Efficient Aliphatic C?H Bond Oxidation Catalyzed by Manganese Complexes with Hydrogen Peroxide

Article abstract of DOI:10.1002/asia.201800068

A tetradentate nitrogen ligand containing a benzimidazole ring and an electron-rich pyridine ring was developed, the resulting manganese complex exhibited good activity in the C?H oxidation of simple alkanes. In particular, cyclic aliphatic alkanes were transformed into ketones in very good yields (up to 89 %) by using environmentally benign H₂O₂ as the terminal oxidant. This protocol was also applied successfully in benzylic C?H oxidation, giving the corresponding ketones with very good selectivities. In addition, tertiary C?H bond oxidation of complex molecules by the manganese complex showed potential utility for assembling alcohols with good selectivity in late-stage chemical synthesis.

Full text of DOI:10.1002/asia.201800068

CHEMISTRY
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Accepted Article
Title: Efficient Aliphatic C-H Bonds Oxidation Catalyzed by Manganese
Complex with Hydrogen Peroxide
Authors: Wei Sun, Wenfang Wang, Daqian Xu, and Qiangsheng Sun
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Chemistry - An Asian Journal
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Efficient Aliphatic C-H Bonds Oxidation Catalyzed by Manganese
Complex with Hydrogen Peroxide
[a,b]
[a]
[a]
[a]
Wenfang Wang,
Daqian Xu, Qiangsheng Sun,* and Wei Sun*
Abstract: A tetradentate nitrogen ligand containing a benzimidazole
ring and an electron-rich pyridine ring was developed, the resulting
manganese complex exhibited good activity in C-H oxidation of
simple alkanes. In particular, cyclic aliphatic alkanes were
transformed into ketones in very good yields (up to 89%) using
2 2
environmentally benign H O as the terminal oxidant. This protocol
was also applied successfully in benzylic C-H oxidation giving the
corresponding ketones with very good selectivities. In addition,
tertiary C-H bonds oxidation of complex molecules by the
manganese complex showed potential utility of assembling alcohol
with good selectivity in late-stage chemical synthesis.
Introduction
Oxidation of aliphatic C-H bonds has been viewed as a powerful
yet valuable reaction, which is the fundamental industrial
process for the transformation of saturated hydrocarbons into
Scheme 1. Selected examples of alkane oxidation catalyzed by Mn
complexes.
[1]
functionalized building blocks. Hence, the development of
efficient and selective procedure for C-H bond oxidation is a
long-standing task. Highly selective C-H bond oxidation under
mild conditions is common in biological enzymes, however, has
[
12]
ligand in the presence of H
Costas reported an
monosubstituted cyclohexane achieved by
2
O
2
and acetic acid. Very recently,
enantioselective oxidation of
mol% of
2 2
Mn( ecp), H O and cyclopropanecarboxylic acid (Scheme
[
2]
rarely been achieved by chemical methodology. Inspired by
properties of metal enzymes, large number of metal
complexes catalyzed C-H oxidations have been explored in the
a
2
TIPS
[
3]
[13]
past decades. As a result, metal complexes that can mimic the
reactivity and selectivity of enzymes have emerged as promising
catalysts for alkane oxidation with broad substrate scope. In
1). To improve the efficiency of metal complexes catalysis in
alkane oxidation, a variety of artificial catalysts were explored
[
14]
[15]
[16]
[17]
including manganese,
iron,
copper,
ruthenium,
[18]
[19]
1980, Hill demonstrated that manganese(III) porphyrin catalyzes
nickel
and vanadium
complexes. Despite these important
the hydroxylation and halogenation of cyclohexane with largely
accomplishments, the development of more efficient catalytic
system is still highly desirable toward the practical synthetic use.
Taking into account the structure-activity correlation and the
influence of different substituents on ligand, our group has been
devoted to the design of enzyme models with new metal
[
4]
excess iodosylbenzene as the oxidant (Scheme 1). Then, a
[
5]
5
variety of Mn catalysts with different oxidants (such as KHSO ,
[
6]
[7]
[8]
TBHP, PhIO, peroxy acids ) were investigated intensively.
[
9]
[10]
Among them, dioxygen
and hydrogen peroxide
have
increasingly drawn attention of chemists since they are
environmentally friendly. Shul'pin found that the dinuclear Mn
complex of nitrogen ligands and their applications in oxidation
IV
[20]
reactions.
