Bifunctional Ru-loaded Porous Organic Polymers with Pyridine Functionality: Recyclable Catalysts for N-Formylation of Amines with CO2 and H2

Article abstract of DOI:10.1002/adsc.202001336

A series of pyridine functionalized porous organic polymers (POPs-Py&PPh₃) have been synthesized by polymerizing tris(4-vinylphenyl)phosphane and 4-vinylpyridine. The pyridine moieties in the copolymer materials contribute to CO₂ adsorption and promote the subsequent conversion of CO₂. The POP supported Ru catalyst (Ru/POP₃-Py&PPh₃) shows a high catalytic activity (TON up to 710) in the N-formylation of various primary and secondary amines with CO₂/H₂, affording the corresponding formamides in good yields (55–95%) under mild reaction conditions. The heterogeneous catalyst can be easily separated from the reaction system and reused for at least eight cycles in the N-formylation of morpholine. (Figure presented.).

Full text of DOI:10.1002/adsc.202001336

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DOI: 10.1002/adsc.202001336
Bifunctional Ru-loaded Porous Organic Polymers with Pyridine
Functionality: Recyclable Catalysts for N-Formylation of Amines
with CO2 and H2
Kai Zhang,a Lingbo Zong,a,* and Xiaofei Jiaa,*
a
Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, College of Chemistry and Molecular
Engineering, Qingdao University of Science and Technology, Qingdao 266042, People’s Republic of China
E-mail: jiaxiaofei139@163.com; lingbozong@qust.edu.cn
Manuscript received: October 29, 2020; Revised manuscript received: January 12, 2021;
Version of record online: January 21, 2021
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202001336
ical. Therefore, catalyzed N-formylation of amines
with CO2/H2 as the formylating reagent afforded a
Abstract: A series of pyridine functionalized po-
rous organic polymers (POPs-Py&PPh3) have been
green route for the synthesis of formamides. Since
synthesized by polymerizing tris(4-vinylphenyl)
Haynes first reported the preparation of dimeth-
phosphane and 4-vinylpyridine. The pyridine moi-
ylformamide from dimethylamine and CO2/H2 in
eties in the copolymer materials contribute to CO2
1970,[5] a series of homogeneous catalysts based on the
adsorption and promote the subsequent conversion
complex of Ru,[6] Fe,[7] Co,[8] Pd,[9] and Pt[10] have been
of CO2. The POP supported Ru catalyst (Ru/POP3-
developed for the N-formylation of amines with CO2/
Py&PPh3) shows a high catalytic activity (TON up
H2.
to 710) in the N-formylation of various primary and
secondary amines with CO2/H2, affording the corre-
However, heterogeneous catalysts generally possess
significant advantages in terms of recyclability and
sponding formamides in good yields (55–95%)
catalyst separation, and thus, they are more desirable
under mild reaction conditions. The heterogeneous
for industrial applications. Inorganic materials (e.g.,
catalyst can be easily separated from the reaction
system and reused for at least eight cycles in the N-
metallic oxides, carbon)-supported metal catalysts
have been reported, such as Cu/ZnO,[11] Ir/HSA-TiO2
formylation of morpholine.
(HAS, high surface area),[12] Au/TiO2,[13] Pd/
Al2O3À NRÀ RD (NR, nanorod; RD, reductive
deposition),[14] Pd/NC (NC, N-doped carbons),[15] Pd/
Keywords: porous organic polymers; N-formylation;
formamides; ruthenium; heterogeneous catalysis
Palygorskite,[16] and Pd/MgÀ Al LDH (MgÀ Al layered
double hydroxide).[17] In addition, composite material
and metal-organic framework material-immobilized
catalysts have also been developed for the N-formyla-
Formamide compounds are important chemicals with tion of amines with CO2/H2.[18] In recent years, porous
widespread applications in the industry, which not only organic polymers (POPs) have received great attention
can be used as solvents and raw materials for the for their application as the supporting materials of
synthesis of high value-added fine chemicals, bio- catalysts in heterogeneous reaction systems owing to
logical intermediates, and pharmaceuticals,[1] but also the high surface areas, excellent thermal stabilities, and
can be used as Lewis base organocatalysts in synthetic structural diversities.[19] Mesoporous imine-functional-
transformations.[2] Among the methods for the syn- ized POP-supported Pd catalyst (Imine-POP@Pd)[20]
thesis of formamides, N-formylation of amines with and pyridine-functionalized POP-immobilized Ru
gas carbonyl sources (such as CO2 and CO[3]) and (CarPy-CMP@Ru)[21] were developed for the N-for-
reducing reagents in the presence of catalysts has mylation of amines with CO2/H2 by Liu’s group. More
attracted long-term interest owing to high atom recently,
Ding
and
Yan
reported
a
efficiency. As an abundant and cheap C1 building RuÀ PPh3À SO3Na@POP catalyst that incorporated
block, CO2 is nontoxic and exhibits higher security SO3Na as the base for the N-formylation of amines,
than CO in organic synthesis. Furthermore, compared which was mainly effective for the N-formylation of
with the expensive reducing reagents of organic secondary aliphatic amines.[22] Alkali is generally
silicones,[4] hydrogen is more abundant and econom- required as a co-catalyst in the N-formylation of
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amines with CO2/H2, and it is difficult to be recovered phosphane (vPPh3) and 4-vinylpyridine (4-vPy) with
in a homogeneous reaction. It seems that the alkali not AIBN (azobisisobutyronitrile) as the initiator in tetra-
only can be reused in a heterogeneous system, but also hydrofuran. The treatment of the copolymers, POPs-
the species and amount of alkali in supporting Py&PPh3, with RuCl3 in toluene readily afforded the
materials affect the catalytic activity and substrate Ru/POPs-Py&PPh3 as dark solids (for details, see the
scope. Herein, we report a series of pyridine-doped Supporting Information). In addition, to further under-
PPh3-based POPs (POPs-Py&PPh3), in which both the stand the relationship between the catalytic activity
doped “CO2-philic” pyridine moieties and the PPh3 and compositions of POPs, POP-PPh3, and Poly(4-
based porous framework could increase the CO2 vPy) were also prepared for the N-formylation of
adsorption.[23] The alkaline pyridine moieties further amines with CO2/H2 (see SI).
facilitate the subsequent conversion of CO2 to formic
The FT-IR (Fourier-transform infrared) spectra of
acid salt by shifting the thermodynamic equilibrium of various Ru-based catalysts are presented in Figure 1
the CO2 hydrogenation.[6a,24] The copolymer supported (for details, see Figure S1–6, SI). The peaks at 2925
Ru catalyst (Ru/POP3-Py&PPh3) exhibited high activ- and 1404 cmÀ 1 are attributed to the stretching vibration
ities (TON up to 710) in the N-formylation of primary of CÀ H and bending vibration of newly formed cross-
and secondary amines under relatively mild CO2 and linking bridges (À CHÀ CH2À ). The peak at 1599 cmÀ 1
H2 pressures (2/2 MPa) to afford the formamides with was assigned to the À C=NÀ bond stretching vibration
good yields (55–95%).
of pyridine ring. Compared with that of POP3-
As shown in Scheme 1, a series of POPs-Py&PPh3 Py&PPh3 (Figure S6, SI), the characteristic peak of the
including different molar ratios of PPh3 and pyridine phenyl-phosphorus group at 1016 cmÀ 1 was weakened
moieties (m:n=1:1, 3:1, and 5:1), were prepared by dramatically in the spectrum of Ru/POP3-Py&PPh3
the free radical copolymerization of tris(4-vinylphenyl) (Figure S3, SI),[25] which was attributed to the coordi-
nation of Ru with the PPh3 moieties.
The porosities of various supported Ru catalysts
were investigated (Figure S7–S12, SI), and the result is
summarized in Table 1. Ru/POP-PPh3 catalyst has the
highest BET surface area and pore volume in these
catalysts (entry 4), while the Ru/Poly(4-vPy) catalyst
afforded the lowest results (entry 5). Increasing the
molar ratio of PPh3/pyridine moieties from 1:1 to 5:1
in copolymers led to the enhancements of both surface
area and pore volume. The results indicated that PPh3
moiety was crucial for the synthesis of the porous
organic framework. The nitrogen sorption isotherms of
Ru/POPs-Py&PPh3 exhibit a combined curve of type-I
and type-IV (Figure S7–S9, SI). The rise sorption at P/
P0 <0.1 indicates the filling of micropore, and the
hysteresis loops at a relatively high pressure (0.4<P/
P0 <1.0) suggests the presence of mesopores. Based
on the calculations of the nonlocal density functional
theory (NLDFT), the pore sizes of Ru/POPs-Py&PPh3
are mainly distributed at 1–2 nm and 2–30 nm. As a
representative catalyst, Ru/POP3-Py&PPh3 exhibits a
Scheme 1. Synthesis of POPs-Py&PPh3, POP-PPh3 and Poly(4-
vPy).
Table 1. Textural parameters of the various supported Ru
catalysts and porous polymer.[a]
entry
sample
surface area
[m2 gÀ 1]
pore volume
[cm3 gÀ 1]
1
2
3
4
5
6
Ru/POP1-Py&PPh3
Ru/POP2-Py&PPh3
Ru/POP3-Py&PPh3
Ru/POP-PPh3
Ru/Poly(4-vPy)
POP3-Py&PPh3
254.1
430.4
583.3
690.7
0.4
0.3
0.5
0.8
0.9
6.5×10À 4
0.7
618.6
Figure 1. FT-IR spectra of supported Ru catalysts and porous
polymer.
[a] Analysed by BET (Brunauer-Emmett-Teller) method.
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high BET surface area of 583.3 m2 gÀ 1 and pore volume Figure S17 and S20, SI). The results revealed that Ru
of 0.8 cm3 gÀ 1 (Figure S9, SI), which is lower than coordinated with PPh3 moieties, but not with pyridine
those of POP3-Py&PPh3 (Figure S12, SI), due to the moieties in Ru/POP3-Py&PPh3 catalyst. In the solid-
load of RuCl3. The SEM (scanning electron micro- state 31P NMR spectrum of Ru/POP3-Py&PPh3 (Fig-
scopy) and TEM (transmission electron microscopy) ure 2e), the peak observed at 20.8 ppm can be
images in Figures 2a and 2b display rough morpholo- attributed to the P atoms of the polymerized vPPh3
gies with abundant pores on the surface and in the coordinated to Ru, which is consistent with the
internal structure, which further demonstrate the literature.[26] The peak at À 12.7 ppm is assignable to
porosity of Ru/POP3-Py&PPh3. In addition, Ru/POP3- the phosphorus signals of PPh3 moieties. The 13C MAS
Py&PPh3 had a good CO2 uptake capacity (up to NMR spectrum exhibited two peaks at 179.7 and
41.5 mggÀ 1 under 1 bar at 298 k), and the result was 126.5 ppm, corresponding to the carbon signals of the
similar to those of the phosphine-rich polymers- pyridine and benzene ring (Figure 2f). In addition, the
supported catalysts in the literature.[22,23] The CO2 peak centered at 38.6 ppm could be ascribed to the
uptake capacity of Ru/POP-PPh3 was also detected and polymerized vinyl groups. The thermal stability of Ru/
exhibited a slightly higher capacity (45.2 mggÀ 1) than POP3-Py&PPh3 was characterized by thermogravimet-
Ru/POP3-Py&PPh3, which may be owing to the ric analysis (TGA). The first weight loss of 5% was
°
relatively high surface area of the catalyst.
observed starting from 100 C. Additional heating up
°
X-ray photoelectron energy spectroscopy (XPS) to 373 C, revealed the high thermostability of Ru/
was carried out to analyze the catalyst of Ru/POP3- POP3-Py&PPh3 (Figure S14, SI). Inductively coupled
Py&PPh3. The binding energies of P2p for Ru/POP3- plasma-mass spectrometry (ICP-MS) indicated a Ru
Py&PPh3 at 132.3 and 130.5 eV are observed in loading of 2.73 wt% in Ru/POP3-Py&PPh3. The
Figure 2c, which are higher than those of POP3- elemental analysis showed that the content of nitrogen
Py&PPh3 (132.2 and 130.4 eV, Figure S16, SI).[22] The and phosphine in the catalyst was consistent with the
binding energies of Ru3p1/2 and Ru3p3/2 moved from stoichiometric relationship of the monomers.
484.4 and 462.2 eV for RuCl3 (Figure S15, SI) to
We initiated the study of N-formylation with CO2/
486.2 and 463.4 eV for Ru/POP3-Py&PPh3 (Figure 2d). H2 using morpholine as the model substrate and Ru/
In addition, POP3-Py&PPh3 and Ru/POP3-Py&PPh3 POP3-Py&PPh3 as the catalyst. Various reaction con-
show the same binding energies of N1s (399.4 eV, ditions, including solvent, temperature, and pressure of
CO2/H2, were investigated, and the results are summar-
ized in Table S1 (for details, see SI). N-formylation of
morpholine was best performed in NMP (N-methyl-2-
°
pyrrolidone) at 100 C under at 2/2 MPa for CO2/H2,
affording N-formylmorpholine in excellent yield (93%,
entry 1, Table S1). Under the optimized reaction
conditions, a variety of catalysts were evaluated, as
shown in Table 2. In the comparative experiment with
Ru/POPs-Py&PPh3 (entries 1–3, Table 2), Ru/POP3-
Py&PPh3 exhibited the best catalytic activity while Ru/
POP1-Py&PPh3 was less reactive (entry 1). When using
RuCl3 as a precatalyst in the absence of ligands and
basic additives, a 55% yield was obtained (entry 4).
Moreover, the POP-PPh3-supported RuCl3 catalyst
(Ru/POP-PPh3) showed a better performance than
RuCl3 (83%, entry 5), but an inverse result was
observed when using Ru/Poly(4-vPy) as the catalyst
(28%, entry 6). Ru/POP3-Py&PPh3 showed a higher
catalytic activity than Ru/POP-PPh3, although the latter
had higher CO2 uptake capacity, proving that pyridine
moieties could promote the conversion rate of N-
formylation. Based on these results, we concluded that
the catalytic activity of the catalyst depended on the
molar ratio of PPh3 and pyridine moieties in copoly-
mers. A proper ratio of pyridine and PPh3 moieties was
Figure 2. (a) SEM image, (b) TEM image, (c) P 2p XPS
spectra, (d) Ru 3p XPS spectra, (e) 31P MAS NMR spectrum
(MAS, Magic Angle Spinning), (f) 13C MAS NMR spectrum of
Ru/POP3-Py&PPh3.
favorable for improving the catalytic activity, whereas
excessive pyridine moieties in the copolymer resulted
in decreased catalytic activity due to the coordination
effect of Ru with pyridine. Additionally, the heteroge-
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Table 2. Catalytic activities of various Ru-based catalysts for
Table 3. N-formylation of amines catalyzed by Ru/POP3-
the N-formylation of morpholine with CO2/H2.[a]
Py&PPh3 with CO2/H2.[a]
entry
catalyst
yield[b](%)
1[c]
2[d]
3[e]
4[f]
5[g]
6[h]
7[i]
8[j]
Ru/POP1-Py&PPh3
Ru/POP2-Py&PPh3
Ru/POP3-Py&PPh3
RuCl3
Ru/POP-PPh3
Ru/Poly(4-vPy)
Ru/PPh3/Py
66
77
93
55
83
28
90
64
entry
substrate
product
yield[b] (%)
Ru/POP3-Py&PPh3
[a] Reaction conditions: morpholine (1 mmol), S/C=222, CO2/
°
H2 =2/2 MPa, NMP (1.0 mL), 100 C, 24 h, decane as the
internal standard.
[b] Yields were determined on the basis of GC analysis.
[c] 20.1 mg of Ru/POP1-Py&PPh3 (Ru loading at 2.27 wt%).
[d] 17.2 mg of Ru/POP2-Py&PPh3 (Ru loading at 2.64 wt%).
[e] 16.5 mg of Ru/POP3-Py&PPh3 (Ru loading at 2.73 wt%).
[f] 0.93 mg of RuCl3.
[g] 12.4 mg of Ru/POP-PPh3 (Ru loading at 3.67 wt%).
[h] 6.33 mg of Ru/Poly(4-vPy) (Ru loading at 7.19 wt%.
[i] 0.93 mg of RuCl3, RuCl3:PPh3:Py=1:10:2.
[j] S/C=1110.
neous Ru/POP3-Py&PPh3 gave a similar yield to that
of the homogeneous Ru/PPh3/Py system (entries 3 vs
7). The catalyst loading of 0.111 mol% (S/C=1110)
was tested, affording the N-formylmorpholine in 64%
yield (TON=710, entry 8). Compared with the re-
ported heterogeneous Ru catalysts of CarPy-CMP@Ru
(TON=188,
CO2/H2 =4/4 MPa)[21]
and
RuÀ PPh3À SO3Na@POPs (TON=216, CO2/H2 =3/
3 MPa),[22] Ru/POP3-Py&PPh3 showed the highest
catalytic activity under a relatively low pressure of
CO2/H2.
Under optimal reaction conditions, various amines
were investigated as substrates for Ru/POP3-Py&PPh3-
catalyzed N-formylation. As shown in Table 3, cyclic
secondary amines, such as morpholine, pyrrolidine,
and piperidine, are readily amenable to the N-
formylation procedure, affording the corresponding
formamides 2a–2c in excellent yields (93–99%,
entries 1–3). When using linearly aliphatic amines
dimethylamine (1d) and dibutylamine (1e) as the
substrates, products of 2d and 2e were obtained with
good yields, respectively (60% and 68%, entries 4 and
5). The N-methylbenzylamine (1f) also worked well in
this catalytic system with an excellent yield (95%,
entry 6). Moreover, its derivatives, bearing electro-
donating or electro-withdrawing substituents on
benzene ring, proceeded smoothly and formed the
desired corresponding products (2g–2i) in excellent
yields (92–97%, entries 7–9). Encouraged by these
[a] Reaction conditions: amines 1a–m (1 mmol), 16.5 mg of Ru/
POP3-Py&PPh3 (Ru loading at 2.73 wt%), S/C=222, CO2/
°
H2 =2/2 MPa, NMP (1.0 mL), 100 C, 24 h, decane as the
internal standard.
[b] Yields were determined by GC analysis.
[c] Yields of isolated products.
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results, the N-formylation of primary amines was then and secondary amines are amenable to the procedure,
investigated in the presence of Ru/POP3-Py&PPh3 as affording the corresponding formamides in good yields
the catalyst. For linear primary amine (1j) and cyclo- and excellent recyclability under relatively mild reac-
hexanamine (1k), 70% and 67% yields of the tion conditions. Moreover, through multiple comparing
corresponding formamide products were obtained, experimental studies, it was confirmed that the cata-
respectively, (entries 10 and 11). Benzylamine and the lytic activities of the catalysts depended on the molar
derivative were good reaction partners, delivering the ratios of PPh3 and pyridine moieties in copolymers.
desired formamides with good yields (entries 12 and
13).
Experimental Section
The reusability of the Ru/POP3-Py&PPh3 catalyst in
the N-formylation was investigated. As shown in General Procedure for the N-Formylation of
Figure 3, with the morphine as the substrate for Amines
reaction time of 12 h, the catalyst was at least reused
eight times and the yield of 2a was considerably
retained (Table S2, SI). Additionally, 1.4 ppm Ru
species were detected in the residual liquids by ICP-
MS analysis. Further, the recovered catalyst was
characterized by N2 adsorption-desorption analysis and
In a glove box, an autoclave with a magnetic stirring bar was
successively charged with Ru/POP3-Py&PPh3 (16.5 mg), the
corresponding amines (1 mmol), N-methyl pyrrolidone
(1.0 mL), and decane (10 μL, 0.05 mmol) as the internal
standard. The autoclave was sealed and purged with CO2 three
times and subsequently charged with CO2 (20 atm) and H2
XPS. The used catalyst also had a high surface area (20 atm) at room temperature. The autoclave was moved to an
(569.9 m2 gÀ 1, Figure S13, SI), and the XPS spectra
(Figure S21–23, SI) was similar to that of the fresh Ru/
POP3-Py&PPh3 catalyst. Finally, a hot filtration test
was carried out using Ru/POP3-Py&PPh3. After 12 h of
the initial reaction, the mixture was immediately
filtered and the resultant filtrate was conducted for an
additional 12 h. After the removal of the solid catalyst,
the reaction stopped, and the conversion of morpholine
remained constant (69%). The results indicated the
stability of the polymeric framework and the strong
coordination ability of Ru with the copolymer support,
which resulted in the excellent recyclability of the Ru/
POP3-Py&PPh3 catalyst.
In summary, a series of porous copolymers (POPs-
Py&PPh3) were synthesized by polymerizing the vinyl-
functionalized PPh3 and pyridine. Among the Ru
species-loaded porous polymers, Ru/POP3-Py&PPh3
catalyst showed the best catalytic activity in the N-
formylation of amines with CO2/H2. Various primary
°
oil bath of 100 C and stirred for 24 h. The autoclave was
cooled in ice water, and the gas was carefully released in a
well-ventilated hood. The mixture was subsequently analyzed
by gas chromatography (GC). After the reaction, the catalyst
was removed by centrifugation. The supernatant was washed
with H2O, and the mixture was extracted by ethyl acetate.
Afterward, the ethyl acetate solution of the product was
gathered and dried by MgSO4. The solvent was removed by
rotary evaporation and the residue was directly purified by
silica gel column chromatography to give the desired product.
GC analysis condition: SE-54, 30 m×0.32 mm×0.33 mm, flow
À 1
°
rate 2.0 mL min , method: 50 C was maintained for 5 min,
À 1
°
°
°
and then ramped from 50 C to 250 C at a rate of 20 C min ,
250 C was maintained for 10 min.
°
Acknowledgements
We are grateful for the financial support from the National
Natural Science Foundation of China (No. 21703116,
51702180, 22002067) and the Youth Innovative Talents Recruit-
ment and Cultivation Program of Shandong Higher Education.
We thank Jinhe Lv, Lizhi Du and Guoying Zhang for their
assistance in synthesis of catalysts and reaction testing. We
thank Congxia Xie, Yubing Zhang Jianbin Chen, Jiaxin Song
and Jinrong Zhang for their assistance in characterization of
catalysts.
References
[1] a) A. Dömling, Chem. Rev. 2006, 106, 17–89; b) S.
Ding, N. Jiao, Angew. Chem. Int. Ed. 2012, 51, 9226–
9237; c) K. Weissermel, H.-J. Arpe, Industrial Organic
Chemistry, 3rd Edition; translated by C. R. Lindley,
Wiley-VCH: Weinheim, Germany, 1997; d) C. J. Gerack,
L. McElwee-White, Molecules 2014, 19, 7689–7713.
[2] a) S. B. Jagtap, S. B. Tsogoeva, Chem. Commun. 2006,
45, 4747–4749; b) S. Jones, C. J. A. Warner, Org.
Biomol. Chem. 2012, 10, 2189–2200.
Figure 3. Recycling studies of the Ru/POP3-Py&PPh3 in the N-
formylation of morpholine with CO2/H2. Reaction condition:
Ru/POP3-Py&PPh3 (40 mg), 1a (2.42 mmol), S/C=222, CO2/
°
H2 =2/2 MPa, NMP (1.0 mL), 100 C for 12 h.
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[3] a) J. Zhang, W. Zhang, M. Xu, Y. Zhang, X. Fu, H. [11] J. L. Liu, C. K. Guo, Z. F. Zhang, T. Jiang, H. Z. Liu,
Fang, J. Am. Chem. Soc. 2018, 140, 6656–6660; b) C. J.
Gerack, L. McElwee-White, Chem. Commun. 2012, 48,
J. L. Song, H. L. Fan, B. X. Han, Chem. Commun. 2010,
46, 5770–5772.
11310–11312; c) Y. Wang, J. Zhang, H. Chen, Z. Zhang, [12] Q.-Y. Bi, J.-D. Lin, Y.-M. Liu, S.-H. Xie, H.-Y. He, Y.
C. Zhang, M. Li, F. Wang, Green Chem. 2017, 19, 88– Cao, Chem. Commun. 2014, 50, 9138–9140.
92; d) W. Li, X.-F. Wu, Chem. Eur. J. 2015, 21, 14943– [13] T. Mitsudome, T. Urayama, S. Fujita, Z. Maeno, T.
14948; e) Y.-S. Choi, Y. N. Shim, J. Lee, J. H. Yoon,
C. S. Hong, M. Cheong, H. S. Kim, H. G. Jang, J. S. Lee,
Appl. Catal. A 2011, 404, 87–92.
Mizugaki, K. Jitsukawa, K. Kaneda, ChemCatChem.
2017, 9, 3632–3636.
[14] X. Cui, Y. Zhang, Y. Deng, F. Shi, Chem. Commun.
2014, 50, 189–191.
[4] a) X. Frogneux, O. Jacquet, T. Cantat, Catal. Sci.
Technol. 2014, 4, 1529–1533; b) W. Zhao, X. Chi, H. Li, [15] X. Luo, H. Zhang, Z. Ke, C. Wu, S. Guo, Y. Wu, B. Yu,
J. He, J. Long, Y. Xu, S. Yang, Green Chem. 2019, 21, Z. Liu, Sci. China Chem. 2018, 61, 725–731.
567–577; c) H. Lv, W. Wang, F. Li, Chem. Eur. J. 2018, [16] X. Dai, B. Wang, A. Wang, F. Shi, Chin. J. Catal. 2019,
24, 16588–16594; d) W.-D. Li, D.-Y. Zhu, G. Li, J. 40, 1141–1146.
Chen, J.-B. Xia, Adv. Synth. Catal. 2019, 361, 5098– [17] Y. Wang, B. Chen, S. Liu, X. Shen, S. Li, Y. Yang, H.
5104; e) Z. Huang, X. Jiang, S. Zhou, P. Yang, C.-X. Du, Liu, B. Han, ChemCatChem. 2018, 10, 5124–5127.
Y. Li, ChemSusChem. 2019, 12, 3054–3059; f) X.-D. Li, [18] a) P. Ju, J. Chen, A. Chen, L. Chen, Y. Yu, ACS
S.-M. Xia, K.-H. Chen, X.-F. Liu, H.-R. Li, L.-N. He,
Green Chem. 2018, 20, 4853–4858; g) C. D. N. Gomes,
O. Jacquet, C. Villiers, P. Thuéry, M. Ephritikhine, T.
Sustainable Chem. Eng. 2017, 5, 2516–2528; b) J. Mu, J.
Liu, Z. Ran, M. Arif, M. Gao, C. Wang, S. Ji, Ind. Eng.
Chem. Res. 2020, 59, 6543–6555.
Cantat, Angew. Chem. Int. Ed. 2012, 51, 187–190; h) O. [19] a) P. Kaur, J. T. Hupp, S. T. Nguyen, ACS Catal. 2011, 1,
Jacquet, C. D. N. Gomes, M. Ephritikhine, T. Cantat, J.
Am. Chem. Soc. 2012, 134, 2934–2937.
[5] P. Haynes, L. H. Slaugh, J. F. Kohnle, Tetrahedron Lett.
1970, 11, 365–368.
[6] a) L. Zhang, Z. Han, X. Zhao, Z. Wang, K. Ding, Angew.
Chem. Int. Ed. 2015, 54, 6186–6189; b) P. G. Jessop, Y.
Hsiao, T. Ikariya, R. Noyori, J. Am. Chem. Soc. 1996,
819–835; b) Q. Sun, Z. Dai, X. Meng, F.-S. Xiao, Chem.
Soc. Rev. 2015, 44, 6018–6034; c) S. Kramer, N. R.
Bennedsen, S. Kegnæs, ACS Catal. 2018, 8, 6961–6982;
d) Z. B. Shifrina, V. G. Matveeva, L. M. Bronstein,
Chem. Rev. 2020, 120, 1350–1396; e) T. Zhang, G. Xing,
W. Chen, L. Chen, Mater. Chem. Front. 2020, 4, 332–
353.
118, 344–355; c) O. Köcher, R. A. Köppel, A. Baiker, [20] X. Yu, Z. Yang, S. Guo, Z. Liu, H. Zhang, B. Yu, Y.
Chem. Commun. 1997, 5, 453–454. Zhao, Z. Liu, Chem. Commun. 2018, 54, 7633–7636.
[7] a) C. Federsel, A. Boddien, R. Jackstell, R. Jennerjahn, [21] Z. Yang, H. Wang, G. Ji, X. Yu, