Switching from biaryl formation to amidation with convoluted polymeric nickel catalysis

Article abstract of DOI:10.1021/acscatal.0c03888

A stable, reusable, and insoluble poly(4-vinyl-pyridine) nickel catalyst (P4VP-NiCl₂) was prepared through the molecular convolution of poly(4-vinylpyridine) (P4VP) and nickel chloride. We proposed a coordination structure of the Ni center in the precatalyst based on elemental analysis and Ni K-edge XANES, and we confirmed that it is consistent with Ni K-edge EXAFS. The Suzuki?Miyaura-type coupling of aryl halides and arylboronic esters proceeded using P4VP-NiCl₂ (0.1 mol % Ni) to give the corresponding biaryl compounds in up to 94% yield. Surprisingly, when the same reaction of aryl halides and arylboronic acid/ester was carried out in the presence of amides, the amidation proceeded predominantly to give the corresponding arylamides in up to 99% yield. In contrast, the reaction of aryl halides and amides in the absence of arylboronic acid/ester did not proceed. P4VP-NiCl₂ successfully catalyzed the lactamization for preparing phenanthridinone. P4VP-NiCl₂ was reused five times without significant loss of catalytic activity. Pharmaceuticals, natural products, and biologically active compounds were synthesized efficiently using P4VPNiCl₂ catalysis. Nickel contamination in the prepared pharmaceutical compounds was not detected by ICP-MS analysis. The reaction was scaled to multigrams without any loss of chemical yield. Mechanistic studies for both Suzuki?Miyaura and amidation were performed.

Full text of DOI:10.1021/acscatal.0c03888

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Research Article
Switching from Biaryl Formation to Amidation with Convoluted
Polymeric Nickel Catalysis
Abhijit Sen, Raghu N. Dhital, Takuma Sato, Aya Ohno, and Yoichi M. A. Yamada*
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ABSTRACT: A stable, reusable, and insoluble poly(4-vinyl-
pyridine) nickel catalyst (P4VP-NiCl2) was prepared through the
molecular convolution of poly(4-vinylpyridine) (P4VP) and nickel
chloride. We proposed a coordination structure of the Ni center in
the precatalyst based on elemental analysis and Ni K-edge XANES,
and we confirmed that it is consistent with Ni K-edge EXAFS. The
Suzuki−Miyaura-type coupling of aryl halides and arylboronic
esters proceeded using P4VP-NiCl2 (0.1 mol % Ni) to give the
corresponding biaryl compounds in up to 94% yield. Surprisingly,
when the same reaction of aryl halides and arylboronic acid/ester
was carried out in the presence of amides, the amidation proceeded
predominantly to give the corresponding arylamides in up to 99%
yield. In contrast, the reaction of aryl halides and amides in the absence of arylboronic acid/ester did not proceed. P4VP-NiCl2
successfully catalyzed the lactamization for preparing phenanthridinone. P4VP-NiCl2 was reused five times without significant loss of
catalytic activity. Pharmaceuticals, natural products, and biologically active compounds were synthesized efficiently using P4VP-
NiCl2 catalysis. Nickel contamination in the prepared pharmaceutical compounds was not detected by ICP-MS analysis. The
reaction was scaled to multigrams without any loss of chemical yield. Mechanistic studies for both Suzuki−Miyaura and amidation
were performed.
KEYWORDS: reusable catalyst, nickel catalysis, heterogeneous catalysis, Suzuki−Miyaura coupling, amidation reaction
decomposed, and therefore, the development of highly active,
reusable, and bench-stable heterogeneous nickel catalysts is
challenging. We reported a methodology for the preparation of
highly active and reusable polymeric palladium and copper
catalysts, also known as the molecular convolution method-
ology.7 Considering the lack of metal leaching, high activity,
and reusability of the nickel catalysts developed with this
approach, this methodology was applied to the development of
polymeric nickel catalysts.
