NaH-mediated direct C-H arylation in the presence of 1,10-phenanthroline

Article abstract of DOI:10.1039/d0cc00730g

Transition-metal-free coupling of haloarenes with unactivated arenes has been developed in the presence of NaH and 1,10-phenanthroline. Various haloarenes bearing methyl, methoxy, halogen (fluoride, chloride, and bromide), cyano, trifluoromethyl, ester, and amide groups can be cross-coupled with unactivated arenes, or heteroarenes in this reaction.

Full text of DOI:10.1039/d0cc00730g

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DOI: 10.1039/D0CC00730G
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NaH-mediated direct C–H arylation in the presence of 1,10-
phenanthroline
Kanako Nozawa-Kumada,* Yuki Iwakawa, So Onuma, Masanori Shigeno, and Yoshinori Kondo*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Transition-metal-free coupling of haloarenes with unactivated the direct C–H arylation of unactivated arenes with haloarenes
arenes has been developed in the presence of NaH and 1,10- is one of the most attractive method because it enables
phenanthroline. Various haloarenes bearing methyl, methoxy, straightforward synthesis of biaryls. Most of the method have
halogen (fluoride, chloride, and bromide), cyano, trifluoromethyl, extensively employed several transition metals (Pd, Rh, Ru, Ir,
ester, and amide groups can be cross-coupled with unactivated Ni, Fe and Cu etc.) for mediating this transformation.7 However,
arenes, or heteroarenes in this reaction.
some catalysts are typically expensive, due to which, the
development of inexpensive and environment-friendly
methods is in high demand. As an alternative approach, the
construction of biaryls via transition-metal-free coupling of
haloarenes with unactivated arenes has been achieved using
radical sources such as Bu3SnH and (Me3Si)3SiH, albeit, with the
use of stoichiometric or super stoichiometric amounts of these
reagents.8 The recent development of strong base-induced
radical cross-coupling with bases such as t-BuOK and t-BuONa
could be an excellent alternative to the aforementioned
drawbacks.9 Herein, we report a NaH-mediated cross-coupling
of haloarenes with unactivated arenes, which are used as the
solvents, in the presence of 1,10-phenanthroline. This reaction
proceeds under transition-metal-free conditions via a radical
process and can be successfully applied to various haloarenes
bearing methyl, methoxy, halogen (fluoride, chloride, and
bromide), cyano, trifluoromethyl, ester, and amide group
substitutions on the benzene rings, and the unactivated arenes
or heteroarenes are used as the solvents.
First, we investigated the optimal conditions for the
coupling reaction using 4-iodoanisole 1a and benzene 2a, which
was used as the solvent. When the reaction was conducted
using NaH (2.0 equiv.) in the presence of 1,10-phenanthroline
(30 mol%) as the additive in benzene (1.5 mL) at 100 °C for 18
h, the cross-coupled biaryl product 3aa was obtained in good
yield (entry 1). Interestingly, the reaction did not proceed at all
in the absence of 1,10-phenanthroline (entry 2), and other
additives such as neocuproine and bipyridine were not effective
for the coupling reaction (entry 3). We tested next, the use of
LiH instead of NaH, and found that it was not effective for the
reaction (entry 4). The lowering of the reaction temperature to
80 °C resulted in decreased yield of the desired product 3aa
(entry 5).
Sodium hydride (NaH) is an inexpensive and structurally simple
reagent. In addition to its extensive use as a Brønsted base in
organic synthesis,1 it has been used for reducing carbonyl
compounds, disulfides, aryl iodides, benzylic halides, and
related functionalities.2 Recently, several advances toward
expanding the use of NaH as a reagent for various novel
transformations are being reported.3-5 For example, Chiba et al.
have developed a NaH/iodide composite system which acts as
a hydride donor and mediates a variety of transformations, such
as hydrodecyanation,3a hydrodehalogenation,3c amide-directed
C–H sodiation,3d nucleophilic amination of methoxy arenes,3e
reduction of amides to aldehydes,3f dearylation of
arylphosphine oxides.3g Zhang and Wang et al. have reported
Pd-catalyzed debenzylation and deallylation of ethers and
esters,4a and reductions of α,β-unsaturated carbonyl
compounds with NaH as the reductant.4b Furthermore, Studer
et al. reported radical-mediated hydrodehalogenation of
haloarenes using NaH and 1,4-dioxane as the reagents and 1,10-
phenanthroline as the initiator.5 While these studies expanded
the use of NaH in synthetic organic transformations, further
investigation is required for further development in this area.
