Room Temperature Ni0/PCy3-Catalyzed Coupling Reactions of Aryl Arenesulfonates with Bis(pinacolato)diboron

Article abstract of DOI:10.1002/ejoc.201701300

Room temperature Ni⁰/PCy₃-catalyzed cross-coupling reactions of aryl arenesulfonates with bis(pinacolato)diboron are described. The Ni⁰/PCy₃ catalysts, generated from Ni(COD)₂ and PCy₃, or air-stable 4-MeOC₆H₄Ni^II(PCy₃)₂OTs, were efficient catalyst systems for the Miyaura borylation reactions of a variety of aryl arenesulfonates with bis(pinacolato)diboron. The mild reaction condition, the easy availability of the catalysts and good yields make these reactions potentially useful in organic synthesis (Cy = cyclohexyl, COD = cyclooctadiene, OTs = tosyl).

Full text of DOI:10.1002/ejoc.201701300

A Journal of
Accepted Article
Title: Room Temperature Ni(0)/PCy3-Catalyzed Coupling Reactions of
Aryl Arenesulfonates with Bis(pinacolato)diboron
Authors: Qiao-Sheng Hu, Jie Dong, and Hui Guo
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701300
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701300
Supported by

European Journal of Organic Chemistry
10.1002/ejoc.201701300
FULL PAPER
Room Temperature Ni(0)/PCy
3
-Catalyzed Coupling Reactions of
Aryl Arenesulfonates with Bis(pinacolato)diboron
[
a]
[a]
[a]
Jie Dong, Hui Guo and Qiao-Sheng Hu*
Abstract: Room temperature Ni(0)/PCy
reactions of aryl arenesulfonates with bis(pinacolato)diboron are
described. The Ni(0)/PCy catalysts, generated from Ni(COD)
PCy or air-stable 4-MeOC Ni(II)(PCy OTs, were efficient
3
-catalyzed cross-coupling
3
2
and Results and Discussion
3
,
H
6 4
3 2
)
catalyst systems for the Miyaura borylation reactions of a variety of
aryl arenesulfonates with bis(pinacolato)diboron. The mild reaction
condition, the easy availability of the catalysts and good yields make
these reactions potentially useful in organic synthesis.
3
We have previously showed that Ni(0)/PCy readily undergoes
oxidative addition with aryl tosylates and this step should not be
a rate-determining step,8c we reasoned that the transmetalation
3 2
of ArNi(II)(PCy ) OTs with bis(pinacolato)diboron might likely be
the key step for the generation of arylborates. Since the
transmetalation step has been reported to be influenced by the
base employed,1 we started our study by examining different
bases and our results are listed in Table 1. As KOAc was the
Introduction
best base in reported Pd(OAc)
tested, but a low conversion was observed (Table 1, entry 1).
Other common inorganic bases, K PO , K CO3, KF and t-BuOK,
were then tested and K PO was found to give a better result
Table 1, entries 2-5). Because the existence of a small amount
of water in the reaction system helped Ni(0)/PCy -catalyzed
2
/DPPF system,3a KOAc was first
Arylborons have been extensively employed for bond-forming
reactions including the Suzuki cross-coupling reaction.1 In the
past decades, transition metal-catalyzed coupling reactions of
aryl (pseudo)halides with diborons has become one of attractive
ways for the preparation of arylborons,2-6 While aryl halides and
aryl triflates have been the most common substrates for this
borylation reaction, readily available aryl tosylates and
mesylates have rarely been used as coupling partners for this
reaction.7 In the few reports of borylation reaction with aryl
3
4
2
3
4
(
3
Suzuki cross-coupling reactions,8b we next examined the
reaction with only degassed, but not dried THF, higher
conversions were observed except for the reaction with t-BuOK
as the base (Table 1, entries 6-10), with K
Table 1, entry 7). Two other solvents, toluene and dioxane,
were also tested and THF was found to be the best solvent
Table 1, entries 6, 11-12). Reducing the amount of the base
3 4
PO as the best base
tosylates or mesylates as substrates, elevated temperatures, 80
oC or higher, were generally needed for the reaction.7
(
(
In our laboratory, we have been interested in employing aryl
arenesulfonates as reaction partners for transition metal-
catalyzed bond-forming reactions, particularly under mild
reaction conditions. We have documented room temperature
hindered the reaction and 3-4 equivalents of base gave the best
results (Table 1, entries 13-15). The use of 1.5 equivalents of
bis(pinacolato)diboron led to a lower conversion (Table 1, entry
1
6). As a comparison, the reaction without Ni(COD)
also carried out and no product was observed (Table 1, entry
7).