Amide linkages play crucial roles in pharmaceuticals, natural
products, and synthetic intermediates,8 including paracetamol,9
acebutolol,10 and phenanthridinone11 (Figure 1). The most
widely used method for amide synthesis is amidation of
carboxylic acid derivatives,12 and N-arylation of amides can be
a useful alternative.13 Unfortunately, there are few reports on
nickel-catalyzed amidation of aryl/alkyl amide and aryl
halides,5h probably because of the poor nucleophilicity of the
INTRODUCTION
■
Transition-metal-catalyzed cross-coupling reactions are one of
the most convenient, versatile, and straightforward methods for
C−C or C−N bond construction.1,2 Despite the widespread
application of palladium-catalyzed cross-coupling reactions,
such processes are not preferable at industrial scales owing to
the high cost of palladium. Compared with palladium, nickel is
an inexpensive and earth-abundant metal, which renders
nickel-catalyzed cross-coupling reactions a highly economical
prospect. However, the relatively high toxicity3 and the low
turnover numbers in catalysis, which requires high catalyst
loadings, are the key challenges with its use. Despite several
reports on homogeneous nickel-catalyzed C−C4 and C−N5
coupling reactions, the development of recoverable and
reusable heterogeneous nickel catalysts with high catalytic
activity is still in its infancy. While homogeneous catalysis is
associated with nickel contamination of the desired products,
heterogeneous nickel catalysis, ideally, could provide oppor-
tunities for catalyst recovery and reuse without the nickel
contamination challenges. Few examples of nickel catalyst
immobilization are known;6 however, their catalytic activity
and reusability requires further improvement and is an ongoing
challenge. Owing to the higher lability of nickel to ligands,
heterogeneous nickel catalysts are unstable and readily
Received: September 6, 2020
Revised: November 5, 2020
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Scheme 2. Preparation of a P4VP-Supported Nickel Catalyst
Figure 1. Representative examples of biologically active molecules
containing an amide linkage.
amide nitrogen. Recently, we reported phenylboronic acid/
ester-assisted Buchwald−Hartwig type amination, wherein the
phenylboronic acid/ester acts as an activator for the formation
of an ate complex with the amines.14 In the absence of
phenylboronic acid, the amination did not occur. On the basis
of this observation, we hypothesized that phenylboronic acid
might activate amide substrates via boron−amide complex
formation (Scheme 1), and this complex might enable the N-
1, entry 1). However, when the reaction was performed in the
presence of phenylboronic ester (2a) as an activator, we were
Scheme 1. Hypothesis for Switchable Selectivity from
Suzuki−Miyaura Coupling to Amidation
Table 1. Switchable Selectivity from C−C to C−N Bond
a
Formation
entry deviation from standard conditions yield 4aa (%) yield 5aa (%)
1
2
3
4
without 2a
none
phenylboronic acid instead of 2a
without P4VP-Ni
0
99
98
0
0
0
1
0
arylation of the amides. On the other hand, phenylboronic
acid/ester is itself a good nucleophile in Suzuki−Miyaura-type
couplings. The Suzuki−Miyaura carbon−carbon bond for-
mation is widespread with applications in both academia and
industry. Despite the several reports on these reactions,1,4
switchable selectivity15 between these two reactions has not yet
been reported. Therefore, we explored the possibility for
switchable selectivity between Suzuki−Miyaura-type coupling
and amidation depending on the presence or absence of
amides. Herein, we report switchable selectivity from biaryl
formation to amidation, promoted by a heterogeneous, bench-
stable, reusable, and convoluted polymeric nickel catalyst,
poly(4-vinylpyridine)7 (P4VP)-NiCl2 polymer.
5
6
7
8
9
10
11
without K3PO4
0
0
2
KOtBu instead of K3PO4
NaOtBu instead of K3PO4
toluene instead of 1,4-dioxane
without 3a
without 3a and 5 mol equiv of 2a
air instead of nitrogen
97
55
60
0
0
94
33
0
55
91
0
a
Standard reaction conditions: 1a (1 mol equiv), 2a (1.5 mol equiv),
3a (3 mol equiv), II (0.1 mol % Ni), K3PO4 (3 mol equiv), and 1,4-
dioxane (2 mL) at 115 °C for 30 h under N2.
pleased to find that the desired amidation product 4aa was
obtained in 99% yield with >99% selectivity, in the absence of
the typical Suzuki−Miyaura reaction product 5aa (entry 2).