Biaryls are one of the most important structural motifs in
organic synthesis and have found use in various fields such as
medicinal, agrochemical, and material sciences.6 Therefore,
much effort has been devoted to the development of new
synthetic methods for accessing these compounds. Particularly,
Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aoba,
Aramaki, Aoba-ku, Sendai 980-8578, Japan.
E-mail: kumada@m.tohoku.ac.jp, ykondo@m.tohoku.ac.jp
†
Electronic
Supplementary
Information
(ESI)
available.
See
DOI: 10.1039/x0xx00000x
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Table 1 Effect of reaction parameters
a mixture of regioisomers, which indicated the involvement of
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aryl radicals (entry 14). Next, we appliDedOI:t1h0e.10m39e/tDh0oCdC0t0o73t0hGe
coupling reaction of aryl bromides (1a’, 1e’, and 1h’) with
benzene 2a, and were pleased to find the formation of the
corresponding biaryls in good to high yields (entries 15–17).
Finally, the intramolecular reaction of 1n was carried out,
affording the corresponding cyclized product in high yield (entry
18).
NaH (2.0 equiv.)
1,10-phen (30 mol%)
+
MeO
1a (0.20 mmol)
I
H
MeO
100 °C, 18 h
2a (1.5 mL)
3aa
Entry
Variation from standard conditions
none
without 1,10-phen
neocuproine or bipyridine instead of 1,10-phen
Yield (%)a
72(72)b
0
0–20
0
1
2
3
4
5
LiH instead of NaH
at 80 °C
Having completed the cross-coupling of a variety of
substituted arenes, we turned attention to the use of
heteroarenes under the developed conditions (Table 3). After
detailed optimization of the reaction conditions with 4-
iodoanisole 1a and pyrazine 4a as the solvent, we found that
the use of 2.0 equiv. of NaH and 10 mol% of the 1,10-
phenanthroline additive in pyrazine (1.5 g) at 60 °C for 3 h was
the optimal condition for the coupling reaction, which delivered
the desired product 5aa in good yield (entry 1). Next, various
aryl iodides such as iodobenzenes bearing methyl or halogen
atom substitutions (entries 3–6), 2-iodopyridine (entry 7), and
6-iodoquinoline (entry 8) were tested and formed the
corresponding biaryls in moderate yields. When using
substrates bearing chloro or bromo atoms on the benzene ring,
decreasing of the amount of NaH was effective to prevent the
formation of the triaryl byproduct 2-(4-pyrazin-2-
ylphenyl)pyrazine which results from the reaction at both
halogen atoms of the substrate (entries 5 and 6). Investigation
of substrates bearing a methoxy group on one of the benzene
rings was tested next (entries 9 and 10), and steric effects were
observed in the reaction of 2-iodoanisole 1p with 4a (entry 9).
In addition, the coupling reaction of iodobenzene 1b with other
heteroarenes such as quinoxaline (4b) or quinoline (4c)
proceeded and afforded the corresponding biaryls albeit in low
9
Determined by 1H-NMR using 1,1,2-trichloroethane as an internal standard.
a
b Isolated yield in parentheses.
With the optimized reaction conditions in hand, we
investigated next, the substrate scope of this coupling reaction
(Table 2). First, the coupling reaction with benzene 2a was
conducted using various iodoarenes (entries 1–12). While the
corresponding biaryls (3ba–3ma) were obtained in moderate to
high yields, the equivalents of NaH and benzene (2a) required
optimization for each starting material. The reactions with
iodobenzene (1b) and 4-iodotoluene (1c) proceeded smoothly
to furnish the products in good yields (entries 1 and 2).
