Nickel-catalyzed cross-coupling of carboxylic anhydrides with arylboronic acids

Article abstract of DOI:10.1039/c4ra11520a

A nickel-based catalyst was employed in the cross-coupling of carboxylic anhydrides with arylboronic acids, and the reaction was carried out under mild conditions. This new protocol provides an efficient, cheap and convenient alternative to synthesizing aromatic ketones.

Full text of DOI:10.1039/c4ra11520a

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Nickel-catalyzed cross-coupling of carboxylic
anhydrides with arylboronic acids†
Cite this: RSC Adv., 2014, 4, 53885
a
a
Qiang Chen,ab Xin-Heng Fan, Li-Peng Zhangab and Lian-Ming Yang
*
*
Received 30th September 2014
Accepted 17th October 2014
DOI: 10.1039/c4ra11520a
www.rsc.org/advances
A nickel-based catalyst was employed in the cross-coupling of Suzuki–Miyaura acylation.13 Thus, it was of strong interest to us
carboxylic anhydrides with arylboronic acids, and the reaction was to explore the application of nickel-based catalysts in cross-
carried out under mild conditions. This new protocol provides an couplings of boronic acids with carboxylic acid derivatives.
efficient, cheap and convenient alternative to synthesizing aromatic Herein, we wish to disclose our new ndings concerning nickel-
ketones.
catalyzed Suzuki–Miyaura acylation reactions.
The cross-coupling of p-methoxybenzoic anhydride with
p-tolylboronic acid was used as a model reaction to screen
reaction conditions (Table 1). Initially, we selected a NiII–aryl
complex (C-1) as pre-catalyst. This is because we have success-
Major advantages of the Suzuki–Miyaura cross-coupling reac-
tion in carbon–carbon bond-forming reactions encourage
synthetic chemists to continuously expand its scope and enrich
its content.1,2 Accordingly, the utility of carboxylic acid deriva-
tives as electrophilic substrates in the Suzuki–Miyaura reaction
for ketone synthesis has drawn intensive attention.3 Over the
past decade, transition metal-catalyzed coupling reactions of
boronic acids with carboxylic acid derivatives, including acid
chlorides,4 anhydrides,5,6 thioesters,7 2-pyridyl esters,8 and even
carboxylic acids,5a,9 have been investigated. This Suzuki–
Miyaura type acylation represents a highly valuable alternative
to such classic procedures as the Friedel–Cras acylation10 and
nucleophilic addition of organometallics to carboxylic acid
derivatives11 because of its pronounced advantages such as mild
conditions, the ease of manipulation, regioselectivity, and high
yields, etc.
From economic and practical points of view, the develop-
ment of cheap metal catalysts for replacing precious metal-
based systems is highly desirable in transition metal-catalyzed
reactions. To date, however, Suzuki–Miyaura type acylation
reactions have largely depended on noble metal-based catalysts
(particularly palladium).4–9 In striking contrast, much cheaper
nickel, being a well-established counterpart of palladium in
Suzuki–Miyaura reactions,2,12 remains missing in the special
fully
used
NiII–(s-aryl)
complexes,
trans-haloarylbis-
(triphenylphosphane)nickel(II) (Fig. 1), as catalyst precursors in
the Suzuki–Miyaura reaction.12d,l,m These NiII–aryl complexes are
easily prepared from cheap and commercially available starting
materials14 and conveniently used due to their stability to air
and moisture.
As shown in Table 1, although C-1 alone or with common
ligands such as PPh3 did not mediate this coupling reaction
(Table 1, entries 1 and 2), a combination of C-1 and electron-
rich, bulky PCy3 ligand is a very effective catalytic system,
giving the desired product in 85% yield (entry 3). And the role of
ligand PCy3 was conrmed by the following observations: the
yield decreases gradually as the ratio of PCy3 to Ni is reduced
(entries 4 and 5). The use of common nickel(II) compounds,
such as NiCl2$6H2O, Ni(PPh3)2Cl2 and Ni(acac)2, afforded no
ketone product at all (entries 6–8). The reason should be that
these NiII precursors are not able to produce the catalytically
active Ni0 species in the current reaction system.12d Further-
more, bidentate phosphine ligands, such as DPPE, DPPP and
DPPF, appeared to be ineffective ligands (entries 9–11). An
attempt to reduce loading amounts of the catalyst led to a
substantially reduced yield (entry 12). For the bases used,
weaker K2CO3 (entry 13) and Na2CO3 (entry 14) did not work at
all; moreover, the reaction was sluggish without the use of
excess amounts of base K3PO4 (entry 15). Toluene appeared to
be the solvent of choice for the reaction and far superior to
ethereal solvents such as dioxane (entry 16) and THF (entry 17).
Reaction temperatures were essential for this transformation as
well. For example, lower reaction temperatures caused a slower
aBeijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Green
Printing, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R.
China. E-mail: yanglm@iccas.ac.cn; xinxin9968@iccas.ac.cn; Fax: +86-10-62559373
bUniversity of Chinese Academy of Sciences, Beijing 100049, P. R. China
† Electronic supplementary information (ESI) available: General experimental
procedures, characterization details, 1H and 13C NMR spectra of products. See
DOI: 10.1039/c4ra11520a
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Table 1 Screening of conditions for nickel-catalyzed cross-coupling between p-methoxybenzoic anhydride and p-tolylboronic acida
Entry
[Ni(II)] (mol%)
Ligand (mol%)
Base
Solvent
Temp. (ꢀC)
Yieldb (%)
1
2
3
4
5
6
7
8
C-1c (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-2d (5)
C-3e (5)
C-4f (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (2.5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (5)
C-1 (5)
None
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
K2CO3
Na2CO3
K3PO4
K3PO4
K3PO4
K3PO4
K3PO4
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Dioxane
THF
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
30
70
Trace
Trace
85
71
57
0
0
0
PPh3 (10)
PCy3 (10)
PCy3 (7.5)
PCy3 (5)
PCy3 (10)
PCy3 (10)
PCy3 (10)
DPPE (5)
DPPP (5)
DPPF (5)
PCy3 (5)
PCy3 (10)
PCy3 (10)
PCy3 (10)
PCy3 (10)
PCy3 (10)
PCy3 (10)
PCy3 (10)
9
Trace
Trace
7
10
11
12
13
14
15
16
17
18
19
39
Trace
0
33g
12
Trace
46
67
Toluene
Toluene
a
Conditions: p-methoxybenzoic anhydride (1.0 mmol), p-tolylboronic acid (1.5 mmol), base (3.0 mmol), 5.0 mL of solvent, 12 h. b Isolated yields.
c
g
C-1: Ni(PPh3)2(1-naphthyl)Cl. d C-2: NiCl2$6H2O. e C-3: NiCl2(PPh3)2. f C-4: Ni(acac)2. 1.5 mmol of K3PO4 used.
On the part of arylboronic acids, electron-rich and -neutral
ones showed excellent reactivity and delivered the products in
good yields (Table 2, entries 1–6, and 9–14); but electron-
decient boronic acid performed poorly (entries 8 and 16).
Fig. 1 NiII–(s-aryl) complexes.
Several heteroaryl boronic acids were also examined under the
conversion (entry 18), but elevating reaction temperatures did
not bring about a positive effect (entry 19), possibly because the
competitive hydrolysis of the anhydride would be aggravated at
higher temperatures. Finally, our standard conditions were set
up as entry 3 in Table 1.
Under the optimized conditions, the scope and limitations
of this cross-coupling reaction were investigated, and the
results were summarized in Table 2. Generally, electron-neutral
(entries 1–6), -rich (entries 9–14) and -poor (entries 17–19)
anhydrides were all viable electrophilic substrates for the reac-
tion. Further, we noticed an interesting tendency in the anhy-
dride reactivity that the yield would decrease in the order:
electron-rich > -neutral > -poor (e.g., entry 9 vs. 1 vs. 17; entry
11 vs. 3 vs. 18; and entry 13 vs. 5 vs. 19). This phenomenon
appeared contrary to usual metal-catalyzed cross-couplings. The
reason may be that a competitive hydrolysis side-reaction of
anhydrides occurs in the reaction system, and thus the more
electron rich the anhydride is, the more substantially its
hydrolysis is suppressed. Neither aliphatic carboxylic anhy-
drides nor aliphatic boronic acids were suitable for this reaction
and no coupled product was obtained (entries 21 and 22).
Scheme
1 A possible mechanistic pathway for the Ni-catalyzed
Suzuki–Miyaura acylation.
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Table 2 Ni-catalyzed cross-couplings of carboxylic anhydrides with arylboronic acidsa
Entry
1
Acid anhydride
Boronic acid
Product
Yieldb (%)
81
2
3
70
74
4
5
6
77
71
68
7
8
9
0
33
88
10
76
11
12
85
84
13
14
15
16
81
75
0
39
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Table 2 (Contd.)
Entry
17
Acid anhydride
Boronic acid
Product
Yieldb (%)
67
18
19
61
56
20
0
21
22
23
24
0
0
69
69
25
26
66
0
27
0
a
Reagents: carboxylic anhydride (1.0 mmol), arylboronic acid (1.5 mmol), K3PO4 (3.0 mmol), C-1 (0.05 mmol), PCy3 (0.1 mmol), toluene (5.0 mL).
Isolated yields.
b
reaction conditions. Thiophen-3-ylboronic acid could be used system by the reaction of Ni(PPh3)2(1-naphthyl)Cl and an aryl-
in this reaction with appreciable yields (entries 23–25), while boronic acid under basic conditions, which is consistent with
thiophen-2-ylboronic acid and 3-pyridinylboronic acid were our experimental observations: (i) very small amounts of biaryl
ineffective (entries 26 and 27).
were detected in almost all cases; (ii) a deep red colour, usually
Additionally, this coupling reaction seemed to be very as an indicator implying the presence of Ni0 species in solu-
sensitive to the steric effects of both types of substrates. For tions, occurred in the reaction mixture at the initial stage of the
example, slightly bulky 1-naphthyl boronic acid gave a relatively reaction. Therefore, a possible mechanism for the nickel-
lower yield than the phenyl one did (Table 2, entry 6 vs. 5; entry catalyzed acylation reaction is proposed (Scheme 1): oxidative
14 vs. 13), and the steric effects of both types of substrates addition of the aromatic carboxylic anhydride 1 to the Ni0
completely retarded the reaction (entries 7, 15, and 20).
species generates an acylnickel(II) complex 4; subsequent
Based on our previous studies,12d,l,m we believed that the transmetallation of the organic group on an arylboronic acid 2
catalytically active Ni0 might be in situ generated in the reaction onto NiII complex 4 takes places at the Ni–O bond; and nally,
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reductive elimination of an aromatic ketone 3 from the NiII
complex 5 and regenerates the Ni0 species, and then the next
cycle starts again.
In summary, we have for the rst time demonstrated the
feasibility for Ni-catalyzed acylation of arylboronic acids with
carboxylic anhydrides. This protocol provides an efficient,
cheap and convenient route to synthesizing aromatic ketones. A
possible mechanism for this reaction was proposed. Further
work to expand the scope of substrates and elucidate the
mechanistic details is currently underway in our lab.
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Acknowledgements
We thank National Natural Science Foundation of China
(Project nos 20872142 and 21102150) for nancial support of
this work.
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`
`
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