The use of phenylboronic acid instead of phenylboronic
ester 2a had no significant effect on the product outcome
(entry 3). In the absence of the nickel complex, no reaction
took place, thus proving the role of nickel as a catalyst (entry
4). In addition, when the reaction was performed in the
absence of a base, no reaction occurred (entry 5). KOtBu was
also an effective base and afforded 4aa in 97% yield and 97%
selectivity (entry 6). On the other hand, NaOtBu provided a
mixture of products suggesting that the presence of strong
potassium bases is critical for achieving high selectivity (entry
7). Although the use of toluene as a solvent afforded a 60%
yield, the amidation proceeded exclusively (entry 8).
Importantly, II was also useful as a catalyst for Suzuki−
Miyaura-type coupling in the absence of 3a and provided the
corresponding biaryl compound 5aa in up to 91% yield with
RESULTS AND DISCUSSION
■
Preparation of Convoluted P4VP-Nickel Catalysts.
When a methanol solution of a commercially available linear
poly(4-vinylpyridine), P4VP (I), was treated with an aqueous
solution of NiCl2·6H2O and stirred for 6 h at room
temperature, molecular convolution occurred to yield II as a
greenish precipitate (Scheme 2).
Catalyst II was insoluble in water, methanol, dioxane,
chloroform, and hexane. The structure of the catalyst
[Ni(P4VP)4(H2O)2]Cl2 (II) is shown in Scheme 2 (for
more details, see Figures S1−S3 in the Supporting
Information).
Catalysis. The catalytic activity of II was examined for the
amidation reaction (for more details, see p S5 in the
Supporting Information). When p-tolyliodide (1a) and
benzamide (3a) were reacted in the presence of P4VP-Ni
(1000 mol ppm (0.1 mol % Ni)), no reaction occurred (Table
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>99% selectivity (entries 9 and 10). A use of air instead of N2
was also successful (entry 11).
With the optimized reaction conditions in hand, the
amidation of various aryl iodides with 3a was investigated
(Table 2); it indicated a broad functional group tolerance.
yields, respectively. The electron-deficient 4-trifluoromethyl-,
3-trifluoromethyl-, 4-acetyl-, and 4-ethoxycarbonyl-iodoben-
zene 1l−1o were readily converted to the corresponding
amidation products 4la−4oa. Unfortunately, the aldehyde
(1p) and nitrile (1q) containing substrates were not able to
generate the desired product. The reactions of alcohol (1r)
and amine (1s) substrates proceeded with 55% and 43% yields,
respectively. Although 2-iodopyridine (1u) did not provide the
desired reaction but the reaction of 3-iodothiophene (1t), 3-
iodopyridine (1v), and 5-iodo-1-methyl-1H-indole (1w)
afforded 4ta, 4va, and 4wa in 69, 88, and 89% yields,
respectively. Notably, bioactive compounds could be synthe-
sized in a single step: N-(pyridin-3-yl)benzamide (4va)
exhibited antiviral8f and NAMPT inhibition activities,8g and
N-(thiophen-3-yl)benzamide (4ta) is a GK activator.8h The
naphthalene series substrates, 1-iodonapthalene (1x), and 2-
iodonapthalene (1y) generated the desired products in 42 and
77% yields, respectively. The N-(naphthalen-2-yl)benzamide
(4ya) obtained from 2-iodonapthalene (1y) possesses miR−
122 inhibition ability.8c
a
Table 2. Amidation of Various Aryl Iodides
Next, the amidation of a variety of amide counterparts was
investigated (Table 3). The electronic perturbation of aromatic
a b
,
Table 3. Amidation with Various Amides
a
All reactions were performed with 1 (1 mol equiv), 2a (1.5 mol
equiv), 3a (3 mol equiv), II (0.1 mol % Ni), K3PO4 (3 mol equiv),
and 1,4-dioxane (2 mL) at 115 °C for 30 h under N2.
