Room temperature Pd(0)/Ad3P-catalyzed coupling reactions of aryl chlorides with bis(pinacolato)diboron

Article abstract of DOI:10.1016/j.tetlet.2019.01.042

Room temperature Pd(0)/Ad₃P-catalyzed cross-coupling reactions of aryl chlorides with bis(pinacolato)diboron are described. The Pd(0)/Ad₃P catalyst, generated from Ad₃P-coordinated acetanilide-based palladacycle complex, proved to be an efficient catalyst system for the Miyaura borylation reactions of a variety of aryl chlorides with bis(pinacolato)diboron. The mild reaction condition, the easy availability of the catalyst and good coupling yields make these reactions potentially useful in organic synthesis.

Full text of DOI:10.1016/j.tetlet.2019.01.042

Accepted Manuscript
Room Temperature Pd(0)/Ad P-Catalyzed Coupling Reactions of Aryl Chlor-
3
ides with Bis(pinacolato)diboron
Jie Dong, Hui Guo, Wei Peng, Qiao-Sheng Hu
PII:
S0040-4039(19)30083-8
https://doi.org/10.1016/j.tetlet.2019.01.042
TETL 50575
DOI:
Reference:
To appear in:
Tetrahedron Letters
Received Date:
Revised Date:
Accepted Date:
17 December 2018
19 January 2019
22 January 2019
Please cite this article as: Dong, J., Guo, H., Peng, W., Hu, Q-S., Room Temperature Pd(0)/Ad P-Catalyzed Coupling
3
Reactions of Aryl Chlorides with Bis(pinacolato)diboron, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/
j.tetlet.2019.01.042
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Graphical Abstract
Room Temperature Pd(0)/PAd -Catalyzed
Leave this area blank for abstract info.
3
Coupling Reactions of Aryl Chlorides with
Bis(pinacolato)diboron
Jie Dong, Hui Guo, Wei Peng and Qiao-Sheng Hu*
H
N
5
mol%
O
Pd -OTs
+
O
O
O
O
Ad P
3
Ar B
ArCl +
B B
K PO , THF, r.t., 24-48 h
O
8-93%
O
3
4
5
2

Tetrahedron
journal homepage: www.elsevier.com
Room Temperature Pd(0)/Ad P-Catalyzed Coupling Reactions of Aryl Chlorides with
3
Bis(pinacolato)diboron
Jie Dong, Hui Guo, Wei Peng and Qiao-Sheng Hu*
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, United States
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Room temperature Pd(0)/Ad P-catalyzed cross-coupling reactions of aryl chlorides
3
with bis(pinacolato)diboron are described. The Pd(0)/Ad
3
P catalyst, generated from
Ad P-coordinated acetanilide-based palladacycle complex, proved to be an efficient
3
catalyst system for the Miyaura borylation reactions of a variety of aryl chlorides with
bis(pinacolato)diboron. The mild reaction condition, the easy availability of the
catalyst and good coupling yields make these reactions potentially useful in organic
synthesis.
Available online
Keywords:
Palladium; Tris(1-adamantyl)phosphine; Aryl
chlorides; Borylation reaction.
2009 Elsevier Ltd. All rights reserved.
Introduction
3
could readily generate 12-electron (Ad P)Pd(0) species, was
found to catalyze the Suzuki cross-coupling reaction of aryl
chlorides with arylboronic acids under mild condition,
1
8
