Nickel-catalyzed regioselective C-H acylation of chelating arenes: A new catalytic system for C-C bond formation: Via a radical process and its mechanistic explorations

Article abstract of DOI:10.1039/c9nj02191d

An unprecedented acylation at the ortho C-H bond of chelating arenes via the Ni(ii)-catalyzed cross dehydrogenative coupling strategy has been developed here. This new procedure exhibits excellent regioselectivity and good functional group tolerance. This discovery could be of great importance for the C-H acylation reactions of chelating arenes without any extraneous directing group and for the application of nickel-catalyzed C-H activation. Mechanistic investigations into the reaction process are also described.

Full text of DOI:10.1039/c9nj02191d

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DOI: 10.1039/C9NJ02191D
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Nickel-catalyzed regioselective C–H acylation of chelating arenes:
new catalytic system for C–C bond formation via a radical process
and its mechanism explorations
Received 00th January 20xx,
Accepted 00th January 20xx
Ze-lin Lia, Peng-yu Wua, Kang-kang Suna, and Chun Cai*a
DOI: 10.1039/x0xx00000x
An unprecedented acylation at the ortho C-H bond of chelating arenes via Ni(II)-catalyzed cross dehydrogenative coupling
strategy has been developed here. This new procedure exhibits an excellent regioselectivity and accomplished with good
functional group tolerance. This discovery could be of great importance on the C-H acylation reactions of chelating arenes
without any extraneous directing group and the application of nickel-catalyzed C-H activations. Mechanistic investigations
into the reaction process are also described.
www.rsc.org/
described a facile and efficient protocol for palladium-catalyzed
ortho-acylation of 2-aryl pyridines. The reported procedure
utilized arylmethyl amines as the new, cheap and readily
Introduction
The synthesis of aryl ketones plays a very important role in
modern organic chemistry due to the widespread application of
functionalized carbonyl compounds in natural products, drug
compounds, functional materials and disease treatment1. For
available acylation reagent and exhibited high regioselectivity
for 2-aryl pyridines. Furthermore, a general and selective
ruthenium-catalyzed acylation with carbon monoxide of
(hetero)arenes bearing ortho-directing groups was provided by
Beller’s team3k, opening up new possibilities for the first
ruthenium catalyzed carbonylative C-C bond formation by
directed C H functionalization. All the previous developed
methodologies were regioselective and tolerated good
functional compatibility. However, they were generally limited
by the high-cost of noble metal catalyst, by efficiency, or by the
use of poisonous reagents. Apart from these, there is still a need
for complementary methods to attain a broader utility of this
transformation.
examples (Scheme 1,
estrogen), Toicapone
1
2
,
2
and
(for the treatment of Parkinson's
(for the treatment of
3), Raloxifene 1 (a seletive
disease),
Fenofibrate
3
hypercholesterolemia).
Scheme 1. Examples of drugs containing benzophenones.
Over the past decade, transition metal-catalyzed C–H bond
activation has become one of the most facile and powerful tools
to construct C–C bonds.2 Among a series of reliable C–H
activation procedures, the directing group (DG) assisted C–H
bond activation has received significant attention. In the regard
of acylation in chelating arenes with DG, catalytic systems of
transition metals including Pd and Ru catalyzed C–H acylation in
chelating arenes have been well established.3,4 Representative
examples include the first acylation of ortho-C–H bonds
developed by Cheng‘s group in 2009,3a who discovered that
ortho-C–H bonds of 2-arylpyridines could be directly acylated
under palladium catalysis system using aldehydes as acylation
reagents in the presence of air. Then, Wu3h and co-workers
Scheme 2. Previous strategies for C-H acylation in chelating arenes.
Very recently, nickel5 has displayed its superiority in C–H
activation of chelating arenes due to the abundance, low-cost,
environmental friendliness and good catalytic activity. Our
a.. College of Chemical Engineering, Nanjing University of Science & Technology, 200
Xiaolingwei, Nanjing, 210094, China. E-mail: c.cai@njust.edu.cn
†Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
group5a
has
developed
a
nickel-catalyzed
cross-
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dehydrogenative coupling of α-C(sp3)−H bonds in Table 1
N-methylamides with C(sp3)−H bonds in cyclic alkanes to form
C–C bonds. So we next consider whether the low-cost catalytic
systems could be used in acylation of chelating arenes with DG
in order to make the introduction of acyl group more efficiently
and cheaply.
.
Optimization of the reaction conditions[a]
View Article Online
DOI: 10.1039/C9NJ02191D
Entry
Cat.