For instance, a series of benzimidazole-based N4
complex could catalyze oxidation of cyclohexane using H
2
O
2
ligands and their manganese complexes has been developed,
which demonstrate excellent catalytic activity in the
and acetic acid. In this case, both cyclohexanol and
cyclohexanone were obtained and the ratio was 71:51 (Scheme
[
20b,20d]
enantioselective epoxidation
of olefins as well as site- and
[
11]
II
1).
Bryliakov and coworkers reported that cyclohexane could
enantioselective oxidation C-H bonds (e.g., S-PMB-Mn ,
II
[21]
be oxidized by Mn complex with pyridine modified tetradentate
Scheme 1).
In general, benzimidazole and electron-rich
pyridine are used as a pivotal structural motif of linear N4
[
22]
ligands.
In addition, pyridine can be readily modified with
different electron-donating or electron-withdrawing groups,
thereby regulating the catalytic activity and selectivity in an
elaborate manner. For example, Costas and co-workers
reported that iron and manganese complex of PDP (PDP = N,N′-
[
[
a]
b]
W. Wang, D. Xu, Dr. Q. Sun, Prof. Dr. W. Sun
State Key Laboratory for Oxo Synthesis and Selective Oxidation,
Center for Excellence in Molecular Synthesis, Suzhou Research
Institute of LICP, Lanzhou Institute of Chemical Physics (LICP)
Chinese Academy of Sciences
Lanzhou 730000 (P.R. China)
E-mail: wsun@licp.cas.cn
W. Wang
bis(2-pyridylmethyl)-2,2′-bipyrrolidine)
ligand
bearing
dimethylamino group on the pyridine ring show excellent
enantioselectivity in the asymmetric epoxidation of various
University of Chinese Academy of Sciences
Beijing 100049 (P.R. China)
[23]
olefins.
The same group demonstrated that the spin state of
metal center could be tuned by modification of N4 ligands
[24]
thereby resulting in different activities.
Taken together, the
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
development of manganese complexes of chiral N4 ligands that
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Chemistry - An Asian Journal
10.1002/asia.201800068
FULL PAPER
possessed benzimidazole and pyridine rings would be
reasonable toward the further improvement of catalytic acitivity
in the oxidation reaction.
The synthesis of new N4 ligands bearing both of benzimidazole
and pyridine rings and manganese complexes was established
according to Scheme 2. First, the N4 ligands were readily
Herein, we describe a new manganese complex bearing both
benzimidazole and pyridine rings for simple C-H bonds oxidation
of alkanes (Scheme 1). This work features efficient
transformation of simple alkanes into the corresponding ketones
with very good yields (up to 89%, Ketone/Alcohol up to 89:2). In
addition, this protocol was also applied successfully in benzylic
C-H oxidation giving the corresponding ketones with very good
selectivities.
prepared
dimethylcyclohexanediamine
benzimidazole and 2-(chloromethyl)-pyridine
respectively. Then the manganese complexes were prepared
using Mn(OTf) in MeCN at room temperature (Scheme 2).
via
a
stepwise
alkylation
with 2-(chloromethyl)
derivatives
of
N,N-
4
2
2
Although the N4 ligands contained two different sp N-donors,
the ligands still coordinated with manganese center in a cis-α
[
20b,20d]
topology (crystal structure of C2, CCDC 1587264.).
[
a]
Table 1. Screening of the C-H oxidation condition.
Results and Discussion
[
b]
[b]
Entry
Cat.
C1
C2
C1
C2
C1
C1
C1
C1
C1
C1
C3
C4
C5
Oxidant
Acid
T
K/%
39
31
68
61
33
31
47
57
89
82
70
30
75
A/%
1
2
3
4
5
6
7
8
9
H
H
H
H
H
H
H
H
H
H
H
H
H
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
O
2 2
(1.3 eq)
(1.3 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
(3.5 eq )
HOAc
HOAc
HOAc
HOAc
PVA
RT
RT
RT
RT
RT
RT
RT
7
7
2
2
1
DMBA
ACA
5
-
o
HOAc
HOAc
HOAc
HOAc
HOAc
HOAc
40 C
2
o
0 C
2
o
10
11
12
13
-10
C
2
o
0 C
6
o
0 C
4
o
0 C
2
[
a] Unless otherwise noted, all reactions were performed in CH
with substrates (0.2 mmol), Mn complex (0.5 mol%), and acid (14 eq.). 50 %
in 0.5 mL MeCN was added dropwise via a syringe pump over 30 min
with further stirring for 30 min. Pivalic acid (PVA), 2,2-dimethylbutanoic acid
3
CN (1.0 mL)
2 2
H O
(DMBA), 1-adamantyl carboxylic acid (ACA). [b] GC yield.