Substrates bearing halogens at the 4-position afforded
monoarylated products (3da–3ga) with good to high selectivity
(entries 3–6). The reactions of substrates containing electron-
withdrawing groups such as cyano, trifluoromethyl, ester, and
amide moieties on the benzene ring delivered the
corresponding products in moderate to good yields (entries 7–
10). Moreover, 1-iodonaphthalene (1l) and 2-iodopyridine (1m)
afforded the corresponding biaryls (3la and 3ma) in moderate
yields (entries 11 and 12). The coupling reaction of 1a with
monosubstituted benzene 2c as the solvent gave the product as
Table 2 Coupling reaction of haloarenes with unactivated arenes
NaH (x equiv.)
1,10-phen (30 mol%)
+
X
H
Ar
Ar
Ar'
Ar'
100 °C, 18 h
1 (0.20 mmol)
2 (y mL)
3
Entry
1
Ar-X
H-Ar’
x (equiv.)
1.5
1.5
1.5
1.5
1.5
1.5
1.7
2.0
3.0
4.0
1.5
1.5
2.0
2.0
1.5
1.2
y (mL)
5.0
1.0
3.0
3.0
4.0
2.0
4.0
5.0
2.0
2.0
3.0
3.0
1.5
2.0
5.0
1.5
5.0
Product
3ba
3ca
3da
3ea
3fa
3ga
3ha
3ia
3ja
3ka
3la
3ma
3ab
3ac
3aa
3ea
3ha
Yield (%)a
74
C6H5-I (1b)
4-MeC6H4-I (1c)
4-FC6H4-I (1d)
4-ClC6H4-I (1e)
4-BrC6H4-I (1f)
4-IC6H4-I (1g)
4-CNC6H4-I (1h)
4-CF3C6H4-I (1i)
benzene (2a)
2
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
48
69
76
80
47
69
40
58
43
58
64
64
76d
70
59
81
3b
4b
5
6
7
8b
9b
4-t-BuOCOC6H4-I (1j)
4-Me2NCOC6H4-I (1k)
1-C10H7-I (1l)
10c
11
12b
13
14
15
16
17
2-pyridyl-I (1m)
4-OMeC6H4-I (1a)
4-OMeC6H4-I (1a)
4-OMeC6H4-Br (1a’)
4-ClC6H4-Br (1e’)
1,4-difluorobenzene (2b)
benzonitrile (2c)
2a
2a
2a
4-CNC6H4-Br (1h’)
1.5
Me
N
18b
–
2.0
–
3n
96
(1n)
Br
a Isolated yields. b The reaction was conducted at 120 °C. c The reaction was conducted at 140 °C. d Regioisomers of 2-/3-/4- = 56/19/25.
2 | J. Name., 2012, 00, 1-3
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Table 3 Coupling reaction of haloarenes with heteroarenes
View Article Online
DOI: 10.1039/D0CC00730G
NaH (x equiv.)
1,10-phen (10 mol%)
+
X
H
Ar
Ar
Het
4 (y g)
Het
60 °C, 3 h
1 (0.20 mmol)
5
Entry
1
2
Ar-X
H-Het
x (equiv.)
2.0
2.0
2.0
1.5
1.5
1.5
1.5
2.0
2.0
2.0
4.0
2.0
y (g)
1.5
3.0
2.0
2.0
2.0
2.0
1.5
2.0
1.5
1.5
2.0
1.5
Product
5aa
5ba
5ca
5da
5ea
5fa
5ma
5oa
5pa
5qa
5bb
5bc
Yield (%)a
76
4-OMeC6H4-I (1a)
C6H5-I (1b)
pyrazine (4a)
4a
4a
4a
4a
4a
4a
4a
4a
4a
66
71
65
52
62
34
47
38
3
4-MeC6H4-I (1c)
4-FC6H4-I (1d)
4-ClC6H4-I (1e)
4-BrC6H4-I (1f)
2-pyridyl-I (1m)
6-quinolyl-I (1o)
2-OMeC6H4-I (1p)
3-OMeC6H4-I (1q)
C6H5-I (1b)
4b,c,d
5b,c
6b,c,d
7b
8e
9e
10b
11f
12g
64
43
33h
quinoxaline (4b)
quinoline (4c)
C6H5-I (1b)
a Isolated yields. b The reaction was conducted at 80 °C. c The reaction was conducted for 6 h. d 20 mol% of 1,10-phenanthroline was used. e The reaction was conducted
at 100 °C. f The reaction was conducted at 90 °C. Obtained only C-2 substituted product. g The reaction was conducted at 120 °C. h Regioisomers of 2-/3-/4- = 21/25/54.
yields (entries 11 and 12).
