforts on the understanding the relationship
between catalyst structure and catalytic properties, have been
systematically investigated. It revealed that C3 bearing
ancenaphthyl backbone and “bulky flexible steric” was found to be
highly efficient precatalysts and successfully employed in Suzuki-
Miyaura reactions of (hetero)aryl chlorides with (hetero)arylboronic
acids at low palladium loading, in the presence of weak inorganic
base of K2CO3 in air.
The palladium-catalyzed Suzuki-Miyaura cross-coupling has
been recognized as dominant and indispensable tool for biaryl
formation, whereas the biaryl is of interest as fundamental motif
in various fields such as pharmaceuticals, natural products, and
functional materials.[1] The catalyst structures, especially the
ligands, defines the electronic and steric properties toward the
palladium center and therefore played vital roles in the
transformation reactions.[2] Since the initial work reported by
Herrmann,[3] the N-Heterocyclic carbenes (NHCs)-based ligands,
Scheme 1. The design strategy of “bulky-yet-flexible” Pd-PEPPSI complexes
with their strong σ-donor ability, have been well established as
the most powerful and efficient supporting ligands in Pd-
catalyzed cross-coupling reactions. Consequently, a family of
bulky, electron-rich NHCs developed have made great
improvements in Suzuki-Miyaura cross-coupling reactions.[4]
Despite the significant progress, several drawbacks were still
existed. For instance, the reactions typically required inert
atmosphere, while the highly sensitive of NHCs-Pd(0) toward
oxygen molecule would terminate the catalytic cycle.[4b,5]
Besides, the requisite strong bases limited the functional group
tolerance when aryl chlorides were selected as the electrophilic
reagents.[4g,6] In contrast, the weak bases, such as K2CO3,
K3PO4 and Cs2CO3 were rarely achieved.[4d,4j,7] Furthermore, the
coupling of heteroaryl chlorides with heteroarylboronic acids
remained a quite challenging task on the grounds of the
heteroatoms tends to poison the catalytic active center.[8]
Generally, a high palladium loading was employed for the
biheteroaryls syntheses.[4e,9]
on backbones and N-Aryl moieties.
great importance in this theme. Inspired by Glorius’ elegant work
for “bulky-yet-flexible” NHCs
[4c]
as well as our efforts in this
field,[4k] we envisioned that a combination of ancenaphthyl
backbone-based NHCs with flexible bulky substitution on N-aryl
moieties might allow a new modular and systematic way to fine-
tune the electronic and steric environment of the palladium
center (Scheme 1). Herein, we designed and synthesized a
number of Pd-PEPPSI complexes bearing “bulky-yet-flexible”
substitution, which exhibited high catalytic activity in the Suzuki-
Miyaura cross-coupling of (hetero)aryl chlorides and
(hetero)arylboronic acids at low palladium loading in the
presence of weak base in air.
The α-diimine compound were readily synthesized via one-
pot model reaction by ZnCl2/HOAc,[10] then the procedures for
the synthesis of the corresponding N-heterocarbene salts and
Pd-PEPPSI complexes (C1-C5) were according to previous
synthetic routes.[4k, 5c, 5d] All these prepared palladium complexes
are air and moisture stable. Single crystals for the solid-state
structure of C1 (see ESI†) and C4 were determined and a
thermal ellipsoid representation at the 30% probability level was
shown. As depicted in Figures 1, the N-aryl moieties are roughly
perpendicular to the coordination plane, while the bulky steric of
the 2-benzhydryl on N-aryl moieties are oriented over one
direction of the axial sites of the palladium atom, which may
greatly enhance the stability of metal center.[11] On the other
hand, the other N-aryl group of 6-methyl would be flexible and
leaves open sites for the oxidative addition and subsequent
transformation process in the transformation. Therefore, the
well-defined “bulky-yet-flexible” palladium complexes would
provide preferential space for tuning the catalytic properties.
To further extend application of this reaction, it is highly
desirable to perform the reaction under mild conditions.