2 3
/PCy was
Ni(0)/PCy
3
-calayzed cross-coupling reaction of aryl/alkenyl
8
arenesulfonates with arylboronic acids. The mild reaction
condition and our understanding of the reaction mechanism
prompted us to wonder whether the borylation reaction of aryl
arenesulfonates with diborons could be achieved at room
temperature with Ni(0)/PCy
room temperature Ni(0)/PCy
of aryl arenesulfonates with bis(pinacolato)diboron is reported.
1
Table 1. Room Temperature Ni(COD)
p-Tolyl Tosylate with Bis(pinacolato)diboron
2 3
/PCy -Catalyzed Borylation Reaction of
a
3
as the catalyst. Herein our study on
-catalyzed cross-coupling reactions
3
[
a]
Initial(s), Surname(s) of Author(s) including Corresponding Author(s)
Department of Chemistry
College of Staten Island of the City University of New York
Staten Island, New York, 10314
and the Ph.D. Program in Chemistry, the Graduate Center of the
City University of New York, New York, NY 10016
E-mail: qiaosheng.hu@csi.cuny.edu
Supporting information for this article is given via a link at the end of the
document.
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European Journal of Organic Chemistry
10.1002/ejoc.201701300
FULL PAPER
O
O
O
5% Ni(COD)2/20% PCy3
Base, Solvent, 4 h
O
O
O
O
3%Ni(COD) /12% PCy3
O
2
OTs
B B
B
Ar OSO Ar' +
2
B B
Ar B
O
O
O
K PO , THF, r.t., 6-12 h
3 4
O
Conversion (%) b
Entry
Yield (%)b
87
Entry
Base
KOAc (3 equiv.)
K PO (3 equiv.)
Solvent
Ar-OSO Ar'
2
1
2
3
THF (dried & degassed)
THF (dried & degassed)
THF (dried & degassed)
6
1
2
OTs(1a)
OTs (1b)
3
4
33
6
85
88
K CO (3 equiv.)
2
3
3
4
5
6
MeO
OTs (1c)
4
5
6
KF (3 equiv.)
KO-t-Bu (3 equiv.)
KOAc (3 equiv.)
THF (dried & degassed)
THF (dried & degrassed)
THF (degassed)
13
0
10
79 c
OTs
(1d)
82
7
K PO (3 equiv.)
THF (degassed)
THF (degassed)
77
23
OTs (1e)
3
4
8
9
K CO (3 equiv.)
2 3
87
OTs(1f)
OTs (1g)
KF (3 equiv.)
THF (degassed)
THF (degassed)
Toluene (degassed)
29
0
12
10
KO-t-Bu (4 equiv.)
K3PO4 (3 equiv.)
7
8
O
90
83
c
c
c
1
1
OTs
(1h)
1
1
1
2
3
4
K3PO4 (3 equiv.)
K PO (1 equiv.)
Dioxane (degassed)
THF (degassed)
THF (degassed)
44
18
47.5 c
OTs
3
4
(1i)
82 c
9
K3PO4 (2 equiv.)
K3PO4 (4 equiv.)
K PO (4 equiv.)
O
1
5
THF (degassed)
THF (degassed)
THF (degassed)
95
10
OTs(1j)
OTs(1k)
87
85
d
1
1
6
7
46
0 e
O
3
4
11
Ph
K PO (4 equiv.)