Ligand
Oxidant
Additive 3a(%)[b]
Inspired by these, we herein demonstrated the first example of
nickel-catalyzed regioselective C–H acylation of chelating
arenes by using toluene derivatives as the acylation reagent.
Compared with previous research studies, our transformation
(1) is the first cheap transition-metal catalyzed C-H acylation of
chelating arenes; (2) explores the reaction process; (3) achieves
regioselective C–H acylation; (4) employs low toxic, stable,
commercially available toluene derivatives, thus avoiding the
harm of high toxicity to human body; (5) tolerates a variety of
functional groups; (6) does not require an extraneous directing
group to be used, thus avoiding the preparation of raw
materials and waste of resources.
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1
2
Ni(acac)2
Ni(OAc)2
Ni(OTf)2
NiCl2
MePh2P
MePh2P
MePh2P
MePh2P
PCy3
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
DTBP
DCP
Ag2O
Ag2O
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10
39
trace
30
29
21
50
78
33
15
34
13
43
0
3
Ag2O
4
Ag2O
5
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ni(acac)2
Ag2O
6
L0
Ag2O
7
PPh3
Ag2O
8
dppe
Ag2O
Results and discussion
9
dppbz
dtbpy
Ag2O
As indicated in Table 1, we started our model study by
investigating the direct C-H acylation of 2-phenylpyridine 1a
with tert-Butyl hydroperoxide (TBHP) as the oxidant in the
presence of Ni(acac)2/MePh2P and Ag2O in toluene (Table 1).
Initially, a number of Ni catalysts were surveyed, including
Ni(acac)2, Ni(OAc)2, Ni(OTf)2 and NiCl2 (Table 1, entries 1-4). The
results showed that Ni(acac)2 displayed the highest catalytic
activity for this process and the anion bound to nickel plays a
critical role in the catalysis system (entry 1). Next, the choice of
ligands was made; dppbz (entries 5–16) proved to be more
suitable to the activation of the catalyst. Thereafter,
replacement of TBHP with other peroxides, such as Di-t-butyl
peroxide (DTBP) and Dicumyl peroxide (DCP) fails to give better
results (entries 17-18). In addition, we are also interested in the
influence of different Ag salts on the yield (entries 19–20), we
found that the reaction could proceed well by using Ag2CO3 and
generate the acylation product in 89% yield. Unfortunately,
when we changed the additive from Ag salts to K2S2O8 or Oxone,
the acylation reaction could not proceed well (entries 21–22).
Moreover, optimizations in various solvents were conducted
(entries 23-24), with toluene proving the most suitable for this
transformation. Finally, we have made experiments with lower
catalyst and ligand loading (entry 25-26). Good results have also
been achieved (entry 25)
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23[c]
24[d]
25[e]
26[f]
Ag2O
bpy
Ag2O
phen
Ag2O
TMEDA
BINAP
DME
Ag2O
Ag2O
Ag2O
BDMAE
dppbz
dppbz
dppbz
dppbz
dppbz
dppbz
dppbz
dppbz
dpppz
dpppz
Ag2O
trace
50
36
47
89
46
51
59
37
88
52
Ag2O
Ag2O
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
TBHP
AgSbF6
Ag2CO3
K2S2O8
Oxone
Ag2CO3
Ag2CO3
Ag2CO3
Ag2CO3
With the optimized reaction conditions in hand, the acylation of
various chelating arenes by toluene were tested. As shown in
Table 2, a wide range of functional groups on the phenyl ring of
the 2-arylpyridines were compatible under this procedure and
the reaction efficiency was not sensitive to the electronic
property of the substituents, as both electron-donating groups
[a]Reaction condition: 1a (0.5 mmol), cat. (20 mol %), ligand (40 mol %), oxidant
(2.0 equiv.), additive (50 mol %), toluene (1 mL), 90 oC, 12h. [b]Isolated yield. [c]
toluene (5.0 equiv.), DMSO (1 mL). [d] toluene (5.0 equiv.), PhCl (1 mL). Dppbz = 1,2-
bis(diphenylphosphino)benzene,
L0=1,2-bis(dimethylphosphino)benzene.[e] cat. (10 mol %), ligand (20 mol %). [f] cat.
(5 mol %), ligand (10 mol %).
(
3b) and electron-withdrawing groups at para position on the
phenyl ring could be tolerated well (3c-3e). Next, substrates
with a Br group on the phenyl ring at the meta-position and a
methyl group on the pyridine ring at the 3-position were
investigated, furnishing (3f) and (3g) in 70% and 75% yield
respectively, thus indicating high steric tolerance
BDMAE=bis(2-dimethylaminoethyl)ether,
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of this catalytic system. To our delight, the arene ring can also by GC-MS), indicating that the acylation might proceed through
View Article Online
DOI: 10.1039/C9NJ02191D
be extended to thiazole ring (3h), oxazole ring (3i), quinoline (3j
)
a radical pathway.
and pyrazole (3k). They underwent the reaction to give good
Subsequently, other experiments were also conducted (Scheme 4).
When the acylation reaction was run without Ni(acac)2, no ortho
product was obtained, suggesting that the catalyst is critical for this
Table 2. Screening of substrate scope in the acylation reaction of substituted
chelating arenes.[a]
Table 3. Representative examples in the acylation reaction of chelating
arenes with toluene derivatives.
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[a]Reaction condition: 1a (0.5 mmol), cat. (10 mol %), ligand (20 mol %), oxidant
(2.0 equiv.), additive (50 mol %), toluene derivatives (1 mL), 90 oC, 12h. [b]2-
methylnaphthalene (5.0 equiv.), DMSO (1 mL) .
[a]Reaction condition: 1 (0.5 mmol), cat. (10 mol %), ligand (20 mol %), oxidant (2.0
equiv.), additive (50 mol %), toluene (1 mL), 90 oC, 12h.
yields of the corresponding products, which further expanded
the substrate scope.
Encouraged by the above results, we investigated the tolerance
of this catalysis system for toluene derivatives (Table 3).
Gratifyingly, these transformations showed excellent tolerance
for various toluenes bearing donating as well as withdrawing
Scheme 3. Control experiments.
groups
(4a-4d). Furthermore, methylcyclohexane and
methylnaphthalenes also reacted with 1a to afford
corresponding products in good yields (4f-4h). Unfortunately,
ortho-substituted toluene such as 1-chloro-2-methylbenzene
(4e) can’t couple with 1a well in this procedure and this might
be due to steric effect.
To gain more understanding of this reaction mechanism, some
control experiments were carried out. As is shown in Scheme 3,
we added 4 equivalents of TEMPO (2,2,6,6-tetramethyl-1-
piperidinyloxyl), BHT (butylated hydroxytoluene) or 1,1-
diphenylethene to the acylation reaction as a radical scavenger
and the coupling process was completely inhibited (determined
Scheme 4. Control experiments.
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transformation (Scheme 4, B1). In addition, the procedure did not reaction process. This discovery could be of greaVtieswigAnrtiicfliecaOnnlcinee
proceed well under ligand-free condition (determined by GC-MS), on expanding the field of nickel-catalyzedDCO-HI: 1f0u.n10c3t9io/Cn9aNliJz0a2t1io91nDs
indicating that the procedure is very dependent on dppbz (Scheme 4, and provides an important complement to C-H acylation
B2). Moreover, when 2-phenylprydine treated with benzaldehyde in reactions. Further studies in our laboratory are devoted to
the absence of TBHP, we failed to get the desired product (Scheme developing a milder method and performing a more detailed
4, B3 and B4). The results showed that the TBHP may have two mechanistic investigation
different effects, oxidizing toluene and promoting the formation of
radicals. It should be noted that this reaction could not proceed
smoothly when we removed Ag2CO3 (Scheme 4, B5).
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Experimental
General experimental method
All compounds are characterized by 1H NMR, 13C NMR and MS.
Analytical thin-layer chromatography is performed on glass
plates precoated with silica gel impregnated with a fluorescent
indicator (254 nm), and the plates are visualized by exposure to
ultraviolet light. 1H NMR and 13C NMR spectra are recorded on
an AVANCE 500 Bruker spectrometer operating at 500 MHz and
125 MHz in CDCl3, respectively, and chemical shifts are reported
in ppm.GC analyses are performed on an Agilent 7890A
instrument (Column: Agilent 19091J-413:30 m × 320 μm × 0.25
μm, H, FID detection). GC-MS data was recorded on a 5975C
Mass Selective Detector, coupled with
a 7890A Gas
Chromatograph (Agilent Technologies). High resolution mass
spectral data were acquired on Agilent Technologies Accurate-
Mass Q TQF LC/MS 6520 operated by China Pharmaceutical
University.
General procedure for C–H acylation of chelating arenes: To a
mixture of 2-phenylpyridine (0.5 mmol) 1a, Ni(acac)2 (10 mol %),
dppbz (20 mol %), TBHP (2.0 equiv.), Ag2CO3 (50 mol %) and
toluene derivatives (1mL) were added in a reaction tube. The
reaction mixture was stirred at 90°C for 12h. The reaction
mixture was extracted with ethyl acetate (15 mL × 3). The
Scheme 5. Control experiments.