Undoubtedly, the development of new ligands continues to be of
[a]
J.-S. Ouyang, Y.-F, Li, H.-D. Huang, D.-D. Lu, Dr F.-S. Liu
School of Chemistry and Chemical Engineering, Guangdong
Cosmetics Engineering & Technology Research Center
Guangdong Pharmaceutical University
Zhongshan, Guangdong, 528458, China
E-mail: fengshou2004@126.com
‡Both authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
both isopropyl and benzhydryl would retard the oxidative
addition process, and therefore diminish the efficiency of the
palladium precatalyst.[15] Thus, the optimization of the
precatalyst showed that C3 gave the highest yields and it was
selected as the palladium source for further study.
Table 1. Screening of the palladium precatalysts on Suzuki-Miyaura cross-
coupling reactiona
Run
Pd complex
Loading
(mol%)
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.025
0.01
Base
Yield
(%)b
NR
NR
10
Figure 1. ORTEP drawing of C4 (ellipsoids are drawn at the 30% probability
level).
1
PdCl2
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
2
PEPPSI-IPr
PEPPSI-IPrAn
PEPPSI-IPr*
3
Furthermore, the electron-donor ability of the synthesized
NHCs ligand was evaluated. The [(NHC)IrCl(CO)2] was prepared
(see ESI†) and the CO stretching frequencies on IR spectrum
recorded at 1979 and 2062 cm−1, respectively. It is significant
that the TEP effect is determined as 2047.4 cm-1, which is lower
4
30
5
PEPPSI-IPent
14
6
C1
C2
C3
C4
C5
C3
C3
91
7
89
98 (97)c
than the value of the classical [(IPr)IrCl(CO)2] (2050.2 cm-1) [12]
therefore indicating the incorparation of ancenaphethyl
backbone would led to stronger σ-donor ability on the NHCs[13]
,
8
9
96
.
10
11
12
10
To explore the effect of catalytic structure on biaryl
formation, Suzuki-Miyaura coupling of 4-chlorotoluene with
phenylboronic acid was selected as a model reaction (see ESI†
86
0.005
51
[a] Reaction conditions: 4-chlorotoluene (1.0 mmol), phenylboronic acid (1.2
mmol), K2CO3 (2 mmol), EtOH (4 mL), in air. [b] GC yields. [c] Isolated yields.
o
for other model reaction). The reaction was carried out at 80 C
using K2CO3 as the base in air. As illustrated in Table 1, in the
presence of a low palladium of 0.025 mol%, commercially
available PdCl2 and Pd-PEPPSI-IPr were tested and no product
generated under the reaction conditions. Other most powerful
precatalysts, such as Pd-PEPPSI-IPrAn, Pd-PEPPSI-IPr* and Pd-
PEPPSI-IPent, were also conducted. However, only low to
moderate yields were obtained. In contrast, the Pd-PEPPSI
complexes of C1 and C2 bearing 2-benzhydryl-4,6-dimethyl on
N-aryl moieties in this study, giving the product of 4-methyl-1,1'-
biphenyl (3aa) in high yields of 91 and 89%, respectively. These
results illustrated that the strong σ-donor ability as well as
“flexible steric bulk” on N-aryl moieties have considerable
influence on the stabilization of the active Pd(0) center and
promote the catalytic process under mild reaction conditions.[4c]
To our delight, replacing the methyls into benzhydryl groups on
the para-position of the N-aryl moieties, the precatalysts of C3
and C4 turned out to be highly efficient and nearly quantitative
yields of 98 and 96% were obtained, respectively. When the
concentrations of C3 was further reduced to 0.01 and 0.005
mol%, the cross-coupling product was obtained in a satisfying
yields of 86 and 51%, respectively. Probably, the excellent
catalytic performance of C3 could be resulted from an extra
attractive π-stacking interaction between the para-benzhydryl
groups and the aryl chlorides, which would further accelerated
the oxidative addition step in the cross coupling.[14] Moreover, C5
with bulkier ortho-isopropyl group on N-aryl moieties was also
applied. Quite out of our expectation, a poor yield of 10% was
observed. Although the reason is unclear, it might be that the
rather congested rigid structure derived from the combination of
With the optimal reaction conditions established, we probed
the substrate scope of the (hetero)aryl chlorides with various
arylboronic acid (more examples see ESI†). As can be seen
from Table 2, electron-donation, -neutral and –withdrawing as
well as sterically hindered groups on the aryl chlorides are
tolerant to provide products in excellent yields. For instance, aryl
chlorides with a methyl group on the ortho-, meta- and para-
position of the phenyl ring, gave the coupling products 5aa-5cc
in 82-98% yields. Other valuable functional groups such as -
MeO, -NO2, -CN and -CH3CO, were also accomplished in
moderate to good yields under optimal conditions (Table 2, 5ed-
5ke).
In
particular,
the
acid
unactivited
and 1-chloro-2-
3,5-
bis(trifluoromethyl)phenylboronic
methoxybenzene were successfully coupled to synthesize 5ed
even at a 0.05 mol% palladium loading (Table 2). Furthermore,
the key industrial precursors of 5jf and 5ke were also proceeded
in excellent yields at a concentration palladium loading of 0.1
mol%.[16] When the sterically hindered 2-chloro-1,3-
dimethylbenzene was used as electrophilic reagent, the tri-ortho-
substituted biaryls 5lc was isolated in a high yield of 91%.
Moreover, reactions were extended to triple coupling, producing
the corresponding ployaryls in very good to excellent yields
(Table 2, 6 and 7).[4h] Encouraged by the excellent performance
of C3, we next explored the scope of a variety of heteroaryl
chlorides with the arylboronic acid bearing ortho-substituents. To
our delight, a wide variety of heteroaryl chlorides, such as 2-
substituted chloropyridines (-Me, -OMe, -CN, -F), 3-
chloropyridine, 2-chloropyrazine, 2-chloroquinoline and 2-
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
chlorothiophene, were all compatible under these reaction
To highlight the catalytic applicability of C3 further, we set
out to develop the most challenging protocols for the synthesis
of biheteroayls and ployheteroarenes,[9] as the heteroaryl
boronic acids tend to undergo deboronation at elevated
temperatures and the heteroatoms would poison palladium
species.[8] Under our optimal conditions, various heteroaryl
chlorides coupled well with heteroarylboronic acids and gave
good product yields (see ESI† for more substrates scope). For
conditions.
Particularly,
this
protocol
successfully
accommodated free amino groups without additional protection
procedures to obtain product 8ec in 98% yield. Double coupling
of 2,6-dichloropyridine and 2,6-dichloropyrazine with o-
tolylboronic acids, also carried efficiently to give the coupling
products 12 and 13 in high yields.
example,
3-thienyl,
2-furanyl,
benzo[b]thien-2-yl
and
Table 2. Suzuki-Miyaura cross-coupling reaction of (hetero)aryl chlorides with
arylboronic acidsa
benzo[b]furan-2-yl boronic acids, were all successfully reacted
with 2-chloropyridine containing a variety of functional groups (-
Me, -F, -CN, -OMe, -NH2) in high yields (Table 3, 14ah-14gh).[8]
In addition, 2-chloropyrazine and 2-chloroquinoline coupled
smoothly with 2-thiopheneboronic acid to form the
corresponding biheteroaryls in excellent yields (Table 3, 16al
and 17ai). Nevertheless, no reaction occurred when 2-
Table 3. Suzuki-Miyaura cross-coupling reaction of heteroaryl chlorides with
heteroarylboronic acidsa
[a] Reaction conditions: (hetero)aryl chloride (1.0 mmol), (hetero)arylboronic
acid (1.2 mmol), K2CO3 (2 mmol), EtOH (4 mL), in air, C3 (0.025 mol%),
isolated yields. [b] Reaction conditions: C3 (0.05 mol%). [c] Reaction
conditions for triple coupling: (hetero)aryl chloride (1.0 mmol),
(hetero)arylboronic acid (3.6 mmol), K2CO3 (6 mmol), EtOH (4 mL), in air, C3
(0.05 mol%). [d] Reaction conditions: C3 (0.1 mol%). [e] Reaction conditions
for double coupling: (hetero)aryl chloride (1.0 mmol), (hetero)arylboronic acid
(2.4 mmol), K2CO3 (4 mmol), EtOH (4 mL), in air, C3 (0.1 mol%).
[a] Reaction conditions: (hetero)aryl chloride (1.0 mmol), (hetero)arylboronic
acid (1.2 mmol), K2CO3 (2 mmol), EtOH (4 mL), in air, C3 (0.05 mol%),
isolated yields. [b] Reaction conditions: C3 (0.1 mol%). [c] Reaction conditions:
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
The palladium catalyst were synthesized as described in the Supporting
Information.
C3 (0.5 mol%). [d] Reaction conditions of double coupling: (hetero)aryl
chloride (1.0 mmol), (hetero)arylboronic acid (2.4 mmol), K2CO3 (4 mmol),
EtOH (4 mL), in air, C3 (0.1 mol%).
General procedures for the coupling products
thiopheneboronic acid and 2-chloropyridine were selected as
coupling partners. To our delight, increasing the catalyst loading
to 0.5 mol%, the substrates such as 2-chlorothiophene and 3-
chloropyridine were proved active, which gave the desired
cross-coupling products of 15ah, 15ai, 18ah and 18ak in
satisfied yields of 90, 80, 74 and 80%, respectively. Significantly,
the double couplings of 2,6-dichloropyridine and 2,6-
dichloropyrazine with heteroarylboronic acids afforded the
corresponding polyheteroarenes in high yields (Table 3, 19-22).
Encouraged by the above remarkable activities of C3, we
further expanded the coupling reactions of various 5-heteroaryl-
2-chloropyridine with sulfur- and oxygen-containing heteroaryl
boronic acids. As can be seen in Table 4, upon performing the
reactions with 0.5 mol% of palladium, various biheteroaryl
chlorides bearing challenging sterically hindered and electron-
To a mixture of (hetero)aryl chlorides (1.0 mmol), (hetero)arylboronic
acids (1.2 mmol), catalyst C3 (0.5-0.025 mol%) and K2CO3 (2.0 equiv,
276 mg) in EtOH (4.0 mL) under aerobic conditions. The system was
stirred at 80 °C for 2 h. After cooled to room temperature, The reaction
mixturewas diluted with 30 mL of water, and then extracted with EtOAc
(10 mL×3). The organic layer was dried by Na2SO4 and evaporated
under reduced pressure. The residue was purified via flash
chromatography on silica gel (PE/EA = 10:1) to give the desired product,
finally determined by 1H NMR and 13C NMR spectroscopy (see the
Supporting Information).
Acknowledgements
The financial supports from Distinguished Young Talents in
Higher Education of Guangdong (No. Yq2013101) is gratefully
acknowledged.
rich
chloropyridine, 5-(1,2-dimethyl-1H-imidazole)-2-chloropyridine,
5-{imidazole[1,2-a]pyridine}-2-chloropyridine and 5-(3,5-
substituents
such
as
5-(2,4-dimethylthiazole)-2-
dimethylisoxazole)-2-chloropyridine, were also suitable for this
coupling to obtain the corresponding polyheteroarenes in
excellent yields (Table 4, entry 23-30).
Keywords: N-heterocyclic carbene • palladium catalysts •
Suzuki-Miyaura cross-coupling • (hetero)aryl chlorides •
(hetero)arylboronic acids
Table 4. The synthesis of ployheteroarenes via Suzuki-Miyaura cross-coupling
reactiona
[1]
[2]
[3]
a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2475-2483; b) M.
Kertesz, C. H. Choi, S. Yang, Chem. Rev. 2005, 105, 3448-3481; c) L.
Pu, Acc. Chem. Res. 2012, 45, 150-163.
a) H. Li, C. C. C. J. Seechurn, T. J. Colacot, ACS Catal. 2012, 2, 1147-
1164; b) P. G. Gildner, T. J. Colacot, Organometallics. 2015, 34, 5497-
5508.
a) W. A. Herrmann, C.-P. Reisinger, M. Spiegler, J. Organomet. Chem.