Since Miyaura’s first report in 1995, Pd(0)-catalyzed coupling
reaction of aryl halides with bis(pinacolato)diboron has become
one of the most attractive methods to access arylborates and
suggesting the oxidative addition reaction of Pd(0)/Ad P with
3
aryl chlorides readily occurred. We thus reasoned that the
borylation reaction of aryl chlorides with bis(pinacolato)diboron
2
-4
analogs. Aryl iodides/bromides and aryl triflates, which can
readily undergo oxidative addition with Pd(0) catalysts, have
been the common substrates. By employing bulky, electron-rich
ligands including electron-rich phosphines, widely available but
less reactive aryl chlorides also became general partners for this
type of reaction.5,6 However, elevated temperatures were
generally needed in the reported borylation reactions with aryl
chlorides as substrates.
might be achieved under mild conditions with Pd(0)/Ad P as the
3
catalyst. Herein our study on Pd(0)/Ad P-catalyzed-catalyzed
3
cross-coupling
reactions
of
aryl
chlorides
with
bis(pinacolato)diboron is reported.
H
N
(Ad3P)
O
(
1)
P
3
Pd+ -OTs
Ad3P
In our laboratory, we have been interested in employing aryl
chlorides as reaction partners for transition metal-catalyzed cross-
coupling reactions under mild reaction conditions. We have
developed a ferrocenylmethylphosphine-containing polymer as
unique ligands for room temperature Pd(0)-catalyzed Suzuki
cross-coupling reaction of aryl chlorides with arylboronic acids.7a
Figure 1. Tris(1-adamantyl)phosphine (Ad
Coordinated Acetanilide-Based Palladacycle Complex 1
3 3
P) and Ad P-
7
Our study began with the coupling reaction of p-tolyl chloride
with bis(pinacolato)diboron by examining different bases with
complex 1 as the catalyst and tetrahydrofuran (THF) as the
solvent. Our results are listed in Table 1. As KOAc was
established to be the base in most of reported borylation
We have also documented room temperature Ni(0)/PPh
3
-
catalyzed cross-coupling reaction of aryl chlorides with
7
b
arylboronic acids. Our study on these reactions prompted us to
considered that Pd(0) catalysts that could readily undergo
oxidative addition reaction with aryl chlorides might be able to
catalyze the borylation reaction of aryl chlorides with
bis(pinacolato)diboron under mild conditions. Recently, tris(1-
5
,6
reactions, KOAc was first tested and a 35% conversion was
observed (Table 1, entry 1). Other common inorganic bases were
also tested and we found that stronger bases including KOH,
3 4 2 3 3
K PO , K CO and KHCO gave higher conversions, but a
adamantyl)phosphine (Ad
his coworkers, is an electron-rich trialkylphospine.8 Ad
coordinated acetanilide-based palladacycle complex 1, which
3
P), recently reported by Carrow and
significant amount of self-cross-coupling reaction product along
with a small amount of the deboronated product, p-toluene, was
observed (Table 1, entries 2-5). KF and NaOAc were found to
3
P-
3