With the exploration of the scope complete, we investigated
Table 4 Competition experiments with haloarenes
the mechanism of this process. First, the coupling reaction of
MeO
I
MeO
NC
NaH (2.0 equiv.)
1,10-phen (30 mol%)
substituted haloarenes with benzene afforded single
regioisomers, which rules out the intermediacy of benzyne.10 To
investigate the reaction mechanism, we performed the reaction
in the presence of 1.0 equiv. of the radical scavengers TEMPO
and the galvinoxyl free radical, which led to a significant
reduction in the yield of 3aa (Scheme S1). These results indicate
that the reaction likely proceeds via a radical process. Finally, an
electron-paramagnetic resonance (EPR) experiment was
conducted to confirm the generation of radical species (Figure
S1).11 A strong EPR signal was obtained from the reaction
mixture of NaH and 1,10-phenanthroline in toluene after
heating at 100 °C for 2 h, whereas no EPR signal was detected
in the absence of 1,10-phenanthroline. These results indicate
that a radical intermediate generated by the reaction of NaH
1a
3aa
3ha
+
H
100 °C, 3 h
NC
I
2a (1.5 mL)
1h
Entry
1a (equiv.)
1h (equiv.)
3aa (%)a
3ha (%)a
1
2
3
0.5
1.0
–
0.5
–
1.0
0
17
–
21
–
17
Reaction conditions: iodoarene (0.20 mmol), NaH (0.40 mmol), 1,10-
phenanthroline (0.06 mmol), and benzene (1.5 mL), 100 °C, 3 h. a Determined by
1H-NMR using 1,1,2-trichloroethane as an internal standard.
NaH
1,10-phen
Ar
rearomatization
2a
X
Ar
X
Ar
3
Ar
single electron
transfer
X
H
1
6
7
and 1,10-phenanthroline is involved in this reaction. To gain Fig. 1 Plausible mechanism for coupling reaction of 1 with 2a.
further insight into the mechanism of the transformation, a
competition experiment was conducted using the electron-
sufficient and electron-deficient iodoarenes 1a and 1h (Table 4).
The mixture of 4-iodoanisole 1a and 4-iodobenzonitrile 1h was
reacted with benzene for 3 h, and the results indicated that 1h
is more reactive than 1a (entry 1), which suggests that the
reaction involves a single-electron transfer step, as the
electron-deficient haloarene would be a better electron
acceptor.
On the basis of the aforementioned experimental studies
and previous reports, a plausible mechanism for the biaryl
coupling reaction is proposed (Figure 1). First, the aryl radical
intermediate 6 is formed through single-electron transfer from
the radical species generated by the reaction of NaH and 1,10-
phenanthroline. Then, 6 adds to the unactivated arene to afford
the cyclohexadienyl-type radical 7, which undergoes
rearomatization to give the biaryl product 3.
haloarenes and unactivated arenes or heteroarenes were found
to be suitable substrates for this process. Furthermore, we
conducted some mechanistic experiments, which indicated that
this coupling reaction proceeds via single-electron transfer to
haloarenes and a radical intermediate generated by the
reaction of NaH and 1,10-phenanthroline is involved in this
reaction.
This work was financially supported by the Japan Society for
the Promotion of Science (JSPS) KAKENHI Grant no. 19H03346
and 19K16309. This work was also supported by Grand for Basic
Science Research Projects from Yamaguchi Educational,
FUJIFILM Award in Synthetic Organic Chemistry, Japan, and the
Platform Project for Supporting Drug Discovery and Life Science
Research funded by Japan Agency for Medical Research and
Development (AMED).
In conclusion, we developed a new transition-metal-free
coupling reaction for preparing biaryl compounds in the
presence of NaH and 1,10-phenanthroline. Various substituted
Conflicts of interest
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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and K. Itami, Angew. Chem., Int. Ed., 2012, 51, 8V9ie6w0A;r(tijc)lePO. nBli.ne
There are no conflicts to declare.
Arockiam, C. Bruneau and P. H. Dixneuf, Chem. Rev., 2012,
DOI: 10.1039/D0CC00730G
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