In order to further explore the reaction process, more necessary
control experiments were made in Scheme 5 and Scheme 6.
When we replaced 1a with (E)-1,2-diphenyldiazene, N-
phenylacetamide or acetophenone under optimal conditions,
this reaction did not proceeded well (determined by GC-MS),
showing that the nitrogenous heterocyclic is very critical to this combined organic layers were washed with brine, dried over
transformation (Scheme 5 C1, C2 and C3). Notablely, this
procedure under argon resulted in no significant decrease of the
yield (Scheme 6 D1), suggesting that this procedure was not
essential to oxygen. Finally, the GC-MS analysis of the aliquots
taken during an ongoing reaction of 1a with toluene showed the
presence of benzaldehyde.
MgSO4, and concentrated in vacuo. The residue was purified by
column chromatography on silica gel to afford the desired
products 3.
The rest products were prepared by a similar procedure.
phenyl(2-(pyridin-2-yl)phenyl)methanone (3a): The crude
product was purified by column chromatography on silica gel
(petroleum ether/ethyl acetate = 7:3) to give 3a as white solid
(113.96mg, 88%)3f. 1H NMR (500 MHz, Chloroform-d) δ 8.43 (dd,
J = 4.2, 1.4 Hz, 1H), 8.12 (dd, J = 8.3, 1.4 Hz, 1H), 7.83 – 7.79 (m,
1H), 7.74 – 7.69 (m, 2H), 7.65 – 7.58 (m, 3H), 7.54 – 7.50 (m, 1H),
7.41 (t, J = 7.4 Hz, 1H), 7.30 (t, J = 7.7 Hz, 2H), 7.10 – 7.04 (m,
1H). 13C NMR (126 MHz, Chloroform-d) δ 155.7, 147.9, 138.4,
136.8, 135.6, 133.3, 132.3, 131.4, 129.3, 128.5, 128.1, 127.9,
127.7, 127.1, 121.9, 121.1. GC-MS (EI) m/z: 259.
(5-methyl-2-(pyridin-2-yl)phenyl)(phenyl)methanone (3b):
The crude product was purified by column chromatography on
silica gel (petroleum ether/ethyl acetate = 7:3) to give 3b as
white solid (103.74mg, 76%)3i. 1H NMR (500 MHz, Chloroform-
d) δ 8.39 (s, 1H), 7.73 (dd, J = 7.8, 2.9 Hz, 3H), 7.58 (d, J = 7.6 Hz,
1H), 7.52 (d, J = 7.8 Hz, 1H), 7.46 (d, J = 7.6 Hz, 1H), 7.40 (s, 2H),
7.31 (dt, J = 8.2, 4.1 Hz, 2H), 7.03 (dt, J = 7.5, 3.6 Hz, 1H), 2.50 (s,
3H). 13C NMR (126 MHz, Chloroform-d) δ 156.7, 148.9, 139.5,
138.8, 138.0, 136.4, 132.2, 130.9, 129.7, 129.6, 129.4, 128.6,
128.0, 122.5, 121.7, 21.2. GC-MS (EI) m/z: 273.
Scheme 6. Control experiments.
Conclusions
In summary, the first example of nickel(II) catalyzed
regioselective C–H acylation of chelating arenes by using
toluene derivatives as the acylation reagent has been
developed. This procedure features low-cost, excellent
regioselectivity, avoiding of the harm of high toxicity to human
body, avoiding of the preparation of raw materials, a broad
range of substrates and mechanistic explorations into the
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(5-chloro-2-(pyridin-2-yl)phenyl)(phenyl)methanone (3c):
The crude product was purified by column chromatography on The crude product was purified by columDnOcI:h1r0o.1m03a9t/oCg9rNaJp0h2y19o1Dn
silica gel (petroleum ether/ethyl acetate = 7:3) to give 3c as silica gel (petroleum ether/ethyl acetate = 7:3) to give 3h as
white solid (117.20mg, 80%)3i. 1H NMR (500 MHz, Chloroform- white solid (94.50mg, 60%)6r. 1H NMR (500 MHz, Chloroform-d)
d) δ 8.44 (s, 1H), 8.16 (d, J = 7.9 Hz, 1H), 7.80 – 7.73 (m, 3H), 7.64 δ 8.17 (d, J = 7.1 Hz, 1H), 7.99 (d, J = 7.3 Hz, 1H), 7.82 (d, J = 1.4
(d, J = 5.9 Hz, 1H), 7.57 (d, J = 2.3 Hz, 1H), 7.52 (t, J = 7.0 Hz, 1H), Hz, 3H), 7.69 – 7.64 (m, 2H), 7.60 (dd, J = 7.4, 1.4 Hz, 1H), 7.53
7.45 (t, J = 7.2 Hz, 1H), 7.33 (t, J = 7.7 Hz, 2H), 7.09 (dd, J = 7.6, (t, J = 7.8 Hz, 1H), 7.46 – 7.39 (m, 2H), 7.36 – 7.33 (m, 2H). 13
4.9 Hz, 1H). 13C NMR (126 MHz, Chloroform-d) δ 171.1, 155.6, NMR (126 MHz, Chloroform-d) δ 197.6, 165.4, 153.3, 139.7,
ARTICLE
(2-(benzo[d]thiazol-2-yl)phenyl)(phenyl)methaVnieownAerticle O(3nhlin)e:
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149.0, 140.9, 137.8, 137.2, 136.7, 134.9, 133.5, 132.8, 130.1, 137.8, 135.3, 133.8, 132.7, 132.0, 129.7, 129.3, 128.9, 128.5,
129.5, 129.1, 128.2, 122.8, 122.4. GC-MS (EI) m/z: 293.