1998, 557, 93-96; b) C. W. K. Gstöttmayr, V. P. W. Böhm, E.
Herdtweck, M. Grosche, W. A. Herrmann, Angew. Chem. Int. Ed. 2002,
41, 1363-1365.
[4]
a) W. A. Herrmann, Angew. Chem. Int. Ed. 2002, 114, 1342-1363; b) O.
Navarro, R. A. Kelly, S. P. Nolan, J. Am. Chem. Soc. 2003, 125, 16194-
16195; c) G. Altenhoff , R. Goddard , C. W. Lehmann, F. Glorius, J.
Am. Chem. Soc. 2004, 126, 15195-15201; (d) C. J. O’Brien, E. A. B.
Kantchev, C. Valente, N. Hadei, G. A. Chass, A. Lough, A. C.
Hopkinson, M. G. Organ, Chem. Eur. J. 2006, 12, 4743-4748; e) M. G.
Organ, S. Çalimsiz, M. Sayah, K. H. Hoi, A. J. Lough, Angew. Chem. Int.
Ed. 2009, 48, 2383-2387; f) L. Wu, E. Drinkel, F. Gaggia, S.
Capolicchio, A. Linden, L. Falivene, L. Cavallo, R. Dorta, Chem. -Eur. J.
2011, 17, 12886-12890; g) A. Chartoire, M. Lesieur, L. Falivene, A. M.
Slawin, L. Cavallo, C. S. Cazin, S. P. Nolan, Chem. -Eur. J. 2012, 18,
4517-4521; h) T. Tu, Z. Sun, W. Fang, M. Xu, Y. Zhou, Org. Lett. 2012,
14, 4250-4253; i) Y. Zhang, V. César, G. Storch, N. Lugan, G. Lavigne,
Angew. Chem. Int. Ed. 2014, 53, 6482-6486; j) F. Rajabi, W. R. Thiel,
Adv. Synth. Catal. 2014, 356, 1873-1877; k) X.-B. Lan, F.-M. Chen, B.-
B. Ma, D.-S. Sheng, F.-S. Liu, Organometallics. 2016, 35, 3852-3860; l)
P. Lei, G. Meng, M. Szostak, ACS Catal. 2017, 7, 1960-1965; m) T. B.
Halima, W. Zhang, I. Yalaoui, X. Hong, Y.-F. Yang, K. N. Hou, S. G.
Newman, J. Am. Chem. Soc. 2017, 139, 1311-1318.
[a] Reaction conditions: (hetero)aryl chloride (1.0 mmol), (hetero)arylboronic
acid (1.2 mmol), K2CO3 (2 mmol), EtOH (4 mL), in air, C3 (0.5 mol%), isolated
yields.
In summary, a type of well-defined Pd-PEPPSI complexes
for Suzuki-Miyaura coupling reaction have been developed. The
electronic and steric effect of the designed palladium complexes
was systematically investigated, which demonstrated that the
introduction of strong σ-donor ability on bulky backbone and
“flexible steric bulk” environment provided by the N-aryl moieties,
significantly enhanced the catalytic activities with excellent
functional group compatibility. A wide range of biologically
relevant bi(hetero)aryls and poly(hetero)aryls were smoothly
installed under mild reaction conditions, such as low palladium
loading, weak base and aerobic environment.
[5]
a) M. S. Viciu, R. M. Kissling, E. D. Stevens, S. P. Nolan, Org.Lett. 2002,
4, 2229-2231; b) O. Diebolt, P. Braunstein, S. P. Nolan, C. S. J. Cazin,
Chem. Commun. 2008, 3190-3192; c) X.-X. He, Y. Li, B.-B. Ma, Z. Ke,
F.-S. Liu, Organometallics. 2016, 35, 2655-2663; d) X.-B. Lan, Y. Li, Y.-
F. Li, D.-S. Shen, Z. Ke, F.-S. Liu, J. Org. Chem. 2017, 82, 2914-2925.
Experimental Section
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
[6]
[7]
a) N. Marion , O. Navarro , J. Mei , E. D. Stevens , N. M. Scott, S. P.
