Room temperature nickel(II) complexes [(4-MeOC6H 4)Ni(PCy3)2OTs and Ni(PCy3) 2X2]-catalyzed cross-coupling reactions of aryl/alkenyl sulfonates with arylboronic acids

Article abstract of DOI:10.1002/adsc.201100151

Room temperature nickel(II) complexes [(4-MeOC₆H ₄)Ni(PCy₃)₂OTs and Ni(PCy₃) ₂X₂ (X=Cl, Br)]-catalyzed cross-coupling reactions of aryl/alkenyl sulfonates with arylboronic acids are described. The nickel(II) complex (4-MeOC₆H₄)Ni(PCy₃)₂OTs proved to be a general catalyst for the Suzuki-Miyaura cross-coupling reactions of aryl sulfonates with arylboronic acids. By limiting the amount of the water in the initial catalytically active Ni(0) species generation stage, Ni(PCy ₃)₂X₂ (X=Cl, Br) could also be efficient catalysts for the cross-coupling reactions a variety of aryl/activated alkenyl tosylates with arylboronic acids. The mild reaction condition, the easy availability of the catalysts and excellent coupling yields make these catalyst systems potentially useful in organic synthesis. Copyright

Full text of DOI:10.1002/adsc.201100151

FULL PAPERS
DOI: 10.1002/adsc.201100151
Room Temperature Nickel(II) Complexes [(4-MeOC H )Ni-
6
4
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(PCy ) OTs and Ni(PCy ) X ]-Catalyzed Cross-Coupling
A
H
U
G
R
N
N
3
2
3 2
2
Reactions of Aryl/Alkenyl Sulfonates with Arylboronic Acids
a
a
a
a
Chun-Hui Xing, Jeng-Ru Lee, Zhen-Yu Tang, Jin Rong Zheng,
a,
and Qiao-Sheng Hu *
Department of Chemistry, College of Staten Island and the Graduate Center of the City University of New York, Staten
Island, New York 10314, USA
a
Fax : (+1)-718-9823910; phone: (+1)-718-982-3901; e-mail: qiaosheng.hu@csi.cuny.edu
Received: March 2, 2011; Revised: April 29, 2011; Published online: July 22, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adcs.201100151.
Abstract: Room temperature nickel(II) complexes Br) could also be efficient catalysts for the cross-cou-
[
(4-MeOC H )Ni AHCTUNGTRENNUGN( PCy ) OTs and Ni ACHTUNGNERNUT(G PCy ) X (X= pling reactions a variety of aryl/activated alkenyl to-
6 4 3 2 3 2 2
Cl, Br)]-catalyzed cross-coupling reactions of aryl/al- sylates with arylboronic acids. The mild reaction con-
kenyl sulfonates with arylboronic acids are de- dition, the easy availability of the catalysts and excel-
scribed. The nickel(II) complex (4-MeOC H )Ni- lent coupling yields make these catalyst systems po-
6
4
ACHTUNGTRENNUNG( PCy ) OTs proved to be a general catalyst for the tentially useful in organic synthesis.
3 2
Suzuki–Miyaura cross-coupling reactions of aryl sul-
fonates with arylboronic acids. By limiting the Keywords: alkenyl tosylates; aryl arenesulfonates;
amount of the water in the initial catalytically active arylboronic acids; cross-coupling; nickel(II) com-
Ni(0) species generation stage, Ni CAHTUNGTRNEUNG( PCy ) X (X=Cl, plexes
3 2 2
Introduction
Pd
ACHTUNGTNERNU(GN OAc) /Buchwaldꢀs biphenylphosphine ligand-cata-
2
lyzed Suzuki cross-coupling of electron-deficient aryl
[
7]
Aryl/alkenyl arenesulfonates, readily accessible from arenesulfonates at 808C. Due to the easy availability
phenols/enols and arenesulfonyl chlorides, constitute and stability of aryl/alkenyl arenesulfonates, the de-
a large family of widely available organic compounds. velopment of efficient catalyst systems for the cross-
While aryl/alkenyl triflates, analogs of aryl/alkenyl coupling reactions with aryl/alkenyl arenesulfonates
arenesulfonates, exhibited reactivities comparable to as substrates have attracted much attention since 2003
[
9–15]
those of aryl/alkenyl bromides/iodides and have been and a number of reports have appeared.
established as excellent substrates for Suzuki cross-
In our laboratory, we are interested in developing
[
1–3]
coupling reactions,
aryl/alkenyl arenesulfonates highly active/efficient transition metal catalysts for
have not been considered as general coupling partners cross-coupling reactions of cost-effective, widely avail-
for such cross-coupling reactions due to their low re- able substrates including aryl/alkenyl arenesulfo-
[
4–8]
[16,17]
activity when we started our research back in 2003.
Prior to 2003, only scattered reports appeared.
nates.
For Ni(COD) /PCy as the first general catalyst for the
example, Percec reported in 1995 the cross-coupling room temperature cross-coupling reactions of aryl/al-
In this context, we have reported
[
4–9]
ACHTUNGTRENNUNG
2
3
[17]
of aryl tosylates/mesylates at elevated temperatures kenyl arenesulfonates with arylboronic acids. Al-
by using Ni ACHTUNGTRENNUNG( DPPF)Cl /Zn. Kobayashi and Mizojiri though Ni ACHTUTGNREN(NNUG COD) /PCy proved to be an excellent cat-
2
[
4]
2
3
showed that Ni ACHTUNGTRENNUNG( PPh ) Cl could catalyze the coupling alyst system, the air-sensitivity of the Ni AHCUTGNERNNGU( COD) /PCy
3
2
2
2
3
reaction of electron-deficient aryl arenesulfonates catalyst system, especially Ni ACHTUGNTERNN(UNG COD) , prompted us to
2
[
5]
with lithium arylborates. In 2001, Monteiro reported explore the use of operationally convenient nickel(II)
the use of Ni(PCy ) Cl as the catalyst precursor and complexes as catalyst precursors. We found readily
arylboronic acids as reducing reagents under elevated available,
ACHTUNGTRENNUNG
3
2
2
air-stable
Ni(II)
complexes,
and Ni ACHTUNGTRENUNG( PCy ) Br , were
3 2 2
(4-
[6]
[17a]
temperature.