3
4
F3C
a. Reaction conditions: tosylate (1.0 equiv.), diboron (3.0 equiv.), Ni(COD)2
5 mol%), PCy3 (20 mol%), base (1-4 equiv.), THF (2 mL), room temperature.
(1l)
OTs
87
88
1
2
3
(
b. Conversions based on 1H NMR analysis. c. Ground base was used. d. 1.5 equiv. of
MeO2C
(
1m)
1
OTs
diboron was used. e. 0% of Ni(COD)/PCy3was used.
.
MeO2C
MeO
(
1n)
85
80
14
OTs
By using 4 equivalents of K
as the solvent, we next examined a variety of aryl tosylates for
the room temperature Ni(0)/PCy -catalyzed borylation reaction.
Our results are summarized in Table 2. As shown in Table 2,
the Ni(COD) /PCy system was found to be a general catalyst
for both activated and deactivated aryl tosylates, including those
with ortho-, meta- and para-substituents. Complete conversions
and good isolated yields were observed for all aryl
arenesulfonates employed (Table 2, entries 1-14). Aryl
benzenesulfonates were also found to be suitable substrates for
the reaction and good yields were observed (Table 2, entry 15-
3 4
PO as the base and degassed THF
1
1
5
OSO Ph
2
(1o)
(1p)
3
6
OSO Ph
2
77
1
7
8
MeO
OSO Ph (1q)
2
82
2
3
1
(1r)
73 c
OMs
a. Reaction conditions: aryl sulfonates (0.2 mmol), bis(pinacolato)diboron (3 equiv.),
K3PO4 (4 equiv.), THF (1 mL), room temperature. b. Isolated yields.
c. Reaction time: 24 h.
2 3 2
As Ni(COD) /PCy , especially Ni(COD) , are very air-sensitive,
we wondered whether air-stable Ni(II) complexes could be
employed as operationally convenient catalysts for this Miyaura
1
7). An aryl mesylate was observed to be less reactive than aryl
tosylates, and the reaction involving it as the coupling partner
required longer reaction time to go to completion (Table 2, entry
borylation reaction. Because 4-MeOC
oxidative addition adduct of 4-MeOC
is readily accessible and air-stable, and has been established as
Ni(0)/PCy source for the cross-coupling reactions of aryl
arenesulfonates with arylboronic 4-
acids,8
OTs naturally emerged as our choice for
We found that by using 4-
OTs as the catalyst, the cross-coupling
6
H
4
Ni(II)(PCy
3
)
2
OTs, the
6
H
4
OTs with Ni(COD)
2
/PCy ,
3
1
8).
3
Table 2. Room Temperature Ni(COD)
Aryl Arenesufonates with Bis(pinacolato)diboron
2 3
/PCy -Catalyzed Borylation Reaction of
a
MeOC
this
6
H
4
Ni(II)(PCy
exploration.
4
H Ni(II)(PCy
3
)
2
2
MeOC
6
3
)
reactions of aryl arenesulfonates with bis(pinacolato)diboron
occurred smoothly and good to high yields were obtained (Table
3
). These results suggested that 4-MeOC
well as its analogs could be an operationally convenient
substitute for the Ni(COD) /PCy catalyst system for the room
6 4 3 2
H Ni(II)(PCy ) OTs as
2
3
temperature cross-coupling reactions of aryl arenesulfonates
with bis(pinacolato)diboron.
Table 3. Room Temperature 4-MeOC
Couplings of Aryl Arenesulfonates with Bis(pinacolato)diboron
6
H
4
Ni(II)(PCy
3
)
2
OTs-Catalyzed Cross-
a
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European Journal of Organic Chemistry
10.1002/ejoc.201701300
FULL PAPER
General Procedure for Ni(COD)
2
/PCy
3
-Catalyzed Cross-Coupling
O
O
O
O
5% 4-MeOC6H4Ni(II)(PCy3)2OTs
K PO , THF,
Ar
B
Reactions of Aryl Arenesulfonates with Bis(pinacolato)diboron: In a
glovebox with an -atmosphere, to vial containing
Ar OSO Ar'
2
+
B B
3
4
O
N
2
a
O
rt, 12-24 h
bis(pinacolato)diboron (1.5 mmol, 3 equiv.), potassium phosphate (2.0
mmol, 4 equiv.), THF (5 mL), bis(1,5-cyclopentadiene) nickel(0) (0.025
mmol, 5 mol%) and tricyclohexylphosphine (0.1 mmol, 20 mol%), aryl
tosylate or aryl benzenesulfonate (0.5 mmol, 1.0 equiv.) was added. The
mixture was allowed to react at the room temperature for 6-24 h. After
quenching with water, the reaction mixture was extracted with ethyl
acetate. The organic layer was washed with brine and then evaporated
under vacuum. Flash chromatography on silica gel yielded the desired
products.