128.3, 126.2, 125.4, 123.4, 121.4. GC-MS (EI) m/z: 315.
(5-bromo-2-(pyridin-2-yl)phenyl)(phenyl)methanone (3d):
(2-(benzo[d]oxazol-2-yl)phenyl)(phenyl)methanone
(3i):
The crude product was purified by column chromatography on The crude product was purified by column chromatography on
silica gel (petroleum ether/ethyl acetate = 7:3) to give 3d as silica gel (petroleum ether/ethyl acetate = 7:3) to give 3i as
white solid (133.12mg, 79%)3i. 1H NMR (500 MHz, Chloroform- white solid (100.17mg, 67%)6s. 1H NMR (500 MHz, Chloroform-
d) δ 8.44 (d, J = 4.8 Hz, 1H), 8.16 (d, J = 8.2 Hz, 1H), 7.79 (dd, J = d) δ 8.36 (dd, J = 7.3, 1.7 Hz, 1H), 7.85 (d, J = 7.1 Hz, 2H), 7.72
8.3, 2.1 Hz, 1H), 7.72 (dd, J = 4.0, 2.1 Hz, 2H), 7.64 – 7.61 (m, 1H), (td, J = 7.3, 1.6 Hz, 2H), 7.69 – 7.64 (m, 2H), 7.59 (dd, J = 7.1, 1.7
7.55 – 7.50 (m, 2H), 7.45 (td, J = 7.4, 1.4 Hz, 1H), 7.36 – 7.31 (m, Hz, 1H), 7.52 – 7.47 (m, 2H), 7.42 – 7.39 (m, 2H), 7.30 – 7.28 (m,
2H), 7.10 (ddd, J = 7.7, 4.9, 1.2 Hz, 1H). 13C NMR (126 MHz, 1H). 13C NMR (126 MHz, Chloroform-d) δ 197.1, 150.6, 141.6,
Chloroform-d) δ 171.3, 155.6, 149.0, 141.1, 138.2, 136.7, 133.6, 140.1, 137.3, 133.1, 131.1, 130.2, 130.0, 129.5, 129.3, 128.6,
133.2, 132.8, 131.9, 130.4, 129.5, 128.5, 128.2, 122.7, 122.4. 128.4, 125.3, 124.5, 120.3, 110.5, 100.0. GC-MS (EI) m/z: 299.
GC-MS (EI) m/z: 337.
phenyl(2-(quinolin-2-yl)phenyl)methanone (3j): The crude
3-benzoyl-4-(pyridin-2-yl)benzaldehyde (3e): The crude product was purified by column chromatography on silica gel
product was purified by column chromatography on silica gel (petroleum ether/ethyl acetate = 7:3) to give 3j as white solid
1
(petroleum ether/ethyl acetate = 7:3) to give 3e as white solid (97.34mg, 63%)6t. H NMR (500 MHz, Chloroform-d) δ 8.20 –
(103.32mg, 72%).1H NMR (500 MHz, Chloroform-d) δ 10.16 (s, 8.16 (m, 1H), 8.12 (d, J = 8.6 Hz, 1H), 7.99 (d, J = 7.7 Hz, 1H), 7.82
1H), 8.45 (dd, J = 4.7, 1.5 Hz, 1H), 8.18 (dd, J = 8.0, 1.8 Hz, 1H), – 7.79 (m, 2H), 7.73 (td, J = 8.4, 2.6 Hz, 2H), 7.67 – 7.61 (m, 3H),
8.08 (s, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.77 – 7.73 (m, 2H), 7.69 (dd, 7.53 (t, J = 7.7 Hz, 1H), 7.48 (t, J = 7.5 Hz, 1H), 7.39 – 7.34 (m,
J = 7.6, 1.8 Hz, 1H), 7.64 (d, J = 7.4 Hz, 1H), 7.48 (td, J = 7.3, 1.4 1H), 7.27 (t, J = 7.6 Hz, 2H). 13C NMR (126 MHz, Chloroform-d) δ
Hz, 1H), 7.36 (t, J = 7.8 Hz, 2H), 7.15 (ddd, J = 7.4, 4.8, 1.2 Hz, 156.2, 140.3, 139.4, 138.2, 136.8, 133.7, 132.2, 130.2, 130.2,
1H). 13C NMR (126 MHz, Chloroform-d) δ 191.2, 155.4, 149.2, 129.7, 129.5, 129.3, 129.1, 128.9, 128.5, 128.0, 127.3, 126.6,
144.8, 137.3, 136.8, 136.0, 132.8, 130.7, 130.6, 130.1, 129.6, 126.6, 120.1. GC-MS (EI) m/z: 309.
129.5, 128.5, 128.3, 123.0, 122.9. GC-MS (EI) m/z: 287. HRMS
(ESI) m/z: calculated for [C19H13NO2 + H]+ 288.1025, found crude product was purified by column chromatography on silica
288.1029. gel (petroleum ether/ethyl acetate = 7:3) to give 3k as white
(2-(1H-pyrazol-1-yl)phenyl)(phenyl)methanone (3k): The
(4-bromo-2-(pyridin-2-yl)phenyl)(phenyl)methanone (3f): solid (74.40mg, 60%)6u. 1H NMR (500 MHz, Chloroform-d) δ 8.17
The crude product was purified by column chromatography on (d, J = 7.7 Hz, 1H), 7.69 (d, J = 7.7 Hz, 2H), 7.66 (d, J = 3.1 Hz, 2H),
silica gel (petroleum ether/ethyl acetate = 7:3) to give 3f as 7.64 (d, J = 2.6 Hz, 1H), 7.54 (dd, J = 8.1, 6.6 Hz, 2H), 7.47 (d, J =
white solid (117.95mg, 70%). 1H NMR (500 MHz, Chloroform-d) 7.8 Hz, 1H), 7.34 (t, J = 7.7 Hz, 2H), 6.23 (t, J = 2.1 Hz, 1H). 13
C
δ 8.41 (s, 1H), 7.99 – 7.95 (m, 1H), 7.75 – 7.67 (m, 3H), 7.63 (t, J NMR (126 MHz, Chloroform-d) δ 195.9, 141.2, 136.7, 133.9,
= 6.0 Hz, 1H), 7.52 (d, J = 7.6 Hz, 1H), 7.47 – 7.40 (m, 2H), 7.34 – 133.0, 131.3, 130.2, 129.8, 129.1, 128.5, 128.2, 127.6, 123.4,
7.29 (m, 2H), 7.09 (dd, J = 7.3, 3.9 Hz, 1H). 13C NMR (126 MHz, 107.7. GC-MS (EI) m/z: 248.
Chloroform-d) δ 155.3, 149.2, 141.5, 138.3, 137.5, 136.6, 132.6,
(4-methoxyphenyl)(2-(pyridin-2-yl)phenyl)methanone (4a):
131.8, 131.6, 130.7, 129.4, 128.2, 128.2, 124.5, 122.8, 122.5. The crude product was purified by column chromatography on
GC-MS (EI) m/z: 337. HRMS (ESI) m/z: calculated for silica gel (petroleum ether/ethyl acetate = 7:3) to give 4a as
[C18H12BrNO + H]+ 338.0181, found 338.0183.
white solid (95.37mg, 66%)3f. 1H NMR (500 MHz, Chloroform-d)
(2-(3-methylpyridin-2-yl)phenyl)(phenyl)methanone (3g): δ 8.50 (d, J = 4.1 Hz, 1H), 8.10 (d, J = 8.9 Hz, 1H), 7.82 (d, J = 7.7
The crude product was purified by column chromatography on Hz, 1H), 7.73 (d, J = 8.8 Hz, 2H), 7.66 – 7.63 (m, 1H), 7.56 (d, J =
silica gel (petroleum ether/ethyl acetate = 7:3) to give 3g as 4.1 Hz, 1H), 7.52 (d, J = 7.9 Hz, 1H), 7.15 – 7.10 (m, 1H), 6.99 (d,
white solid (102.38mg, 75%)6q. 1H NMR (500 MHz, Chloroform- J = 8.9 Hz, 1H), 6.81 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H). 13C NMR (126
d) δ 8.41 (d, J = 4.9 Hz, 1H), 8.14 – 8.07 (m, 1H), 7.75 – 7.71 (m, MHz, Chloroform-d) δ 163.1, 156.9, 148.9, 136.6, 132.3, 132.0,
2H), 7.67 (d, J = 8.0 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H), 7.56 (d, J = 130.7, 130.1, 129.1, 128.9, 128.6, 123.3, 122.1, 122.0, 113.7,
7.7 Hz, 1H), 7.50 (d, J = 7.7 Hz, 1H), 7.48 – 7.45 (m, 1H), 7.34 (t, 113.4, 55.4. GC-MS (EI) m/z: 289.
J = 7.6 Hz, 2H), 7.10 (dd, J = 7.7, 4.9 Hz, 1H), 2.28 (s, 3H). 13C NMR
(4-fluorophenyl)(2-(pyridin-2-yl)phenyl)methanone (4b):
(126 MHz, Chloroform-d) δ 170.3, 145.8, 137.6, 133.1, 132.5, The crude product was purified by column chromatography on
132.1, 130.6, 130.4, 130.0, 129.9, 129.8, 129.6, 128.3, 128.0, silica gel (petroleum ether/ethyl acetate = 7:3) to give 4b as
127.9, 122.5, 19.5. GC-MS (EI) m/z: 273.
white solid (96.95mg, 70%)6v. 1H NMR (500 MHz, Chloroform-d)
δ 8.48 (d, J = 4.5 Hz, 1H), 8.19 – 8.16 (m, 2H), 7.82 (d, J = 7.7 Hz,
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1H), 7.75 (d, J = 3.2 Hz, 1H), 7.69 – 7.67 (m, 1H), 7.60 (m, 1H), 8.1, 6.8, 1.2 Hz, 1H), 7.46 – 7.42 (m, 2H), 7.22 (dd, JV=iew8.A2rt,ic7le.2OnHlinze,
13
7.56 (d, J = 7.9 Hz, 1H), 7.20 (d, J = 8.6 Hz, 2H), 7.17 – 7.13 (m, 1H), 6.85 (ddd, J = 6.8, 4.9, 2.0 Hz, 1H)D. OI:C10N.1M03R9/C(192N6J0M219H1zD,
1H), 6.98 (s, 1H). 13C NMR (126 MHz, Chloroform-d) δ 170.5, Chloroform-d) δ 172.7, 157.1, 148.8, 136.3, 134.4, 134.0, 132.4,
167.3, 165.3, 132.9, 132.8, 132.1, 130.5, 129.0, 128.9, 125.7, 131.6, 130.8, 130.3, 129.9, 129.1, 128.7, 128.6, 128.0, 127.7,
123.0, 122.3, 115.8, 115.6, 115.3, 115.2, 100.0. GC-MS (EI) m/z: 126.3, 126.0, 124.6, 123.9, 122.7, 121.6. GC-MS (EI) m/z: 309.
277.
(4-chlorophenyl)(2-(pyridin-2-yl)phenyl)methanone (4c):
The crude product was purified by column chromatography on
Acknowledgements
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silica gel (petroleum ether/ethyl acetate = 7:3) to give 4c as
We gratefully acknowledge the Natural Science Foundation of
Jiangsu Province (BK 20131346, BK 20140776) for financial
support. This work was also supported by the National Natural
Science Foundation of China (21476116, 21402093) and the
Chinese Postdoctoral Science Foundation (2015M571761,
2016T90465).
white solid (109.88mg, 75%)3f. 1H NMR (500 MHz, Chloroform-
d) δ 8.39 (d, J = 4.6 Hz, 1H), 7.82 (d, J = 7.7 Hz, 1H), 7.66 (d, J =
8.5 Hz, 3H), 7.61 – 7.57 (m, 3H), 7.30 – 7.24 (m, 3H), 7.09 (dd, J
= 7.5, 4.9 Hz, 1H). 13C NMR (126 MHz, Chloroform-d) δ 156.4,
148.9, 139.1, 138.6, 136.6, 136.4, 130.7, 130.7, 130.4, 129.0,
128.8, 128.6, 128.6 , 128.4, 122.5, 122.2. GC-MS (EI) m/z: 293.
(4-bromophenyl)(2-(pyridin-2-yl)phenyl)methanone (4d):
The crude product was purified by column chromatography on
silica gel (petroleum ether/ethyl acetate = 7:3) to give 4d as
white solid (111.21mg, 66%)3a. 1H NMR (500 MHz, Chloroform-
d) δ 8.39 (d, J = 4.6 Hz, 1H), 7.82 (d, J = 7.6 Hz, 1H), 7.66 (td, J =
7.5, 2.2 Hz, 2H), 7.58 (td, J = 7.6, 6.7, 2.5 Hz, 5H), 7.44 (d, J = 8.4
Hz, 2H), 7.09 (dd, J = 7.5, 4.8 Hz, 1H). 13C NMR (126 MHz,
Chloroform-d) δ 156.3, 148.9, 139.3, 139.1, 136.8, 136.7, 131.4,
130.8, 130.4, 129.0, 128.9, 128.8, 128.6, 127.3, 122.4, 122.2.
GC-MS (EI) m/z: 337.
Conflicts of interest
There are no conflicts to declare.
Notes and references
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solid (90.10 mg, 68%)6w. H NMR (500 MHz, Chloroform-d) δ
8.72 (d, J = 4.8 Hz, 1H), 7.83 (t, J = 7.7 Hz, 1H), 7.73 (d, J = 7.7 Hz,
1H), 7.64 (d, J = 7.9 Hz, 1H), 7.56 (t, J = 7.5 Hz, 1H), 7.53 – 7.45
(m, 2H), 7.34 – 7.27 (m, 1H), 2.41 – 2.32 (m, 1H), 2.27 (td, J =
11.5, 9.8, 5.8 Hz, 1H), 1.98 (dd, J = 13.3, 3.9 Hz, 1H), 1.78 – 1.74
(m, 2H), 1.64 – 1.54 (m, 1H), 1.51 – 1.48 (m, 1H), 1.43 – 1.39 (m,
1H), 1.34 – 1.30 (m, 1H), 1.24 – 1.16 (m, 1H), 1.05 – 1.00 (m, 1H).
13C NMR (126 MHz, Chloroform-d) δ 157.1, 149.2, 141.2, 140.0,
136.9, 129.9, 128.7, 128.7, 128.1, 122.4, 122.3, 100.0, 50.7, 42.9,
29.1, 25.9. GC-MS (EI) m/z: 265.
naphthalen-2-yl(2-(pyridin-2-yl)phenyl)methanone
(4g):
The crude product was purified by column chromatography on
silica gel (petroleum ether/ethyl acetate = 7:3) to give 4g as
white solid (77.25 mg, 50%)3i. 1H NMR (500 MHz, Chloroform-d)
δ 8.47 – 8.38 (m, 1H), 8.15 (m, 1H), 8.05 – 7.94 (m, 1H), 7.89 (d,
J = 7.7 Hz, 2H), 7.86 – 7.80 (m, 3H), 7.74 – 7.69 (m, 1H), 7.64 (ddt,
J = 11.8, 7.7, 3.2 Hz, 4H), 7.60 – 7.56 (m, 1H), 7.51 (t, J = 7.5 Hz,
1H), 7.06 (s, 1H). 13C NMR (126 MHz, Chloroform-d) δ 135.2,
135.2, 132.3, 131.9, 131.5, 131.4, 130.4, 129.5, 129.1, 129.0,
128.5, 128.3, 128.2, 128.1, 127.8, 127.7, 126.7, 126.5, 125.5,
124.8, 122.7, 122.2. GC-MS (EI) m/z: 309.
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(4h):
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white solid (95.79 mg, 62%)3a. 1H NMR (500 MHz, Chloroform-d)
δ 9.13 (d, J = 8.7 Hz, 2H), 8.92 (d, J = 8.6 Hz, 1H), 8.45 (dd, J = 7.3,
1.5 Hz, 2H), 8.29 – 8.23 (m, 1H), 8.14 (d, J = 8.1 Hz, 2H), 7.97 (d,
J = 8.1 Hz, 2H), 7.83 – 7.80 (m, 2H), 7.77 (dd, J = 7.6, 1.3 Hz, 1H),
7.71 – 7.68 (m, 2H), 7.62 (dd, J = 8.0, 6.8 Hz, 3H), 7.56 (ddd, J =
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DOI: 10.1039/C9NJ02191D
O
O
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TBHP
Ni
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DG
H
H
pathway 1
DG
H
R1
O
R1
H
OOtBu
Ni
Ni
R2
9
CH2 TBHP
CH2
Ni
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pathway 2
DG
Ni
R1
=
Ni
L
low-cost catalytic system
Graphical abstract