Soon after, Lakshman reported MeOC H )Ni(PCy ) OTs
A
H
U
G
R
N
N
6
4
3
2
Adv. Synth. Catal. 2011, 353, 2051 – 2059
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2051

Chun-Hui Xing et al.
FULL PAPERS
excellent catalysts for the room temperature Ni(0)- Table 2. Room temperature (4-MeOC
H )Ni ACHTUGNTREUNNG( PCy ) OTs-cat-
4 3 2
alyzed cross-couplings of aryl sulfonates with arylboronic
6
catalyzed cross-coupling reactions of aryl/activated al-
kenyl arenesulfonates with arylboronic acids. Herein
our results on using these Ni(II) complexes as cata-
lysts for the room temperature cross-coupling reac-
tions of aryl/activated alkenyl arenesulfonates with ar-
ylboronic acids are described.
[a]
acids.
Results and Discussions
Nickel(II) Complex 4-MeOC H Ni(II) ACHTUNGTRENUNG( PCy ) OTs as
3 2
6
4
a Catalyst for Cross-Coupling Reactions of Aryl
Sulfonates with Arylboronic Acids
Because the nickel(II) complex (4-MeOC H )Ni-
6
4
ACHTUNGTRENNUNG( PCy ) OTs, the oxidative addition adduct of 4-MeO-
3 2
C H OTs with Ni CAHTUNGTRNEUN(G COD) /PCy , was observed as the
2 3
6
4
intermediate for Ni
ACHTUNGTNRENUNG( COD) /PCy -catalyzed cross-cou-
2 3
pling reactions of 4-methyoxyphenyl tosylate with
[
17a]
phenylboronic acid,
we began our study to test (4-
MeOC H )Ni(PCy ) OTs as the catalyst for the cross-
ACHTUNGTRENNUNG
6
4
3 2
coupling reaction of p-tolyl tosylate with phenylbor-
[18]
onic acid.
(PCy ) OTs was almost as active as the Ni ACHTUNGRETNNUNG( COD) /
2
We found that (4-MeOC H )Ni-
6 4
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
3
2
PCy catalyst (Table 1, entry 1). We also found using
3
additional amounts of PCy for the catalyst was not
3
necessary (Table 1, entries 1–3). By using 2 equiva-
lents of water as an additive, the cross-coupling reac-
tion occurred efficiently (Table 1, entry 4).
By using (4-MeOC H )Ni ACHTUGNTRNEUNG( PCy ) OTs as the cata-
6
4
3 2
lyst, the cross-coupling reactions of a variety of aryl
arenesulfonates with arylboronic acids were examined
and excellent yields were observed for all aryl arene-
sulfonates tested (Table 2, entries 1–15). We also
found that this complex was an efficent catalyst for
the cross-coupling reactions of p-tolyl mesylate with
[a]
Reaction conditions: aryl sulfonate (1.0 equiv.), arylbor-
onic acid (1.5 equiv.), K PO (3 equiv.), THF (2 mL),
3
4
H O (2 equiv.), room temperature.
Isolated yields (average of two runs).
Reaction time: 36 h.
2
Table 1. Room temperature nickel(II) complex (4-
[b]
[c]
MeOC H )Ni ACHTUNGTRENNUNG( PCy ) OTs-catalyzed cross-couplings of p-
3 2
[a]
6
4
tolyl tosylate with phenylboronic acid.
arylboronic acids (Table 2, entries 16 and 17). These
results suggest that (4-MeOC H )Ni(PCy ) OTs as
AHCTUNGTRENNUNG
6
4
3 2
well as its analogs could be an operationally conven-
ient substitute for the Ni(COD) /PCy catalyst system
AHCTUNGTRENNUNG
2
3
for the room temperature cross-coupling reactions of
aryl/alkenyl sulfonates with arylboronic acids.
Bis(tricyclohexylphosphine)nickel(II) Bromide
[
Ni ACHTUNGTERNNUG( PCy ) Br ] as a Catalyst for Room Temperature
3 2 2
Ni(0)/PCy -Catalyzed Suzuki Cross-Coupling
3
[
[
a]
b]
Reactions of Aryl/Activated Alkenyl Arenesulfonates
Reaction conditions: p-tolyl tosylate (1.0 equiv.), phenyl-
boronic acid (1.5 equiv.), K PO (3 equiv.), THF (2 mL),
3
4
room temperature.
Our success in using the nickel(II) complex (4-
1
Based on H NMR analysis.
MeOC H )Ni ACHTNUGTRNNEG(U PCy ) OTs as the operationally conven-
6 4 3 2
2052
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Adv. Synth. Catal. 2011, 353, 2051 – 2059

Room Temperature Nickel(II) Complexes [(4-MeOC H )Ni ACUTHNGTRENNUG(N PCy ) OTs and Ni AHCTUNGERTNNUN(G PCy ) X ]-Catalyzed Cross-Coupling
3 2 3 2 2
6
4
ient catalyst encouraged us to further explore whether of Ni
ACHTUNGTRENN(UG PCy ) Br complex turned to colorless within
3 2 2
readily available, air-stable Ni(PCy ) X (X=Cl, Br) 15 min when mixed with phenylboronic acid, and the
AHCTUNGTRENNUNG
3
2
2
complexes could be suitable catalyst precursors or cross-coupling reaction did not take place (Table 3,
catalysts for the room temperature Suzuki cross-cou- entries 1–3). As commercially available phenylboronic
pling of aryl/alkenyl arenesulfonates with arylboronic acid could contain small amounts of phenol and
acids. In our initial study, we found that the catalyst water, commercially received phenylboronic acid was
generated from Ni
as Ni(COD) /PCy for the cross-coupling of 4-(p-tol- nylboronic acid was washed with hexanes to remove
uenesulfonyloxy)coumarins and 4-(p-toluenesulfonyl- the small amount of phenol; in method two, phenyl-
ACHTUNGTRENNGU( PCy ) Cl /n-BuLi was as efficient thus treated with three methods. In method one, phe-
3 2 2
ACHTUNGTRENNUNG
2
3
[
17b]
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
oxy)-2(5H)-furanone with phenylboronic acid.