Yield (%)b
Entry
Ar-OSO Ar'
2
1
2
OTs(1a)
OTs (1b)
89
87
95
MeO
OTs (1c)
OTs (1d)
OTs (1e)
OTs(1f)
3
4
72
80
General Procedure for 4-MeOC
Coupling Reactions of
Bis(pinacolato)diboron: In a glovebox with an N
6
H
4
Ni(II)(PCy
Aryl Arenesulfonates
3 2
) OTs-Catalyzed Cross-
5
with
8
8
6
1
6
7
2
-atmosphere, to a vial
(
(
10 mL) were added tosylate (0.5 mmol, 1 equiv.), bis(pinacolato)diboron
1.5 mmol, 3 equiv.), potassium phosphate (2.0 mmol, 4 equiv.), THF (5
O
OTs(1g)
OTs (1h)
3 6 4 3 2
mL), and 4-CH OC H Ni(PCy ) OTs (0.025 mmol, 5 mol%). The resulting
8
9
81
mixture was stirred at the room temperature for 12-48 h. After quenching
with water, the reaction mixture was extracted with ethyl acetate. The
organic layer was washed with brine and then evaporated under vacuum.
Flash chromatography on silica gel yielded the desired products. Details.
OTs
(
1i)
83c
81
O
OTs(1j)
OTs(1k)
1
0
O
79
11
Ph
F3C
Acknowledgements
(
1m)
OTs
78
1
2
3
MeO2C
MeO
We gratefully thank the NSF (CHE01519311) for funding. Partial
support from PSC-CUNY Research Award Program is also
gratefully acknowledged.
8
0
1
OTs(1n)
MeO2C
1
4
(1o)
77
78
OTs
OSO Ph
(1p)
Keywords: aryl arenesulfonates • bis(pinacolato)diboron •
nickel(0) • tricyclohexylphosphine • cross-coupling
15
16
17
18
2
OSO Ph (1q)
79
2
MeO
OSO Ph (1r)
92
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70c
OMs
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as efficient as Ni(COD) /PCy3. The mild reaction condition, the
easy availability of the catalyst systems, and good coupling
yields make this Ni(0)/PCy -catalyzed borylation reaction
2
/PCy
Ni(II)(PCy
/PCy with 4-MeOC
3
catalyst system, we explored to use air-stable 4-
OTs, the oxidative addition adduct of
OTs, as the catalyst for the
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European Journal of Organic Chemistry
10.1002/ejoc.201701300
FULL PAPER
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European Journal of Organic Chemistry
10.1002/ejoc.201701300
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Entry for the Table of Contents
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Borylation
Jie Dong, Hui Guo and Qiao-Sheng Hu*
O
O
O
3%Ni(COD) /12%PCy
2
3
O
ArOSO Ar'
Ar B
2
+
B B
or 4-MeOC H Ni(PCy ) OTs
6
4
3 2
O
0-92%
Page No. – Page No.
O
K PO , THF, r.t., 6-48 h
3
4
7
3
Room temperature Ni(0)/PCy -
Catalyzed Coupling Reactions of Aryl
Arenesulfonates with
Room temperature Ni(0)/PCy
arenesulfonates with bis(pinacolato)diboron to form arylborates are described.
3
-catalyzed cross-coupling reactions of aryl
Bis(pinacolato)diboron
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