Nolan, J. Am. Chem. Soc. 2006, 128, 4101-4111; b) A. Chartoire, X.
Frogneux, S. P. Nolan, Adv. Synth. Catal. 2012, 354, 1897-1901.
a) C. C. C. J. Seechurn, S, L. Parisel, T. J. Colacot, J. Org. Chem. 2011,
76, 7918-7932; b) A. Azua, J. A. Mata, P. Heymes, E. Peris, F. Lamaty,
J. Martinez, E. Colacino, Adv. Synth. Catal. 2013, 355, 1107-1116; c) F.
Izquierdo, M. Corpet, S. P. Nolan, Eur. J. Org. Chem. 2015, 1920-1924;
d) K. Alam, S. M. Kim, D. J. Kim, J. K. Park, Adv. Synth. Catal. 2016,
358, 2661-2670.
[8]
[9]
S. Ge, J. F. Hartwing, Angew. Chem. Int. Ed. 2012, 51, 12837-12841.
a) T. Kinzel, Y. Zhang, S. L. Buchwald, J. Am. Chem. Soc. 2010, 132,
14073-14075; b) M. Kuriyama, S. Matsuo, M. Shinozawa, O. Onomura,
Org. Lett. 2013, 15, 2716-2719; c) L. M. Guard, M. M. Beromi, G. W.
Brudvig, N. Hazari, D. J. Vinyard, Angew. Chem. Int. Ed. 2015, 54,
13352-13356; d) J. Almond-Thynne, D. C. Blakemore, D. C. Prydeb, A.
C. Spivey, Chem. Sci. 2017, 8, 40-62.
[10]
[11]
a) M. Gasperini, F. Ragaini, S. Cenini, Organometallics. 2002, 21,
2950-2957; b) L.-D. Li, C. S. B. Gomes, P. T. Gomes, M. T. Duarte, Z.-
Q. Fan, Dalton Trans. 2011, 40, 3365-3380.
a) C. Valente, S. Çalimsiz, K. H. Hoi, D. Mallik, M, Sayah, M. G. Organ,
Angew. Chem. Int. Ed. 2012, 51, 3314-3332; b) S. Meiries, G. L. Duc, A.
Chartoire, A. Collado, K. Speck, K. S. A. Arachchige, Al. M. Z. Slawin,
S. P. Nolan, Chem. Eur. J. 2013, 19, 17358-17368.
[12]
R. A. Kelly, H. Clavier, S. Giudice, N. M. Scott, E. D. Stevens, J.
Bordner, I. Samardjiev, C. D. Hoff, L. Cavallo, S. P. Nolan,
Organometallics. 2008, 27, 202-210.
[13] K. V. Vasudevan, R. R. Butorac, C. D. Abernethy, A. H. Cowley, Dalton
Trans. 2010, 39, 7401-7408.
[14] a) B. R. Dible, R. E. Cowley, P. L. Holland, Organometallics. 2011, 30,
5123-5132; b) T. Szilvási, T. Veszprémi, ACS Catal. 2013, 3, 1984-
1991.
[15] W. C. Fu, Z. Zhou, F. Y. Kwong, Org. Chem. Front. 2016, 3, 273-276.
[16]
L. Chen, P. Ren, B. P. Carrow, J. Am. Chem. Soc. 2016, 138, 6392-
6395.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201701076
ChemCatChem
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
“Bulky-yet-flexible” Pd-PEPPSI
complexes have been developed and
exhibited high reactivity for Suzuki-
Miyaura cross-coupling in the
presence of K2CO3 in air.
Jia-Sheng Ouyang‡, Yan-Fang Li‡, Fei-
Dong Huang, Dong-Dong Lu, and Feng-
Shou Liu *
Page No. – Page No.
The highly efficient Suzuki-Miyaura
cross-coupling
chlorides and (hetero)arylboronic
acids catalyzed by “bulky-yet-
flexible” Pd-PEPPSI complexes in air
of
(hetero)aryl
This article is protected by copyright. All rights reserved.