However, the Ni species in-situ generated from water, and in method three, phenylboronic acid was
Ni(PCy ) Cl /n-BuLi cannot catalyze the Suzuki cou- washed with hexanes and dried under vacuum to
boronic acid was dried under vacuum to remove
ACHTUNGTRENNUNG
3
2
2
pling of aryl arenesulfonates with arylboronic acids. remove both small amounts of phenol and water. The
In addition, the use of n-BuLi as the reducing reagent treated phenylboronic acid was then tested for the re-
is operationally inconvenient as n-BuLi is air/mois- action. We found that similar results were observed
ture-sensitive and incompatible with many functional with phenylboronic acid being used as received and
groups. As Ni
ACHTUNGTRENNUNG( PCy ) Cl has been reported to be re- being washed with hexanes (Table 3, entries 1–6).
3 2 2
duced with arylboronic acids for cross-coupling reac- When dried phenylboronic acid (phenylboroxine) was
[
6]
tions at an elevated temperature, we thus decided to used for the reaction, we observed that the
focus on using arylboronic acids as reducing reagents Ni
to generate catalytic active Ni(0) species.
ACHTUNGTRENN(UG PCy ) Br complex turned to a yellow or orange
color, and found that the cross-coupling reaction oc-
3 2 2
We first tested the use of Ni
ACHTUNGRTNNGE(U PCy ) Cl as the cata- curred (Table 3, entry 7). We further found that
3 2 2
lyst for the room temperature cross-coupling reaction adding K PO portionwise improved the reaction con-
3
4
of p-tolyl tosylate with phenylboronic acid and found version (Table 3, entries 8 and 9). Whether phenylbor-
that Ni(PCy ) Cl was not an efficient catalyst onic acid was washed with hexanes seemed not to be
Scheme 1). We also found even with an additional critical, as evidenced by the similar results observed
reducing agent Zn, Ni(PCy ) Cl still could not cata- for reactions with phenylboronic acid being only
ACHTUNGTRENNUNG
3
2
2
(
AHCTUNGTRENNUNG
3
2
2
lyze the cross-coupling reaction. After a number of dried (Table 3, entries 10–14). These results suggested
unsuccessful trials and careful observations, we found that the amount of water, not the small amount of
the main reasons why Ni ACHTUNGERTNNUN(G PCy ) Cl was an inefficient phenol, should be the key for using Ni ACHTUNGTRNUNEGN( PCy ) X as
3
2
2
3
2
2
catalyst were based on two issues: its low solubility in the catalysts for the cross-coupling reaction. It was
the reaction solvent THF and, more importantly, the also found that if the reaction system was dry (with
amount of the water existing in the reaction system.
The low solubility issue of Ni(PCy ) Cl in THF would take very long to generate the catalytically
could be circumvented by using Ni AHCTUNRTGNEG(UN PCy ) Br which active Ni(0) species. It was thus clear to us that the
3 2 2,
dried K PO and arylboroxine), the reduction process
3 4
AHCTUNGTRENNUNG
3
2
2
is more soluble in THF, as the catalyst. To determine amount of water in the reduction of Ni(II) to Ni(0)
the role of water for this cross-coupling reaction pro- process cannot be too much, which would cause the
cess, we have carried out a systematic study by using Ni
Ni(PCy ) Br as the catalyst and 4-(p-toluenesulfonyl- active catalyst, or too little, which would require a
oxy)coumarin as the substrate.
summarized in Table 3. As K PO is an inorganic base balance to generate catalytically active Ni(0) species
ACHTUNGTRENN(UG PCy ) Br complex to turn into a colorless and in-
3 2 2
ACHTUNGTRENNUNG
3
2
2
[
20,21]
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
Our results are very long Ni(0) generation time. We found a good
3
4
and is insoluble in THF, it was ground (by using a would use dried phenylboronic acid and with ground
porcelain mortar for 10 min) into fine powder in all K PO being added portionwise. Further testing
3
4
our trials. We found when using phenylboronic acid as showed that the use of additional amounts of PCy3
received and ground K PO , the dark green solution was not necessary, but adding 1–3 equivalents of
3
4
water to the reaction system after the generation of
Ni(0) species was beneficial for the reaction (Table 3,
entries 15–22). The beneficial effect of water could be
explained in that water might help to dissolve K PO4
3
better, thus facilitating the transmetalation process.
After identifying the reaction conditions (dried ar-
ylboronic acids, portionwise addition of K PO and
3
4
H O as additive), the Ni ACHTUNGNRTEUNG( PCy ) Br -catalyzed cross-
2
3 2 2
coupling reactions of activated alkenyl tosylates with
[
19b,20–23]
arylboronic acids were examined.
Our results
Scheme 1. Room temperature Ni ACHTGNUTRNEUNG( PCy ) Cl -catalyzed Suzuki
3 2 2
cross-coupling reaction of p-tolyl tosylate with phenylboron- are summarized in Table 4. Good to excellent yields
ic acid.
were observed for all substrates tested.
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Chun-Hui Xing et al.
FULL PAPERS
Table 3. Room temperature Ni
A
H
U
G
R
N
U
(PCy ) Br -catalyzed Suzuki
Table 4. Room temperature Ni ACHTUNTGNERNUG( PCy ) Br -catalyzed Suzuki
3 2 2
3
2
2
cross-coupling reactions of 4-(p-toluenesulfonyloxy)coumar-
cross-coupling reactions of activated alkenyl tosylates with
[a]
[a]
in with phenylboronic acids.
arylboronic acids.
[
[
a]
b]
Reaction conditions: tosylate (1.0 equiv.), arylboronic
acid (1.5 equiv.), Ni(PCy ) Br (5 mol%), K PO4
AHCTUNGTRENNUNG
3
2
2
3
(
3 equiv.), THF (2 mL), H O (2 equiv.), room tempera-
2
ture.
Isolated yields (average of two runs).
By using Ni ACTHUNGTRNEUNG( PCy ) Br as the catalyst, the cross-
3 2 2
coupling reaction of aryl arenesulfonates with arylbor-
onic acids was also examined. Compared to the cross-
coupling reactions with 4-(p-toluenesulfonyloxy)cou-
marin as substrate, the cross-coupling of aryl tosylates
with arylboronic acids needed longer reaction time.