We tried to investigate the performance of two new
manganese catalysts in the oxidation of simple alkanes at the
outset. Cyclohexane was chosen as the model substrate (0.2
II
mmol). Mn catalyst (0.5 mol%) and HOAc (14 equiv.) were
added sequentially in the solution of cyclohexane (in 1 mL
3 2 2 3
CH CN) at room temperature. Aqueous H O (in 0.5 mL CH CN,
1.3 equiv.) was added dropwise through a syringe pump for 30
min. To our delight, the oxidation of cyclohexane catalyzed by
the manganese complexes occurred successfully and the major
product was ketone (K/A = 39/7). However, the conversion of
both reactions was moderate. Thus, the C-H oxidation of
cyclohexane was carried out under higher injection of 3.5 equiv.
II
Scheme 2. Synthesis of Mn complexes with tetradentate nitrogen ligands
(
yellow; S, orange.).
crystal structure of C2, CCDC 1587264. N, blue; Mn, violet; O, red; C, gray; F,
of
2 2
H O , which was widely adopted in the methylene
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Chemistry - An Asian Journal
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FULL PAPER
[
13,15k,21]
oxidation.
As a result, both conversions were improved
[a]
2 2
Table 3. Benzylic C-H bonds oxidation catalyzed by Mn catalyst with H O
giving higher yields and selectivities (Table1, entries 3-4). Based
on the preliminary results, the catalyst C1 exhibited better
catalytic activity than C2 (Table1, entries 1-2). Then, several
common carboxylic acids were also studied in the presence of
[
b]
[c]
Entry
1
Substrate
Product
Conv.
Yield
72%
67%
52%
0
.5 mol% C1 and no better result was obtained (Table1, entries
[
25]
5-7).
Finally, considering the temperature of the reaction
would affect the activity and stability of possible high-valent
metal-oxo generated in situ, the oxidation of cyclohexane
catalyzed by manganese catalyst C1 was carried out under
9
3%
2
3
4
5
o
o
different temperatures varying from -10 C to 40 C (Table1,
entries 8-10). It was found that the reaction gave the best yield
o
and selectivity at 0 C. Therefore, the optimal reaction was
96%
91%
86%
91%
89%
82%
achieved by 0.5 mol% of C1 in the presence of 3.5 eq. H
2
O
2
and
o
1
4.0 eq. HOAc at 0 C in CH CN (Table1, entry 9). We also
3
examined the catalysts bearing two same arms under the
optimal conditions comparing with C1 (Table1, entries 11-13). It
was shown that our new catalyst exhibit better catalytic activity
in the oxidation of cyclohexane.
We next tested various simple alkanes in the C-H oxidation
under the optimized conditions. All cyclic aliphatic alkanes were
transformed to the corresponding ketones with fair to very good
yields (Table 2, entries 1-4). Monosubstituted tert-
butylcyclohexane was also oxidized under the standard
conditions, 78% overall yield of ketone was obtained and the
ratio of 3-ketone/4-ketone was 3.4:1 (Table 2, entry 5). Then, we
explored the oxidation of n-hexane, both 2-hexanone and 3-
hexanone were produced and the overall yield was 33% (Table
6
7
8
9
45%
30%
39%
20%
2, entry 6). In addition, tetrahydrofuran was transformed to
butyrolactone in 26% yield (Table 2, entry 7).
[
a]
Table 2. C-H oxidation of simple cyclic aliphatic alkanes.
[
d]
d]
[e]
79%
64%
73%
56%
[
b]
[c]
Entry
1
substrate
product
Conv.
Yield
[
[e]
94%
81%
98%
98%
89%
2
3
4
68%
72%
86%
[
e]
10
31%
17%
[
a] Unless otherwise noted, all reactions were performed in CH
with substrates (0.2 mmol) and C1 (0.5 mol%), HOAc (14 eq.), 3.5 eq. 50 %
in 0.5 mL MeCN was added dropwise via a syringe pump over 30 min
with further stirring for 30 min at 0 C. [b] Determined by GC. [c] GC yield. [d]
Determined by HNMR with 1,3,5-trimethoxybenzene as an internal standard.
3
CN (1.0 mL)
2 2
H O
o
1
[e] Isolated yield.
5
95%
78%
After converting the cyclic aliphatic alkanes into ketones, the
3
.4:1
:1.5
benzylic C-H oxidation was further investigated using the
established method. A variety of substituted phenylethanes
were applied in this established system, and these compounds
were all converted into the corresponding ketones successfully
6
7
76
44
36%
26%
1
(
Table 3, entries 1-5). 4-Methylphenylethane was oxidized
smoothly with moderate yield (Table 3, entry 2). Halogenated
phenylethanes were well tolerated giving ketones with good to
excellent yields (Table 3, entries 3-5). Phenylpropane could also
be transformed in fair yield without primary C-H bond oxidation
[
a] Unless otherwise noted, all reactions were performed in CH
with substrates (0.2 mmol) and C1 (0.5 mol%), HOAc (14 eq.), 3.5 eq. 50 %
in 0.5 mL CH CN was added dropwise via a syringe pump over 30 min
with further stirring for 30 min at 0 C. [b] Determined by GC. [c] GC yield.
3
CN (1.0 mL)
H
O
2 2
3
(
Table 3, entry 6). Isobutyrophenone was produced when
o
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Chemistry - An Asian Journal
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FULL PAPER
isobutylbenzene was subjected to the oxidation system (Table 3,
entry 7). Furthermore, for the oxidation of diphenylmethane, the
reaction gave the benzophenone in 73% yield (Table 3, entry 8).
The oxidation of 1,2,3,4-tetrahydronaphthalene occurred
preferentially at one of the both benzylic sites with 56% yield of
ketone (Table 3, entry 9). Phenethyl acetate was also tested
under the standard conditions, and the benzylic C-H oxidation
took place successfully albeit with 17% yield (Table 3, entry 10).
temperature gave 1-adamantanol with improved yield (Table 4,
entry 2). In both cases of adamantane, adamantane-1,3-diol was
[
26]
obtained (Table 4, entries 1 and 2). Then, the enantiomers of
menthyl acetate were also investigated in the established
manganese complex catalyzed C-H oxidation (Table 4, entries
3-4). The results showed that (1S)-(+)-menthyl acetate exhibited
higher activity than (1R)-(-)-menthyl acetate under this catalytic
system (Supporting information, Figure S1 and S2). cis-1,2-
Dimethylcyclohexane was oxidized successfully, giving 69%
yield of dimethylcyclohexanol (Table 4, entry 5).
[
a]
Table 4. Selective tertiary C-H bond oxidation of complex molecules.
Previously, R,R-MCP-Mn(OTf)
bis(2-pyridylmethyl)-cyclohexane-1,2-diamine) showed poor
catalytic activity in the selective oxidation of ethylbenzene.
the present research work, replacing one of pyridine N-donor in
the MCP ligand by a benzimidazole motif, the manganese
complex (C1) with new hybrid N4 ligand (L1) became an
efficient catalyst in the oxidation of various aliphatic C-H Bonds;
in most cases, its performances are better than the previous S-
2
(MCP = N,N’-dimethyl-N,N’-
[
b]
[c]
Entry
Substrate
Product
Conv.
Yield
[
21]
In
[
[
d]
e]
1
2
65%
72%
24%/19%
45%/13%
[
f]
[g]
3
30%
20%
2
PMB-Mn(OTf) (Scheme 1).
Conclusions
[
h]
In summary, we design and prepare a new N4 ligand and the
corresponding manganese complex that contains benzimidazole
and pyridyl groups together. This manganese complex shows
good activities and selectivities in the selcetive oxidation of C-H
with regard to both simple alkanes and benzylic C-H, in the
4
62%
27%/8%
2 2
presence of environmentally benign H O , with AcOH as an
o
additive at 0 C. This protocol is also applied successfully in the
late-stage oxidation of complex molecules albeit with moderate
to low yields. More detailed mechanism and efficient catalysts
on C-H oxidation are still underway in our laboratory.