Phenylboronic ester 2a was recoverable in up to 96% yield
after the C−N bond-forming amidation. The reaction of 3-
methyliodobenzene (1b) and 2-methyliodobenzene (1c)
afforded 4ba and 4ca in 89 and 93% yields, respectively. The
bulky 4-butyl iodobenzene (1d) was converted to 4da in 71%
yield. The electron-rich substrates 4-methoxy- and 4-ethoxy-
iodobenzenes (1e and 1f) furnished the desired product in 92
and 94% yields, respectively. Iodobenzene (1g) gave 4ga in
84% yield. Chemoselective reactions were realized when the
reaction of 1-bromo-4-iodo-(1h) or 1-chloro-4-iodobenzenes
(1i) was carried out with 3a. Although a trace amount of N-(4-
iodophenyl)benzamide was observed in the reaction of 1h, the
aryl chloride did not participate in the reaction. A significant
amount of the substrate remained unreactive in both cases (1h
and 1i). When 1-chloro-3-iodobenzene (1j) and 1,3-dichloro-
5-iodobenzene (1k) were reacted with 3a, the corresponding
amidation products 4ja and 4ka were obtained in 81 and 82%
a
All reactions were performed with 1a (1 mol equiv), 2a (1.5 mol
equiv), 3 (3 mol equiv), II (0.1 mol % Ni), K3PO4 (3 mol equiv), and
b
1,4-dioxane (2 mL) at 115 °C for 30 h under N2. Reaction time is 72
h.
substituents has a crucial effect on product outcomes.
However, irrespective of the position of the methyl group on
the benzamide (p-, m-, and o-), the amidation proceeded
smoothly (entries 2−4). The electron-rich p-methoxybenza-
mide (3e) afforded 4ae in 99% yield (entry 5). Installation of
an electron-withdrawing nitro group (3f) completely sup-
pressed the reaction by reducing the nucleophilicity of
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benzamide (entry 6). Interestingly, nicotinamide (3g, present
in vitamin B3) successfully furnished N-(p-tolyl)nicotinamide
(4ag) (entry 7). Aromatic and aliphatic amides are applicable
in this amidation. When acetamide (3h) was treated under the
reaction conditions, N-(p-tolyl)acetamide (4ah) was obtained
in 82% yield (entry 8). Similarly, butyramide (3i) and
hexanamide (3j) provided 98 and 84% yields of 4ai and 4aj,
respectively (entries 9 and 10). In addition, olefin function-
alities were tolerated in this reaction. When hex-5-enamide
(3k) was treated with p-tolyliodide (1a), the desired amidation
product (4ak) was obtained in 87% yield (entry 11).
(4-iodophenyl)ethan-1-one (1n) was exposed to the reaction
conditions, a 63% yield of the desired product 5na was
obtained, whereas the reaction of the stronger electron-
withdrawing p-trifluoromethyl substitution (1l) hardly pro-
ceeded. Although 3-iodopyridine furnished an 89% yield of the
coupling product (5va), 3-iodothiophene (1t) was not able to
generate a coupling product (5ta). The synthesis of 2-
phenylnaphthalene (5ya) was successful in 55% yield.
We also examined the effect of different boron sources
(Table 5). While 2-phenyl-1,3,2-dioxaborinane 2a provided
With an extensive exploration of the amidation substrate
scope, we turned attention to studying the substrate scope for
the C−C bond-forming Suzuki−Miyaura coupling. When the
reaction of p-tolyliodide (1a) was performed with 2-phenyl-
1,3,2-dioxaborinane (2a) in the presence of 0.1 mol % Ni (II)
and K3PO4 in 1,4-dioxane, 4-methyl biphenyl (5aa) was
obtained in 91% yield (Table 4). The cross-coupling of 3-
Table 5. Reactivity of Boron Species for Suzuki−Miyaura
a b
,
Coupling
Table 4. Substrate Scope for Aryl Iodides in the Suzuki−
a
Miyaura Reaction
a
All reactions were performed with 1a (1 mol equiv), 2 (5 mol
equiv), II (0.1 mol % Ni), K3PO4 (3 mol equiv), and 1,4-dioxane (2
b
mL) at 115 °C for 30 h under N2. N. R.: No reaction.
5aa in 91% yield, phenylboronic acid neopentylglycol ester 2b
could generate a 60% yield of 5aa. Although phenylboronic
acid glycol ester 2c provided an 80% yield of 5aa,
phenylboronic acid pinacol ester 2d failed to construct the
C−C bond under the catalytic conditions, probably because of
the bulky nature of the boron source. Simple phenylboronic
acid 2e was unable to provide a coupling product. Similarly,
the trifluoro(phenyl)-λ4-borane, potassium salt 2f, was unable
to construct the biphenyl derivatives. The electron-donating
tolylboronic ester 2g and (4-methoxyphenyl)boronic ester 2h
furnished the biphenyls in 79 and 87% yields, respectively,
whereas the electron-deficient (4-(trifluoromethyl)phenyl)-
boronic ester 2i afforded the coupling product in 73% yield.
The results of these experiments reveal that phenylboronic
ester derivatives are essential for the P4VP-Ni-catalyzed
Suzuki−Miyaura type C−C bond formation.
Next, we examined the reactivity of different aryl halides in
the amidation reaction. Interestingly, aryl iodides, aryl
bromides, and aryl chlorides all furnished amidation reaction
products (Table 6).
Having assessed the substrate scope, we investigated the
reusability of II (0.1 mol %, 0.42 mg in the 1st run) (for more
details, see p S37 in the Supporting Information). Unlike the
typical nickel catalysts, our catalyst can be reused up to four
times without significant loss of reactivity (Table 7).
a
All reactions were performed with 1 (1 mol equiv), 2a (5 mol
equiv), II (0.1 mol % Ni), K3PO4 (3 mol equiv), and 1,4-dioxane (2
mL) at 115 °C for 30 h under N2.
methyliodobenzene (1b) and 2-methyliodobenzene (1c) also
afforded coupling products 5ba and 5ca in 87 and 84% yields,
respectively. The presence of the bulky butyl group at the 4-
position of iodobenzene did not have any adverse impact, and
the coupling reaction proceeded successfully (5da). The
reactions of 4-methoxyiodobenzene (1e) and 4-ethoxyiodo-
benzene (1f) afforded the corresponding biphenyl derivatives
5ea and 5fa in 92 and 94% yields, respectively. In the case of
the polyhalide-substituted starting materials, the reaction
proceeded with high selectivity. When 1-chloro-4-iodobenzene
(1i) and 1,3-dichloro-5-iodobenzene (1k) were subjected to
biphenyl formation conditions, 4-chloro-1,1′-biphenyl (5ia)
and 3,5-dichloro-1,1′-biphenyl (5ka) were obtained in 86 and
68% yields, respectively. Similarly, 1-bromo-3-iodobenzene
(1z) and 1-bromo-4-iodobenzene (1h) also gave the
corresponding bromobiphenyls (5za and 5ha) in 77 and
72% yields, respectively, and no iodobiphenyls were observed
among the products. The partial electron-withdrawing effect of
the halides reduced the reactivity of the aryl iodides; when 1-
The recovered catalyst can also be used for the sequential
amidation and Suzuki−Miyaura-type cross-coupling sequence
(Scheme 3; for more details, see p S37 in the Supporting
Information). The Suzuki−Miyaura-type cross-coupling of 1a
and 2a was carried out with fresh II under the standard
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Table 6. Reactivity of Different Aryl Halides
Scheme 4. Intramolecular Reaction for Preparation of
Phenanthridinone and the Gram-Scale Reaction
entry
substrate
Y (mol %)
yield (%)
1
2
3
1l, X = I
1l′, X = Br
1l″, X = Cl
0.1
0.5
0.5
75
71
28
Table 7. Catalyst Recovery and Recyclability for the
Amidation Reaction
entry
number of runs
yield 4aa (%)
catalyst recovery yield (%)
1
2
3
4
5
1st
99
93
96
89
88
91
94
85
89
82
2nd
3rd
4th
5th
Scheme 3. Reusability of the Recovered Catalyst in C−C
and C−N Bond-Forming Reactions
Figure 2. Effect of addition of 3a in Suzuki−Miyaura coupling.
addition of 1 equiv of 3a furnished an 82% yield of 4aa, a one
to one ratio of 2a and 3a afforded an 87% yield of 4aa. The use
of excess amide generated a 91% yield of 4aa and afforded 5aa
as a minor product (for more details, see p S30 in the
Supporting Information). In contrast, when phenylboronic
ester 2a was added gradually to the optimal amidation reaction
conditions, a slow nonlinear increase of the formation of 5aa
with a low yield was seen and a sharp increase in the C−N
coupling product was observed (Figure 3). These results
indicate that 2a acts as an activator for the amidation reaction.
Plausible Catalytic Pathway. Mechanistic Studies. Since
the amidation proceeded smoothly with both phenylboronic
conditions to prepare 5aa in 91% yield. The catalyst II was
recovered and reused for the amidation of 1a and 3a, and it
afforded 4aa in 98% yield. Catalyst II was again recovered and
reused for the Suzuki−Miyaura-type cross-coupling and
provided 5aa in 81% yield. These results suggest that the
same catalytic species work in both reactions.
When catalyst II was applied to the intramolecular
amidation reaction (lactam formation) of 2′-iodo-[1,1′-
biphenyl]-2-carboxamide 6 in the presence of phenylboronic
acid 2e as an activator, the cyclization proceeded smoothly to
afford phenanthridinone (7) in 97% yield (Scheme 4a).
Further, in the absence of 2e, cyclization did not proceed.
Notably, phenanthridinone is a biologically active compound
and is an important synthetic intermediate for the synthesis of
several pharmaceutically active molecules.11e
We applied this methodology for the 2 g scale reaction
(Scheme 4b). The desired amidation product methacetin was
observed with 89% yield (1.3 g). We examined the possibility
of nickel contamination of the prepared biologically active
molecules (for more details, see pp S14 and S38 in the
Supporting Information).
The effect of the stoichiometry of 3a and 2a in the Suzuki−
Miyaura coupling and amidation was examined next. The
addition of 10 mol % 3a in the optimal C−C coupling
conditions furnished a 9% yield of the amidation product 4aa
and a 90% yield of 5aa (Figure 2). A gradual increase of 3a in
the reaction mixture increased the amount of 4aa. While the
Figure 3. Effect of the addition of 2a in the amidation.
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acid (2e) and phenylboronic ester (2a), we examined the
plausible catalytic pathway using phenylboronic acid. The
mixture of phenylboronic acid (2e) and benzamide (3a)
provided the reaction intermediate L1 (Scheme 5a). The
nucleophile Nu1 for the C−C coupling reaction and putative
nucleophile Nu2 for the C−N coupling reaction (Scheme 7;
for more details, see p S18 in the Supporting Information).
Scheme 7. Proposed Nucleophiles for C−C and C−N
Coupling Reactions
Scheme 5. Identification of Reaction Intermediates
Initially, a halogen abstraction reaction between the Ni(I)
catalyst and aryl halides generated intermediate B and an aryl
radical (Scheme 8). After that, a radical rebound step provided
structure of L1 was proposed based on the H NMR, 13C
1
Scheme 8. Plausible Reaction Mechanism
NMR, ESI-MS, and DFT calculations (for more details, see pp
S14−S18 in the Supporting Information). The reaction of the
isolated intermediate L1 with 1a in the presence of catalyst II
and K3PO4 efficiently furnished the desired amidation product
4aa in 82% yield (Scheme 5b). The use of the intermediate L1
in the absence of bases did not lead to C−N bond formation
(for more details, see p S15 in the Supporting Information).
To examine the catalytic pathway in greater detail, we
studied the effect of radical inhibitors on the reaction. The
addition of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl, TEMPO,
or butylated hydroxytoluene(BHT) to both reactions com-
pletely suppressed product formation (Scheme 6). These
experiments clearly indicate that both reactions involve a
radical pathway.16
intermediate C. Next, Nu1 or Nu2 underwent transmetalation
to generate intermediate D. The generation of the nucleophile
was the rate-determining step for both C−C and C−N bond
formations. Finally, reductive elimination from intermediate D
produces either C−C or C−N coupling product based on the
nucleophile and regenerates Ni(I) catalyst A.
Scheme 6. Effect of the Radical Inhibitor on Reactivity
CONCLUSIONS
■
In summary, a novel polymer-supported nickel complex was
developed. The structure of this complex was proposed based
on EXAFS, XANES, and DFT analyses. This complex was able
to catalyze both Suzuki−Miyaura-type and amidation reac-
tions. Moreover, perfect switchable selectivity from Suzuki−
Miyaura coupling to amidation was observed. The con-
struction of several biologically active molecules was successful.
The reaction is compatible with large-scale synthesis. Notably,
the catalyst is recoverable and recyclable. A more detailed
investigation of the reaction mechanism and further
application of P4VP-NiCl2 on natural product synthesis is
ongoing in our laboratory.
During the analysis of the reaction products from both
reactions by GC, we observed biphenyl, which originates from
the oxidative coupling of phenylboronic ester 2a, resulting in a
Ni(0) complex, in less than 1% yield. This nickel(0) complex
further reacts with the Ni(II) complex to undergo
comproportionation and forms the catalytically active Ni(I)
complex, A (for more details, see p S38 in the Supporting
Information). The chemical kinetics for the amidation revealed
that the reaction followed zero-order dependence on aryl
iodide and the nickel catalyst, first-order dependence on
arylboronic ester and amide substrates, and second-order
dependence on K3PO4 (for more details, see Figures S5−S9 in
the Supporting Information). On the other hand, the chemical
kinetics for Suzuki−Miyaura-type coupling showed that the
reaction followed zero-order dependence on aryl iodide and
the nickel catalyst, whereas first-order dependence was
observed for arylboronic ester and K3PO4 (for more details,
see Figures S10−S13 in the Supporting Information). On the
basis of these studies, we propose the intermediacy of
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.0c03888.
■
sı
Experimental details for C−C and C−N bond
formations (optimization, reaction procedure, reaction
time-course measurement, and chemical kinetics) and
analytical data (elemental analysis and XAFS) for the
1
nickel catalyst; H NMR, 13C NMR, HRMS, and DFT
1
for reaction intermediate L1; and H NMR, 13C NMR,
melting point, and 19F NMR for all C−C and C−N
coupling products (PDFs)
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berg, 2013; p 17. (m) Palladium-Catalyzed Coupling Reactions:
AUTHOR INFORMATION
Corresponding Author
Yoichi M. A. Yamada − RIKEN Center for Sustainable
Resource Science, Wako, Saitama 351-0198, Japan;
orcid.org/0000-0002-3901-5926; Email: ymayamada@
riken.jp
■
́
́
Practical Aspects and Future Developments, Molnar, A., Ed.; Wiley-
̈
VCH: Weinheim, 2013; p 287. (n) de Meijere, A.; Brase, S.;
Oestreich, M. Metal Catalyzed Cross Coupling Reactions and More,
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Authors
Abhijit Sen − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
Raghu N. Dhital − RIKEN Center for Sustainable Resource
Science, Wako, Saitama 351-0198, Japan
Takuma Sato − RIKEN Center for Sustainable Resource
Science, Wako, Saitama 351-0198, Japan
Aya Ohno − RIKEN Center for Sustainable Resource Science,
Wako, Saitama 351-0198, Japan
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S. L. Biaryl phosphane ligands in palladium-catalyzed amination.
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Soc. Rev. 2013, 42, 9283. (e) Ruiz-Castillo, P.; Buchwald, S. L.
Applications of palladium-catalyzed C-N cross-coupling reactions.
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Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.0c03888
Author Contributions
The manuscript was written through the contributions of all
the authors. All authors have approved the final version of the
manuscript.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank Dr. Tetsuo Honma (JASRI, SPring-8) for assistance
with the XAFS studies (SPring-8, BL14B2). We would like to
thank RIKEN for assistance with elemental analysis (materials
characterization support team, CEMS, RIKEN) and ESI-MS
(molecular structure characterization unit, CSRS, RIKEN)
measurements. We gratefully acknowledge financial support
from AMED (#19ak0101115h) and RIKEN.
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