The need for longer reaction time might be explained
by the fact that aryl arenesulfonates are less reactive
than activated alkenyl tosylates such as 4-(p-toluene-
sulfonyloxy)coumarin, as established in our compari-
son study. By lengthening the reaction time to 24–
[
[
a]
b]
Reaction conditions: tosylate (1.0 equiv.), phenylboronic
acid (1.5 equiv.), Ni(PCy ) Br (5 mol%), K PO
4
AHCTUNGTRENNUNG
3
2
2
3
(
3 equiv.), THF (2 mL), H O (0–4 equiv.), room tempera-
2
48 h, complete conversions and high isolated yields
ture.
1
were observed for all tosylates tested, including both
Yields based on H NMR analysis.
electron-deficient
and
electron-rich
tosylates
2054
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Adv. Synth. Catal. 2011, 353, 2051 – 2059

Room Temperature Nickel(II) Complexes [(4-MeOC H )Ni ACUTHNGTRENNUG(N PCy ) OTs and Ni AHCTUNGERTNNUN(G PCy ) X ]-Catalyzed Cross-Coupling
3 2 3 2 2
6
4
(
Table 5). We have also come back to use lyst loading [3% for Ni ACHTUNGTERNNUG( COD) /PCy vs. 5% for
2 3
Ni
Ni
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(PCy ) Cl as the catalyst and compared it with Ni
A
T
N
T
E
N
N
(PCy ) X ] and longer reaction time [8–12 h for
3
2
2
3
2
2
A( PCy ) Br . We found Ni
C
H
T
U
N
G
T
R
E
N
N
U
N
G
A
H
U
G
R
N
U
G
A( COD) /PCy and 24–48 h for Ni
H
U
G
E
N
N
A
H
U
G
R
N
U
G
3
2
2
3
2
2
2
3
3
2
2
ilar result as that of Ni
except for a longer time for the generation of catalyti- MeOC H )Ni
A
H
U
G
R
N
U
G
sidering the easy availability and air-stability of (4-
(PCy ) Ots and Ni(PCy ) X (X=Cl,
3
2
2
,
A
H
U
G
R
N
U
G
ACHTUNGTRENNUNG
6
4
3
2
3
2
2
cally active Ni(0) species.
Br), even the requirements of the slightly higher cata-
Compared to other reported transition metal cata- lyst loading and longer reaction time would still favor-
lyst systems for the coupling reaction of aryl tosylates ably place nickel(II) complexes (4-MeOC H )Ni-
6
4
with arylboronic acids, e.g., Pd(0)/Buchwaldꢀs biphe-
ACHTUNGTNERNUN(G PCy ) OTs and Ni ACHTNUTGRENUN(G PCy ) X (X=Cl, Br), especially
the latter, into practically useful catalysts.
3 2 3 2 2
[10]
[15b]
nylphosphines,
Rh(I)/N-heterocyclic carbenes
[
11a,b]
and Ni(0)/graphite,
which all required high reac-
tion temperature and/or more expensive ligands, the
4-MeOC H )Ni(PCy ) OTs and Ni
(
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
A
H
U
G
R
N
U
G
6
4
3
2
3
2
2
Br) catalyst systems can catalyze the reaction at room
temperature. Compared to our originally developed In summary, we have demonstrated that air-stable (4-
Ni(COD) /PCy catalyst system, the Ni(PCy ) X (X= MeOC H )Ni(PCy ) OTs was an efficient catalyst for
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
2
3
3 2
Cl, Br) catalyst system required slightly higher cata- the room temperature cross-coupling reactions of aryl
sulfonates with arylboronic acids. We have further
carried out studies to employ air-stable Ni
ACHTUNGTRENNGU( PCy ) X
3 2 2
Table 5. Room temperature Ni
coupling of aryl arenesulfonates with arylboronic acids.
ACHTUNGERTUNN(NG PCy ) X -catalyzed Suzuki
3 2 2
[a]
(
X=Cl, Br) as the catalysts for the cross-coupling re-
actions. We demonstrated that by limiting the amount
of the water in the initial catalytically active Ni(0)
species generation stage, Ni CAHTUNGTRNEU(GN PCy ) X (X=Cl, Br)
3 2 2
could be efficient catalysts for the cross-coupling reac-
tions. The mild reaction conditions, the easy availabil-
ity of the catalyst systems, and excellent coupling
yields make these Ni(0)/PCy catalyst systems poten-
3
tially useful in organic synthesis. Our study also raised
the possibility that the Ni(0) catalysts generated from
Ni
ACHTUNGTRENN(UG PCy ) X and arylboronic acids might catalyze
3 2 2
Suzuki cross-coupling reactions with other related
[
24]
[25,26]
arenesulfonates and aryl/alkenyl esters
temperature.
at room
Experimental Section
General Procedure for (4-MeOC H )Ni ACHTUNGTENRUNG( PCy ) OTs-
3 2
6
4
Catalyzed Cross-Coupling Reactions of Aryl Arene-
sulfonates with Arylboronic Acids
In a glove-box to a vial containing tosylate (0.5 mmol), aryl-
,
boronic acid (0.75 mmol, 1.5 equiv.), (4-MeOC H )Ni-
6
4
[17a]
A
H
U
G
R
N
N
(PCy ) OTs
(5 mol%) and K PO (1.5 mmol, 3.0 equiv.)
3
2
3 4
was added THF (2 mL) and H O (1.0 mmol, 2.0 equiv). The
2
mixture was stirred at room temperature for 8–24 h. The re-
action was quenched by adding water, and then extracted
with CH Cl (30 mLꢂ2). After removal of solvents, column
2
2
chromatography on silica gel with ethyl acetate/hexane af-
forded the product.
General Procedure for Ni ACHTUNGRTNEUNG( PCy ) Br -Catalyzed Cross-
3 2 2
Coupling Reactions of Aryl Tosylates with Aryl-
boronic Acids
[
a]
Reaction conditions: aryl tosylate (1.0 equiv.), arylboronic
acid (1.5 equiv.), Ni(PCy ) Br (5 mol%), K PO (0.6+
AHCTUNGTRENNUNG
3
2
2
3
4
2
.4 equiv.), THF (2 mL), H O (2 equiv.), room tempera-
In a glove-box, to a vial containing tosylate (1.0 mmol), aryl-
2
ture.
boronic acid (1.5 equiv.), Ni
ACHTUNGTRNNGE(U PCy ) Br (5.0 mol%) and
3 2 2
[
[
b]
c]
Isolated yields (average of two runs).
mol% of Ni(PCy ) Cl was used.
K PO (0.6 mmol, 0.6 equiv.) was added THF (4 mL) under
3
4
5
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
N . The mixture was stirred at room temperature for about
2
3
2
2
Adv. Synth. Catal. 2011, 353, 2051 – 2059
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Chun-Hui Xing et al.
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[28]
1
1
hour. When the color of the reaction mixture changed
3-(4-Methylphenyl)pyridine:
H NMR
(CDCl3,
from dark green to light green or light orange, the remain-
ing K PO (2.4 mmol, 2.4 equiv.) was added, and the color
600 MHz): d=8.85 (s, 1H), 8.57 (br.s, 1H), 7.85 (d, J=
8.4 Hz, 1H), 7.48 (d, J=7.8 Hz, 2H), 7.35–7.33 (dd, J=7.8,
4.8 Hz, 1H), 7.29 (d, J=7.8 Hz, 2H), 2.41 AHCTUNGTERUNNN(G s, 3H); C NMR
3
4
1
3
became bright orange. A few minutes later, H O (2.0 mmol,
2
2.0 equiv.) was added. After the reaction mixture had been
(CDCl , 150 MHz): d=148.3, 148.2, 138.0, 136.6, 135.0,
3
stirred at room temperature for 8–24 h, it was quenched by
adding water, and then extracted with CH Cl (30 mLꢂ2).
134.1, 129.8, 127.0, 127.1, 123.5, 21.1.
3-(3-Methylphenyl)pyridine:
[28]
1
H NMR
(CDCl3,
2
2
After removal of solvents, column chromatography on silica
gel with ethyl acetate/hexane afforded the product.
300 MHz): d=8.85 (s, 1H), 8.59 (br.s, 1H), 7.87(d,
J=6.6 Hz, 1H), 7.36 (m, 4H), 7.23 (m, 1H), 7.29 (d, J=
[17a]
1
13
4-Methylbiphenyl:
H NMR (CDCl , 600 MHz): d=
7.8 Hz, 2H), 2.44 (s, 3H). C NMR (CDCl , 150 MHz): d=
3
3
7
.57–7.58 (m, 2H), 7.49 (d, J=7.8 Hz, 2H), 7.42 (t, J=
148.4, 148.3, 138.8, 137.8, 136.8, 134.4, 129.0, 128.8, 127.9,
124.3, 123.5, 21.5.
7.8 Hz, 2H), 7.32 (t, J=7.2 Hz, 1H), 7.23–7.25 (m, 2H), 2.39
13
[29]
1
(s, 3H); C NMR (CDCl , 150 MHz): d=141.2, 138.4, 137.0,
3-(3,5-Dimethylphenyl)pyridine:
H NMR
(CDCl3,
3
1
29.5, 128.7, 126.99, 126.97, 126.96, 21.1.
600 MHz): d=8.83 (s, 1H), 8.57 (br.s, 1H), 7.84 (d, J=
[17a]
1
4,4’-Dimethylbiphenyl:
H NMR (CDCl , 600 MHz):
7.8 Hz, 1H), 7.33 (dd, J=7.2, 4.8 Hz, 1H), 7.19 (s, 2H), 7.04-
3
1
3
d=7.48 (d, J=7.8 Hz, 4H), 7.23 (d, J=7.8 Hz, 4H), 2.39 (s,
A
H
U
G
E
N
N
ACHTUNGTNERUNNG( s, 3H); C NMR (CDCl , 150 MHz): d=148.4,
3
13
6
1
H); C NMR (CDCl , 150 MHz): d=138.3, 136.7, 129.4,
3
[17b]
1
26.8, 21.1.
4-Phenyl-2H-chromen-2-one:
H NMR
(CDCl3,
[17a]
1
4-Methoxy-4’-methylbiphenyl:
H NMR
(CDCl3,
300 MHz): d=7.43–7.61 (m, 8H), 7.28 (d, J=8.1 Hz, 1H),
1
3
6
2
00 MHz): d=7.51 (d, J=6.6 Hz, 2H), 7.45 (d, J=6.6 Hz,
H), 7.23 (d, J=8.4 Hz, 2H), 6.97 (d, J=9.0 Hz, 2H), 3.85
6.41 (s, 1H); C NMR (CDCl , 75 MHz): d=160.5, 155.5,
3
154.0, 135.0, 131.8, 129.6, 128.7, 128.3, 126.9, 124.0, 118.8,
117.1, 115.0.
1
3
(
s, 3H), 2.38 (s, 3H); C NMR (CDCl , 150 MHz): d=
3
[17b]
1
1
2
58.9, 138.0, 136.4, 133.8, 129.4, 128.0, 126.6, 114.2, 55.3,
1.1.
4-(4-Methylphenyl)-2H-chromen-2-one:
H NMR
(CDCl , 600 MHz): d=7.53–7.56 (m, 2H), 7.40–7.42 (td, J=
3
[17a]
1
2
,4’-Dimethylbiphenyl:
d=7.21–7.25 (m, 8H), 2.40 (s, 3H), 2.28 (s, 3H). C NMR
CDCl , 150 MHz): d=141.9, 139.0, 136.3, 135.4, 130.3,
H NMR (CDCl , 600 MHz):
0.6, 9.0 Hz, 1H), 7.33–7.37 (m, 4H), 7.23 (dt, J=1.2, 8.4 Hz,
3
1
3
13
1H), 6.37 (s, 1H), 2.46 (s, 3H);
C NMR (CDCl3,
(
150 MHz): d=160.9, 155.8, 154.2, 139.9, 132.3, 131.8, 129.6,
3
1
29.8, 129.1, 128.8, 127.0, 125.7, 21.2, 20.5.
128.4, 127.1, 124.1, 119.1, 117.3, 114.9, 21.4.
4-(4-Methoxyphenyl)-2H-chromen-2-one:
[27]
1
[17b]
1
4, 4’-Dimethoxybiphenyl:
H NMR (CDCl , 300 MHz):
H NMR
3
d=7.48 (d, J=8.4 Hz, 4H), 6.96 (d, J=9.0 Hz, 4H), 3.85 (s,
(CDCl , 600 MHz): d=7.53–7.57 (m, 2H), 7.39–7.43 (m,
3
13
6
1
H); C NMR (CDCl , 150 MHz): d=158.7, 133.5, 127.7,
3H), 7.23–7.25 (m, 1H), 7.04–7.06 (m, 2H), 6.35 (s, 1H),
3
1
3
14.2, 55.3.
3.90 (s, 3H); C NMR (CDCl , 150 MHz): d=160.9, 160.8,
3
[17a]
1
2-Methylbiphenyl:
H NMR (CDCl , 600 MHz): d=
155.3, 154.2, 131.8, 129.9, 127.4, 127.0, 124.0, 119.1, 117.3,
114.6, 114.3, 55.4.
3
7
4
1
2
.40 (t, J=7.2 Hz, 2H), 7.31–7.34 (m, 3H), 7.21–7.27 (m,
13
[17b]
1
H), 2.27
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(s, 3H); C NMR (CDCl , 150 MHz): d=141.94,
4-(2-Methylphenyl)-2H-chromen-2-one:
H NMR
3
41.91, 135.3, 130.3, 129.8, 129.2, 128.0, 127.2, 126.7, 125.7,
0.5.
(CDCl , 600 MHz): d=7.53 (t, J=8.4 Hz, 1H), 7.39–7.42
3
(m, 2H), 7.31–7.35 (m, 2H), 7.17–7.19 (m, 2H), 7.07 (dd, J=
[17a]
1
13
4-Methoxylbiphenyl:
H NMR (CDCl , 600 MHz): d=
1.2, 7.8 Hz, 1H), 6.32 (s, 1H), 2.16 (s, 3H); C NMR
3
7
7
.55~7.51 (m, 4H), 7.40 (t, J=7.8 Hz, 2H), 7.29 (t, J=
(CDCl , 150 MHz): d=160.7, 160.7, 156.0, 153.7, 135.2,
3
1
3
.2 Hz, 1H), 6.97 (d, J=8.4 Hz, 2H), 3.83 (s, 3H); C NMR
134.6, 131.9, 130.4, 129.2, 128.3, 126.9, 126.0, 124.2, 119.3,
117.0, 115.6, 19.7.
(CDCl , 150.868 MHz): d=159.1, 140.8, 133.8, 128.7, 128.2,
3
[17b]
1
126.7, 126.7, 114.2, 55.3.
6-Methyl-4-phenyl-2H-chromen-2-one:
H NMR
[17a]
1
2-Phenylnaphthalene:
H NMR (CDCl3, 600 MHz):
(CDCl , 600 MHz): d=7.54 (m, 3H), 7.45 (m, 2H), 7.36 (d,
3
d=8.03 (s, 1H), 7.89 (t, J=9 Hz, 2H), 7.8 5(d, J=7.8 Hz,
J=8.4 Hz, 1H), 7.30 (d, J=7.8 Hz, 1H), 7.25 (s, 1H), 2.34
1
3
1
7
H), 7.74 (dd, J=8.4, 1.8 Hz, 1H), 7.71 (d, J=8.4 Hz, 2H),
(s, 3H); C NMR (CDCl , 150 MHz): d=161.0, 155.6, 152.3,
3
1
3
.50 ~7.4 6
A
C
H
T
U
N
G
T
R
E
N
N
U
N
G
(m, 4H), 7.37 (t, J=7.8 Hz, 1H); C NMR
135.3, 133.9, 132.9, 129.6, 128.8, 128.4, 126.7, 118.6, 117.0,
115.1, 20.9.
(CDCl , 150.9 MHz): d=166.4, 141.1, 138.6, 133.7, 132.6,
3
[17b]
1
1
1
28.9, 128.4, 128.2, 127.7, 127.5, 127.4, 126.3, 125.9, 125.8,
25.6.
4-Phenyl-2(5H)-furanone:
H NMR
(CDCl3,
600 MHz): d=7.46–7.52 (m, 5H), 6.38 (s, 1H), 5.23 (s, 2H);
[17a]
1
13
Biphenyl:
H NMR (CDCl , 200 MHz): d 7.61–7.56 (m,
C NMR (CDCl , 150 MHz): d=174.1, 164.2, 132.0, 129.9,
3
3
1
3
4
1
H), 7.47–7.33 (m, 6H); C NMR (CDCl , 50.31 MHz): d=
129.5, 126.7, 113.3, 71.3.
3-Phenyl-2-cyclohexen-2-one:
3
[30]
1
41.5, 129.0, 127.5, 127.4.
H NMR
(CDCl3,
[17a]
1
4-Acetylbiphenyl:
H NMR (CDCl , 600 MHz): d=
600 MHz): d=7.53 (m, 2H), 7.40 (m, 3H), 6.41 (s, 1H), 2.77
(t, J=6.0 Hz, 2H), 2.48 (t, J=6.6 Hz, 2H), 2.15 (m, 2H);
3
8
9
2
1
.02 (d, J=8.4 Hz, 2H), 7.68 (d, J=7.8 Hz, 2H), 7.62 (d, J=
1
3
Hz, 2H), 7.46 (t, J=8.4 Hz, 2H), 7.39 (t, J=7.2 Hz, 1H),
C NMR (CDCl , 75 MHz): d=199.8, 159.7, 138.7, 129.9,
3
13
.63 (s, 3H); C NMR (CDCl , 150.9 MHz): d=197.8, 145.8,
128.7, 126.0, 125.4, 37.2, 28.0, 22.8.
3-(4-Methylphenyl)-2-cyclohexen-2-one:
3
[30]
1
39.8, 135.8, 129.0, 128.9, 128.2, 127.3, 127.2, 26.7.