[
h]
5
6
70%
84%
48%/8%
Experimental Section
69%
General remarks
The chemicals were purchased from commercial suppliers and used
[
a] Unless otherwise noted, all reactions were performed in CH
with substrates (0.2 mmol) and C1 (0.5 mol%), HOAc (14 eq.), 1.3 eq. 50 %
in 0.5 mL MeCN was added dropwise via a syringe pump over 30 min
3
CN (1.0 mL)
1
13
without further purification. H NMR and C NMR spectra were recorded
on a Bruker Avance III 400 MHz spectrometer using CDCl as the solvent
H
O
2 2
3
o
with further stirring for 30 min at 0 C. [b] Determined by GC. [c] GC yield. [d]
-adamantanol and 2-adamantanone (2.9% yield). [e] Reaction was carried
with TMS as an internal reference. High resolution (HR) MS (ESI) was
2
II
determined on a Bruker Daltonics microTOF-Q mass spectrometer. GC–
out at RT. 2-adamantanol and 2-adamantanone (5.0% yield). [f] 70% substrate
was recovered. [g] Isolated yield. [h] Determined by H NMR with nitrobenzene
as internal standard.
MS spectra were recorded on an Agilent Technologies 7890A GC-
system/Agilent 5975 MS (EI) with a HP-5-MS column (0.25 mm×30 m,
Film: 0.25μm). GC analysis was performed on an Agilent 6820 GC with a
HP-5-MS column. X-ray crystallographic data were collected on a Bruker
SMART CCD1000 diffractometer with graphite-monochromated Mo Kα
radiation (λ = 0.71073 Å) at 296(2) K. Column chromatography was
generally performed on silica gel (300-400 mesh) and TLC inspections
were performed on silica gel GF254 plates. Elemental analysis were
performed on a Vario EL cube elementar analyzer.
1
In addition to simple alkanes, the oxidation of complex
molecules at late stage features step-economy and less time-
consuming. Thus, we chose several model substrates, such as
aliphatic hydrocarbons bearing both tertiary and secondary C-H,
to further expand the scope of the substrates. It was found that
all substrates underwent tertiary C-H oxidation with high
selectivities owing to the electrophilic nature of possible
manganese-oxo species. The oxidation of adamantane and cis-
Synthesis of the N4-based ligands and manganese complexes
[
27]
4
-methylcyclohexyl pivalate furnished the corresponding
(1H-benzo[d]imidazol-2-yl)methanol (10) : To a mixture of glycolic
acid (4.6 g, 60.0 mmol) and benzene-1,2-diamine (9) (2.1 g, 20.0 mmol)
was added HCl (4 N, 60 mL). The reaction was refluxed at 100 °C for 6 h
alcohols with low yields (Table 4, entries 1 and 3). It was
noteworthy that C-H oxidation of adamantane under room
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Chemistry - An Asian Journal
10.1002/asia.201800068
FULL PAPER
o
and then quenched with saturated aqueous sodium bicarbonate. The
(2 eq.) in 30 mL of CH
ethyl-1H-benzo[d]imidazole (5) (582 mg, 3.0mmol) which dissolved in 20
mL of CH Cl slowly by constant pressure dropping funnel. After addition,
the resulting mixture was stirred overnight. Then the mixture was filtered,
and the precipitate was washed with CH Cl . The combined filtrates were
2 2
Cl under 0 C was added 2-(chloromethyl)-1-
mixture was filtered through Celite to give a white solid in 58% yield
1
(
7
1.7g, 11.5 mmol). H NMR (400 MHz, DMSO) δ = 8.81 (s, 2H), 7.64-
2
2
13
.41(m, 2H), 7.22-7.08(m, 2H), 4.69 ppm (s, 2H). C NMR (101 MHz,
DMSO) δ = 155.1, 138.7, 121.2, 114.8, 57.7 ppm. HRMS (ESI-MS) calcd.
2
2
+
for C
8
H
9
N
2
O [M+H] : 149.0709, found: 149.0708.
evaporated under vacuo. To the residue a 2 N solution of NaOH was
added to reach pH > 10, and the mixture was extracted with 3 x 20 mL of
[
27]
2 2 4
CH Cl , The organic fractions were combined, dried over NaSO and the
(
(
1-ethyl-1H-benzo[d]imidazol-2-yl)methanol (11) : To a solution of
10) (1.5 g, 10.0 mmol) in DMF (20 mL) were added bromoethane (20.0
solvent was eliminated under vacuum. The obtained brown oil that was
purified by silica column and the collected fractions were removed under
mmol) and potassium carbonate (50.0 mmol), and the reaction mixture
was stirred at room temperature for 24 h. Then the mixture was diluted
with methylene chloride and saturated aqueous sodium chloride. The
organic layer was separated, and the aqueous layer was extracted with
methylene chloride. The combined organic layers were dried over
anhydrous sodium sulfate and concentrated in vacuo to provide a crude
product, which was purified by silica column using EtOAc as eluent to
1
reduced pressure to provide light yellow solid (360 mg, yield 40%). H
NMR (400 MHz, CDCl
H), 7.24 – 7.14 (m, 2H), 4.34 – 4.09 (m, 2H), 3.85 (dd, J = 58.4 Hz, 14.0
Hz, 2H), 2.58 (t, J = 9.2 Hz, 1H), 2.41 (s, 3H), 2.37 – 2.23 (m, 1H), 2.17
s, 3H), 2.12 (d, J = 7.2 Hz, 1H), 1.90 (d, J =8.4 Hz, 1H), 1.80 (d, J = 8.4
Hz, 1H), 1.71 (d, J = 6.8 Hz, 1H), 1.38 (t, J = 7.2 Hz, 3H), 1.35 – 0.97
3
) δ = 7.66 (d, J = 7.6 Hz, 1H), 7.30 (d, J = 7.6 Hz,
1
(
13
1
3
ppm (m, 5H). C NMR (101 MHz, CDCl ) δ = 151.8, 142.2, 135.0, 122.5,
yield the title compound (11) (704 mg, yield 40%). H NMR (400 MHz,
CDCl ) δ = 7.72-7.62 (m, 1H), 7.47 – 6.99 (m, 3H), 5.62 (s, 1H), 4.87 (s,
H), 4.29 (q, J = 7.2 Hz, 2H), 1.45 ppm (t, J = 7.2 Hz, 3H). C NMR (101
MHz, CDCl ) δ = 153.6, 141.5, 134.7, 122.8, 122.2, 119.3, 109.6, 56.6,
8.8, 15.2 ppm. HRMS (ESI-MS) calcd. for C10
found: 177.1025.
1
21.9, 119.5, 109.4, 66.8, 60.1, 51.8, 38.6, 35.7, 33.2, 30.4, 25.2, 24.4,
3
+
13
21.8, 15.0 ppm. HRMS (ESI-MS) calcd. for C18H29N4 [M+H] : 301.2314,
found: 301.2492.
2
3
+
3
13 2
H N O [M+H] : 177.1022,
EtBz
(1R,2R)- MCP (L1): To the stirred mixture of (6) (180 mg, 0.6 mmol)
and dry K
in 30 mL of CH
.9mmol). After addition, the mixture was stirred at 90 C for 20 h. After
cooling to rt, the mixture was filtered, and the precipitate was washed
with CH Cl . The combined filtrates were evaporated in vacuo. To the
residue a 2 N solution of NaOH was added to adjust pH > 10, and the
mixture was extracted with 3 x 20 mL of CH Cl , The organic fractions
2
CO
3
(2.0 mmol) and tetra-(n-butyl)ammonium bromide (20 mg)
CN was added 2-(chloromethyl)pyridine (7) (153 mg,
2
-(chloromethyl)-1-ethyl-1H-benzo[d]imidazole (5): To
solution of (11) (704 mg, 4.0 mmol) in CH Cl (30 mL) was added thionyl
chloride (6.0 mmol) slowly. The resulting mixture was quenched with
aqueous Na CO solution after stirring overnight at room temperature.
The aqueous layer was extracted with CH Cl , and the combined organic
phase was dried over anhydrous Na SO . Volatile components were
removed giving an orange solid (5) (698 mg, yield 90%). H NMR (400
MHz, CDCl ) δ = 8.07 – 7.53 (m, 1H), 7.46 – 6.98 (m, 3H), 4.84 (s, 2H),
a
stirred
3
o
0
2
2
2
2
2
3
2
2
2
2
2
4
1
were combined, dried over NaSO4 and the solvent was eliminated under
vacuum. The obtained brown oil that was purified by silica column and
3
13
the collected fractions were removed under reduced pressure to provide
4.31 (q, J = 7.2 Hz, 2H), 1.51 ppm (t, J = 7.2 Hz, 3H). C NMR (101 MHz,
1
yellow solid (140 mg, yield 60%). H NMR (400 MHz, CDCl
3
) δ = 8.48 (d,
3
CDCl ) δ = 148.5, 142.3, 135.0, 123.6, 122.6, 120.4, 109.8, 39.2, 36.8,
+
J = 4.4 Hz, 1H), 7.73 (dd, J = 6.4, 3.6 Hz, 1H), 7.58 (td, J = 7.6, 1.6 Hz,
15.1 ppm. HRMS (ESI-MS) calcd. for C10
2
H12ClN [M+H] : 195.0684,
1
7
7
2
H), 7.51 (d, J = 8.0 Hz, 1H), 7.46 – 7.29 (m, 1H), 7.28 – 7.21 (m, 2H),
.16 – 7.07 (m, 1H), 4.46 (dq, J = 14.4, 7.2 Hz, 1H), 4.23 (dq, J = 14.4,
.2 Hz, 1H), 4.02 (dd, J = 29.6, 13.2 Hz, 2H), 3.79 (dd, J = 35.6, 14.0 Hz,
H), 2.87 – 2.59 (m, 2H), 2.21 (d, J = 15.2 Hz, 6H), 1.98 (d, J = 12.0 Hz,
found: 195.0684.
(
4-(dimethylamino)pyridin-2-yl)methanol (12): (4-Chloropyridin-2-
yl)methanol (7.0 mmol) and dimethylamine (35.0 mmol) were added to a
o
2H), 1.77 (d, J = 7.2 Hz, 2H), 1.31 (t, J = 7.2 Hz, 3H), 1.26 – 0.95 ppm (m,
2
5 mL Schlenk tube and stirred at 155 C for 24h. After cooling to room
temperature, the mixture was diluted with methylene chloride and
washed with H O, brine and dried over Na SO . Then the solvent was
13
4
1
3
3
H). C NMR (101 MHz, CDCl ) δ = 160.6, 152.5, 148.7, 142.6, 136.3,
35.4, 123.1, 122.2, 121.8, 121.6, 119.6, 109.3, 64.4, 63.6, 60.9, 51.9,
8.6, 36.3, 36.0, 25.8, 25.6, 25.3, 24.3, 15.0 ppm. HRMS (ESI-MS) calcd.
2
2
4
eliminated under vacuum and brown residue was obtained. The residue
were recrystallized from acetone to provide the product (12) as light
yellow solid (755 mg, yield 71%). H NMR (400 MHz, CDCl
+
for C24
H N
34 5
[M+H] : 392.2809, found: 392.2794.
1
3
) δ = 8.11 (m,
EtBz,Me2N
(1R,2R)-
MCP (L2): L2 was prepared in analogous manner to L1
1
H), 6.47 (s, 1H), 6.38 (s, 1H), 5.09 (s, 1H), 4.62 (s, 2H), 3.04 – 2.89
13
starting from (6) and 2-(chloromethyl)-N,N-dimethylpyridin-4-amine (8) to
3
ppm (m, 6H). C NMR (101 MHz, CDCl ) δ = 159.7, 155.0, 148.4, 105.5,
1
+
provide a yellow solid (156 mg, yield 60 %). H NMR (400 MHz, CDCl
8.11 (d, J = 6.0 Hz, 1H), 7.76 – 7.58 (m, 1H), 7.26 – 7.17 (m, 3H), 6.81
d, J = 2.4 Hz, 1H), 6.33 (dd, J = 6.0, 2.8 Hz, 1H), 4.40 (dq, J = 14.4, 7.2
Hz, 1H), 4.21 – 4.04 (m, 1H), 4.06 – 3.86 (m, 2H), 3.68 (dd, J = 74.8,
4.0 Hz, 2H), 2.78 – 2.62 (m, 8H), 2.26 (d, J = 13.2 Hz, 6H), 2.09 – 1.91
m, 2H), 1.79 (d, J = 8 Hz, 2H), 1.30 (t, J = 7.2 Hz, 4H), 1.28 – 1.15 ppm
3
) δ
1
1
02.9, 64.6, 39.2 ppm. HRMS (ESI-MS) calcd. for C
53.1022, found: 153.1032.
8 13 2
H N O [M+H] :
=
(
2
-(chloromethyl)-N,N-dimethylpyridin-4-amine (8): To
Cl (30 mL) was added thionyl
chloride (4.5 mmol) slowly. After addition, the resulting mixture was
stirred at rt overnight. The reaction was quenched with Na CO aqueous
solution, and the organic layer was collected. The aqueous layer was
extracted with CH Cl , and the combined organic phase was dried over
Na SO . Removal of volatile components gave the yellow solid (8) (438
mg, yield 86%). H NMR (400 MHz, CDCl
a
stirred
1
solution of (12) (456 mg，3.0 mmol) in CH
2
2
(
(
1
5
13
m, 3H). C NMR (101 MHz, CDCl
3
) δ = 160.3, 154.9, 152.5, 148.5,
42.6, 135.3, 122.1, 121.5, 119.5, 109.2, 105.3, 105.1, 64.5, 64.1, 60.2,
1.6, 38.7, 38.3, 25.8, 25.7, 25.0, 24.3, 15.1 ppm. HRMS (ESI-MS) calcd.
2
3
2
2
+
for C26
39 6
H N [M+H] :435.3231, found: 435.3231.
2
4
1
3
) δ = 8.15 (s, 1H), 6.64 (s, 1H),
EtBz
13
(1R,2R)- MCP manganese complex (C1): Mn(CF SO ) (0.25 mmol,
1
equiv.) in acetonitrile (3 mL) at room temperature. The reaction mixture
was stirred for 24 h. After dried under vacuum, the result solids were
washed thoroughly with ether for three times. Then dried under vacuum
6.41 (s, 1H), 4.56 (s, 2H), 3.27-2.71 ppm (m, 6H). C NMR (101 MHz,
3
3 2
equiv.) was added to a stirred solution of chiral ligand L1 (0.25 mmol, 1
3
CDCl ) δ = 156.1, 155.3, 148.7, 105.8, 105.3, 47.0, 39.3 ppm. HRMS
+
(
ESI-MS) calcd. for C
8 2
H12ClN [M+H] : 171.0684, found: 171.0683.
N1-((1-ethyl-1H-benzo[d]imidazol-2-yl)methyl)-N1,N2-dimethylcyclo-
hexane-1,2-diamine (6): To the stirred mixture of (1R,2R)-N ,N -
dimethyl-cyclohexane-1,2-diamine (4) (426 mg, 3.0 mmol) and dry K CO
1
2
to yield Mn complex C1 (yield >90 %). HRMS (ESI-MS) calcd. for
C
+
25 33 3 5 3
H F MnN O S
[M-OTf] :595.1631, found: 595.1658. Elemental
2
3
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Chemistry - An Asian Journal
10.1002/asia.201800068
FULL PAPER
analysis Calcd (%) for C26
found C 42.30, H 4.57, N 9.43.
H
33
F
6
MnN
5
O
6
S
2
: C 41.94, H 4.47, N 9.41;
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SO to obtain the
90 %). HRMS (ESI-MS) calcd. for
[M-OTf] :638.2053, found: 638.2085. Elemental
analysis Calcd (%) for C28 MnN ·2H O： C 40.83, H 5.14; N
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analogous manner to C1 starting from L2 and Mn(CF
product as solid (yield
MnN
3
3 2
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We acknowledge financial support of this work from the National
Natural Science Foundation of China (21473226 and 21773273),
Key Research Program of Frontier Sciences, CAS (QYZDJ-
SSW-SLH051) and Natural Science Foundation of Jiangsu
Province (BK20170420).
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Keywords: homogeneous catalysis • oxidation • C-H •
manganese• bioinspired catalysis
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
FULL PAPER
Tetradentate nitrogen ligand
W. Wang, D. Xu, Q. Sun,* W. Sun*
containing a benzimidazole and a
pyridine ring was developed and the
resulting manganese complex served
as efficient catalyst in the oxidation of
cyclic aliphatic alkanes, as well as
benzylic C-H.
Page No. – Page No.
Efficient Aliphatic C-H Bonds
Oxidation Catalyzed by Manganese
Complex with Hydrogen Peroxide
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