give slightly lower conversions (Table 1, entries 6-7). The
existence of water appeared to lead to faster reactions, but the
formation of the deboronated product, p-toluene, was observed to
be more with more amounts of water (Table 1, entries 8-9). We
also examined the reaction with the use of 1:1 to 1:1.5 ratio of
yields were observed for all aryl chlorides employed. Electron-
poor (activated) aryl chlorides were more reactive than electron-
rich aryl chlorides, and reactions involving them as the coupling
partner required shorter reaction time to go to completion (Table
2, entry 10-14).
Pd
generated from 1:1 to 1:1.5 ratio of Pd
efficient than complex 1 as lower conversions were observed
Table 1, entries 10-11). Toluene, dioxane and ethanol were also
tested as the solvent. A lower conversion was observed with
toluene as the solvent and higher conversions along with a
significant amount of side product were observed with dioxane
and EtOH as the solvent (Table 1, entries 12-14). Varying the
amount of the KOAc impacted the reaction and higher
conversion was observed with the use of more amounts of KOAc
2
(dba)
3
and Ad
3
P as the catalyst and found that catalysts
2
(dba) and Ad P were less
3
3
Table 2. Room Temperature Complex 1-Catalyzed Borylation
Reaction of Aryl Chlorides with Bis(Pinacolato)diboron
a
(
O
O
5
mol % 1
O
O
Ar Cl+
Ar B
B B
O
O
K3PO4, THF, r.t., 24 - 48h
Entry
Yield(%)b
Ar-Cl
Cl (1a)
1
2
3
88
Cl
(1b)
(1c)
(1d)
85
87
(
Table 1 entries 15-17). We also examined the reaction with the
Cl
9
10
use of 2-phenylaniline-based complex 2 or 3 as the catalyst
4
and found that lower conversions were observed (Table 1, entries
81
Cl
Cl
1
8-19). By the lengthening the reaction time, a complete
(
1e)
5
6
88
90
conversion was observed (Table 1, entry 20).
Cl (1f)
Cl (1g)
3
Table 1. Room Temperature Pd(0)/Ad P-catalyzed Borylation
Reaction of p-Tolyl Chloride with Bis(pinacolato)diboron a
MeO
MeO
7
8
93
92
(
1h)
Cl
F
H
Cl
O
O
5 mol% Catalyst
Base, THF, 4 h
B
O
O
O
9
Cl
(1i)
80
B B
O
82c
58
1
0
OHC
O
Cl (1j)
CHO
(
A)
(B)
(C)
1
1
(1k)
Solvent Conversion (%) (A:B:C)b
Cl
Entry Base
Catalyst
1
2
3
4
5
6
7
8
KOAc
KOH
1
1
1
1
1
THF
THF
THF
THF
35 (100:0: 0)
96 (31:68: 0)
90 (14: 79: 7)
12
13
Cl (1l)
8
5c
70
90
COCH3
K PO
3
(1m)
4
Cl
K CO
2
85 (12: 88: 0)
56 (52:45:3)
25 (100:0: 0)
3
O
Ph
Cl (1n)
KHCO3
KF
NaOAc
THF
THF
THF
THF
14
1
1
1
a. Reaction conditions: aryl chlorides (0.2 mmol), bis(pinacolato)diboron
(3 equiv.), KOAc (4-5 equiv.), THF (1 mL), room temperature. b. Isolated
yields. c. Reaction condition: 12 h.
28 (100:0: 0)c
KOAc
42 (98:0: 2)
90 (72:0:28)d
24 (92:0:8)
29 (93: 0:7)
33 (100:0:0)
9
KOAc (2M)
1
THF
1
1
1
0
KOAc
KOAc
KOAc
Pd2(dba)3/5%Ad3P
THF
We have also carried out the study of the borylation reaction of
aryl iodides, aryl bromides and aryl chlorides with
bis(pinacolato)diboron. We found under the same reaction
condition, the reaction of aryl iodides occurred much slower than
aryl chlorides and aryl bromides (Table 3). As aryl iodides have
1
2
Pd2(dba)3/7.5%Ad3P THF
1
Toluene
13
14
15
KOAc
KOAc
KOAc
1
1
1
Dioxane
EtOH
THF
60 (89:0:11)
71 (69:0:31)
27 (100:0:0) e
been established to readily undergo oxidative addition with Pd(0)
41 (100:0:0) f
50 (100:0:0) g
1
6
7
KOAc
KOAc
1
1
THF
THF
11,12
catalysts,
the low conversion suggested that the
1
transmetalation step might likely be the rate-determining step for
the borylation reaction of aryl iodides with
THF
23 (99:0:1)g
bis(pinacolato)diboron. We found by lengthening the reaction
time and using 4 equivalents of base, aryl bromides underwent
the borylation reaction smoothly, yielding the desired product in
excellent yields (Table 3, entries 10-13). By using aqueous
solution of KOAc and extending the reaction time, high yields
were also obtained with aryl iodides as the substrates (Table 3,
entries 14-15).
1
2
1
8
9
KOAc
(2)
(3)
Pd NH2
t-Bu3P Cl
31 (100:0:0)g
99 (100:0:0)h
1
KOAc
KOAc
THF
THF
Pd NH2
XPhos Cl
2
0
1
a. Reaction conditions: p-tolyl chloride (1.0 equiv.), bis(pinacolato)diboron (3.0 equiv.),
1
(5 mol%), base (3 equiv.), THF (2 mL), room temperature, 4 h. b. Based on GC-MS data
or 1H NMR analysis. c. KOAc was used as received. d. 2M KOAc (aqueous solution) was used.
e. 2 equivalents of base was used. f. 4 equivalents of base was used. g. 5 equivalents of base was used.
h. Reaction time: 24 h.
Table 3. Room Temperature Complex 1-Catalyzed Borylation
Reaction of Aryl Halides with Bis(pinacolato)diboron
a
With complex 1 as the catalyst, THF as the solvent and KOAc as
the base, we next examined room temperature Pd(0)/Ad P-
3
catalyzed borylation reactions of a number of aryl chlorides. Our
results are summarized in Table 2. As shown in Table 2,
complex 1 proved to be an efficient catalyst for both activated
and deactivated aryl chlorides, including those with ortho-, meta-
and para-substituents. Complete conversions and good isolated
4

O
O
O
5 mol % 1
O
O
O
O
Ar X +
Ar B
B B
B
Cl
O
O
O
5 mol % Catalyst
O
O
KOAc, THF, r.t., 4 h
B
Cl
B B
KOAc, THF, r.t., 60 h
O
Conversion (%)b
O
Entry
Ar-X
Cl
Entry
Ar-X
Catalyst
Yield (%)b
1
2
3
4
5
6
33
72
11
24
70
7
Br
I
1
2
3
Cl
Cl
Cl
1
1
73c
84
Cl
Cl
MeO
Cl
Br
I
77
1
1
2
Cl
Cl
MeO
36d
0
4
5
6
MeO
O
Cl
Cl
5
2
7
8
9
Cl
Br
I
Cl
Cl
O
O
5
5
26e,f
3
7
Cl
90c,d
a. Reaction conditions: aryl halides (0.2 mmol), bis(pinacolato)diboron (6 equiv.), K3PO4 (10 equiv.),
THF (1 ml), room temperature. b. Isolated yields. c. Conversion based on 1H NMR. The ratio of
4-chlorophenylborate to 1,4-phenyldiborate was 61: 39. d. 18% of monochloroborate was observed.
e. 13% of monochloroborate was observed. f. Reaction time: 48 h.
1
0
1
Br
Br
Br
92c,d
93c,d
1
1
2
MeO
O
5c,d
9
1
3
4
Br
I
Compared to other reported Pd(0) catalyst systems for the
coupling reaction of aryl chlorides with bis(pinacolato)diboron,
95c,e
91c,e
1
MeO
O
5
t, 6a
5y
e.g., Pd(0)/Buchwald’s biphenylphosphines,
Pd(0)/PCy3,
1
5
I
which required elevated reaction temperature and/or additional
amounts of ligands, complex 1 catalyzed the reaction efficiently
at room temperature. Considering the easy availability and air-
stability of complex 1, even the requirements of the slightly
higher catalyst loading or longer reaction time would still
favorably place complex 1 into one of useful catalysts.
a. Reaction conditions: aryl halides (0.2 mmol), bis(pinacolato)diboron (3 equiv.),
KOAc (3 equiv.), THF (1 mL), room temperature. b. Based on 1H NMR. c.Isolated
yields.d. Reaction condition: KOAc (5 equiv.), rt, 24 h. e. Reaction condition: KOAc
(
2 M, 5 equiv.), rt, 48 h.
We have also examined the coupling reaction of
dichlorobenzenes with bis(pinacolato)diboron. We found that the
Summary
reaction of 1,4-dichlorobenzene with
1
equivalent of
bis(pinacolato)diboron generated 4-chlorophenylborate and 1,4-
phenyldiborate in a ratio of 61:39. By using more amounts of
bis(pinacolato)diboron, we found that the borylation reaction of
3
We have demonstrated that Ad P-coordinated acetanilide-based
palladacycle complex 1 was an excellent catalyst for room
temperature borylation reactions of readily available aryl
chlorides with bis(pinacolato)diboron. Complex 1 represents a
general transition metal catalyst system that can catalyze the
Miyaura borylation reaction of aryl chlorides with
bis(pinacolato)diboron at room temperature. The mild reaction
condition, the easy availability of the catalyst systems, and
1
,4-dichlorobenzene
and
1,3-dichlorobenzene
afforded
phenyldiborates in good yields (Table 4, entries 2 and 3). The
reaction of 1,2-dichlorobenzene with bis(pinacolato)diboron was
also carried out, 1,2-phenyldiborate was obtained in a moderate
1
3
yield, along with a significant amounts of 2-chlorophenylborate
Table 4, entry 4). Complexes 2 and 3 were also employed as
(
excellent coupling yields make Pd(0)/Ad
potentially useful in organic synthesis.
3
P catalyst system
catalysts for the reaction. No desired product was observed with
complex 2 as the catalyst (Table 4, entry 5). 1,2-Phenyldiborate
was obtained
in 26% yield, along with 13% of 2-
Experimental Section
chlorophenylborate, with complex 3 as the catalyst (Table 4,
entry 6). These results suggested that complex 1 was an useful
catalyst for the room temperature cross-coupling reaction of aryl
dichlorides with bis(pinacolato)diboron to access aryldiborates.
General Procedure for Complex 1-Catalyzed Cross-Coupling
Reactions of Aryl Chlorides with Bis(pinacolato)diboron: In a
glovebox with an N
2
atmosphere, to a vial containing
bis(pinacolato)diboron (0.6 mmol, 3ꢀequiv.), complex 1 (8.5 mg,
0.01 mmol, 0.05 equiv.), potassium acetate (78.5ꢀmg, 0.8ꢀmmol,
Scheme 4. Room Temperature Complex 1-Catalyzed Borylation
Reaction of Aryl Dichlorides with Bis(pinacolato)diboron a
4
ꢀequiv.), THF (1ꢀmL), was added aryl chloride (0.2ꢀmmol, 1ꢀ
equiv.). The mixture was allowed to react at room temperature
for 24-48 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 Flash chromatography on silica gel
(hexane : ethyl acetate = 100 : 0 to 85 : 15) yielded the product.
Acknowledgments
We gratefully thank the NSF (CHE1507839) for funding. Partial
support from PSC-CUNY Research Award Program is also
gratefully acknowledged.
Supporting Information Available: Experimental procedure
5

and data for Pd(0)/Ad
bis(pinacolato)diboron.
3
P-catalyzed coupling of aryl chlorides with
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Highlights
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First general Pd(0) catalyst for room temperature Miyaura borylation of aryl chlorides
Broad substrate scope
Mild reaction condition
High yields
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