H NMR
[19b]
1
3-Phenylpyridine:
H NMR (CDCl , 600 MHz): d=
(CDCl , 600 MHz): d=7.64 (d, J=7.8 Hz, 2H), 7.21 (d, J=
3
3
8
.88 (s, 1H), 8.61 (s, 1H), 7.87 (d, J=7.2 Hz, 1H), 7.58 (d,
7.8 Hz, 2H), 6.41 (s, 1H), 2.75 (t, J=6.0 Hz, 2H), 2.47 (t,
J=6.0 Hz, 2H), 2.38 (s, 3H), 2.15 (m, 2H); C NMR
1
3
J=7.2 Hz, 2H), 7.48 (t, J=7.2 Hz), 7.38–7.42 (m, 1H), 7.37
13
(
s, 1H). C NMR (CDCl , 150 MHz): d=148.3, 148.2, 137.8,
(CDCl , 75 MHz): d=199.9, 159.6, 140.3, 135.8, 129.4, 126.0,
3
3
136.7, 134.3, 129.0, 128.1, 127.1, 123.6.
124.6, 37.2, 27.9, 22.8, 21.3.
2056
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 2051 – 2059

Room Temperature Nickel(II) Complexes [(4-MeOC H )Ni ACUTHNGTRENNUG(N PCy ) OTs and Ni AHCTUNGERTNNUN(G PCy ) X ]-Catalyzed Cross-Coupling
3 2 3 2 2
6
4
[30]
1
13
3-(4-Methoxyphenyl)-2-cyclohexen-2-one:
H NMR
7.36–7.40 (m 1H), 3.95 (s, 3H); C NMR (CDCl , 75 MHz):
3
(
CDCl , 600 MHz): d=7.52 (d, J=9.0 Hz, 2H), 6.93 (d, J=
d=167.0, 141.4, 140.1, 131.5, 130.6, 128.84, 128.80, 128.3,
3
9
2
.0 Hz, 2H), 6.39 (s, 1H), 3.84 (s, 3H), 2.75 (t, J=6.0 Hz,
H), 2.46 (t, J=6.0 Hz, 2H), 2.13 (m, 2H); C NMR
128.2, 127.7, 127.1, 52.1.
1
3
[34]
1
Methyl
(CDCl , 300 MHz): d=8.27 (s, 1H), 7.99 (d, J=7.8 Hz, 1H),
7.76 (d, J=7.8 Hz, 1H), 7.46–7.54 (m, 3H), 7.27 (d, J=
4’-methylbiphenyl-3-carboxylate:
H NMR
(CDCl , 75 MHz): d=99.8, 161.2, 159.1, 130.7, 127.6, 123.6,
3
3
1
14.1, 55.3, 37.2, 27.8, 22.7.
-Methyl-4-phenylpyran-2-one:
00 MHz): d=.55–7.58 (m, 2H), 7.45–7.48 (m, 3H), 6.35 (s,
[21]
1
13
6
H NMR
(CDCl3,
7.8 Hz 2H), 3.94 (s, 3H), 2.40 (s, 3H); C NMR (CDCl ,
75 MHz): d=167.1, 141.3, 137.5, 137.2, 131.3, 130.6, 129.6,
128.7, 128.0, 126.9, 52.1, 21.1.
3
3
1
1
3
H), 6.31 (s, 1H), 2.32 (s, 3H); C NMR (CDCl , 75 MHz):
3
d=163.4, 162.1, 155.4, 135.7, 130.5, 129.1, 126.6, 108.0, 103.4,
0.1.
-Methyl-4-(4-methylphenyl)pyran-2-one:
CDCl , 600 MHz): d=7.67 (d, J=7.8 Hz, 2H), 7.26 (d, J=
2
[21]
1
6
H NMR
(
3
Acknowledgements
7
3
1
.8 Hz, 2H), 6.31 (s, 1H), 6.30 (s, 1H), 2.39
A
H
U
G
R
N
U
(s, 3H), 2.30 (s,
13
H); C NMR (CDCl , 75 MHz): d=163.5, 161.9, 155.4,
3
We gratefully thank the NSF (CHE0911533) for funding.
Partial support from PSC-CUNY Research Award Program
is also gratefully acknowledged. We also thank Frontier Sci-
entific, Inc. for its generous gifts of arylboronic acids.
35.3, 141.1, 132.7, 128.8, 126.5, 107.2, 103.3, 21.3, 20.1.
[21]
1
1-Methyl-4-phenylquinolin-2(1H)-one:
H NMR
(
6
CDCl , 300 MHz): d=7.55–7.60 (m, 2H), 7.41–7.49 (m,
H), 7.15–7.19 (m, 1H), 6.68 (s, 1H), 3.79 (s, 3H); C NMR
3
1
3
(
CDCl , 150 MHz): d=161.9, 150.9, 140.3, 137.0, 130.7,
3
1
28.9, 128.7, 128.5, 127.7, 121.9, 121.2, 120.4, 114.5, 29.5.
References
[30]
1-Methyl-4-(4-methylphenyl)quinolin-2(1H)-one:
1
H NMR (CDCl , 600 MHz): d=7.55–7.59 (m, 2H), 7.41 (d,
3
[
1] For recent reviews of triflate chemistry, see: a) Z.
Gilson, R. Larock, Chem. Rev. 2006, 106, 4644–4680;
b) I. Baraznenok, V. Nenajdenko, E. Balenkova, Tetra-
hedron 2000, 56, 3077–3119.
J=8.4 Hz, 1H), 7.28–7.32 (m, 4H), 7.15 (dt, J=1.2, 7.2 Hz,
1
1
3
H), 6.66 (s, 1H), 3.76 (s, 3H), 2.43 (s, 3H); C NMR
(CDCl , 150 MHz): d=162.0, 150.9, 140.3, 138.6, 134.2,
3
1
2
30.6, 129.2, 128.8, 127.7, 127.69, 121.8, 121.1, 120.6, 114.4,
9.4, 21.3.
[
[
2] For a thematic issue on cross-coupling reactions: Acc.
Chem. Res. 2008, 41, 1439–1564.
3] Also see: a) N. Miyaura, Top. Curr. Chem. 2002, 219,
[19b]
4-(4-Methoxyphenyl)-1-methylquinolin-2(1H)-one:
1
H NMR (CDCl , 600 MHz): d=7.61 (dd, J=1.2, 7.8 Hz,
3
11–59; b) A. Suzuki, J. Organomet. Chem. 1999, 576,
147–168; c) A. F. Littke, G. C. Fu, Angew. Chem. 2002,
114, 4350–4386; Angew.Chem. Int. Ed. 2002, 41, 4176–
4211; d) S. Diez-Gonzalez, N. Marion, S. P. Nolan,
1
H), 7.55–7.58 (m, 1H), 7.41 (d, J=8.4 Hz, 1H), 7.34–7.36
(
m, 2H), 7.15–7.18 (m, 1H), 7.00- 7.02 (m, 2H), 6.65 (s,
1
3
1
1
1
H), 3.87 (s, 3H), 3.76 (s, 3H);
C NMR (CDCl3,
50 MHz): d=161.8, 159.9, 150.5, 140.2, 130.4, 130.1, 129.2,
Chem. Rev. 2009, 109, 3612–3676; e) S. Darses, J. P.
Genet, Chem. Rev. 2008, 108, 288–325; f) L. Yin, J.
Liebscher, Chem. Rev. 2007, 107, 133–173.
27.6, 121.7, 120.8, 120.5, 114.3, 113.9, 55.2, 29.3.
[31]
1
4-Acetyl-4’-methylbiphenyl:
H NMR
(CDCl3,
6
2
00 MHz): d=8.02 (d, J=8.4 Hz, 2H), 7.67 (d, J=8.4 Hz,
[
4] V. Percec, J.-Y. Bae, D. H. Hill, J. Org. Chem. 1995, 60,
H), 7.53 (d, J=7.8 Hz, 2H), 7.28 (d, J=7.8 Hz, 2H), 2.63
1
060–1065.
1
3
(
s, 3H), 2.41 (s, 3H); C NMR (CDCl , 150 MHz): d=
3
[5] The cross-coupling of one example of electron-deficient
aryl tosylate with lithium arylborates was reported: Y.
Kobayashi, R. Mizojiri, Tetrahedron Lett. 1996, 37,
8531–8534.
1
2
97.8, 145.7, 138.2, 137.0, 135.6, 129.7, 128.9, 127.1, 127.0,
6.7, 21.2.
[32]
1
4-Acetyl-4’-methoxybiphenyl:
H NMR
(CDCl3,
6
2
00 MHz): d=8.01 (d, J=8.4 Hz, 2H), 7.65 (d, J=8.4 Hz,
[
6] D. Zim, V. R. Lando, J. Dupont, A. L. Monteiro, Org.
Lett. 2001, 3, 3049–3051.
H), 7.58 (d, J=7.2 Hz, 2H), 7.01 (d, J=6.6 Hz, 2H), 3.87
1
3
(
s, 3H), 2.63 (s, 3H); C NMR (CDCl , 150 MHz): d=
3
[7] M. K. Lakshman, P. F. Thomson, M. A. Nuqui, J. H.
1
5
97.8, 159.9, 145.3, 135.2, 132.2, 128.9, 128.3, 126.6, 114.4,
5.4, 26.6.
Hilmer, N. Sevova, B. Boggess, Org. Lett. 2002, 4,
1
479–1482.
[32]
1
4-Acetyl-2’-methylbiphenyl:
H NMR
(CDCl3,
[8] For Suzuki–Miyaura coupling reactions involving aryl
mesylates: a) M. Ueda, A. Saitoh, S. Oh-Tani, N.
Miyaura, Tetrahedron 1998, 54, 13079–13086; b) W. K.
Chow, C. M. So, C. P. Lau, F. Y. Kwong, J. Org. Chem.
2010, 75, 5109–5112. For Suzuki–Miyaura coupling re-
actions involving vinyl tosylates: c) J. Wu, Q. Zhu, L.
Wang, R. Fathi, Z. Yang, J. Org. Chem. 2003, 68, 670–
673; d) J. Wu, L. Wang, R. Fathi, Z. Yang, Tetrahedron
Lett. 2002, 43, 4395–4397; e) M. A. Huffman, N.
Yasuda, Synlett 1999, 471–473.
[9] For other coupling reactions involving aryl arenesulfo-
nates: a) A. H. Roy, J. F. Hartwig, J. Am. Chem. Soc.
2003, 125, 8704–8705; b) X. Huang, K. W. Anderson,
D. Zim, L. Jiang, A. Klapars, S. L. Buchwald, J. Am.
Chem. Soc. 2003, 125, 6653–6655; c) J. Wu, Y. Liao, Z.
6
2
00 MHz): d=8.01 (d, J=7.2 Hz, 2H), 7.42 (d, J=8.4 Hz,
1
3
H), 7.21–7.30 (m, 4H), 2.65 (s, 3H), 2.27 (s, 3H); C NMR
(CDCl , 150 MHz): d=197.8, 146.9, 140.7, 135.6, 135.1,
3
130.5, 129.5, 129.4, 128.2, 127.9, 125.9, 26.6, 20.4.
[32] 1
4-Acetyl-2’-methoxybiphenyl:
H NMR
(CDCl3,
6
2
00 MHz): d=8.01 (d, J=8.4 Hz, 2H), 7.64 (d, J=8.4 Hz,
H), 7.38 (t, J=7.8 Hz, 1H), 7.36 (d, J=7.8 Hz, 1H), 7.05
(
t, J=7.8 Hz, 1H), 7.01 (d, J=8.4 Hz, 1H), 3.82 (s, 3H),
13
2
1
5
.63 (s, 3H); C NMR (CDCl , 150 MHz): d=197.9, 156.4,
3
43.5, 135.4, 130.7, 129.7, 129.5, 129.3, 128.1, 120.9, 111.2,
5.5, 26.7.
[33]
1
Methyl biphenyl-3-carboxylate:
H NMR (CDCl3,
3
00 MHz): d=8.29 (s, 1H), 8.02 (d, J=7.8 Hz, 1H), 7.79 (d,
J=7.8 Hz, 1H), 7.63 (d, J=8.7 Hz, 2H), 7.44–7.54 (m, 3H),
Adv. Synth. Catal. 2011, 353, 2051 – 2059
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2057

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Room Temperature Nickel(II) Complexes [(4-MeOC H )Ni ACUTHNGTRENNUG(N PCy ) OTs and Ni AHCTUNGERTNNUN(G PCy ) X ]-Catalyzed Cross-Coupling
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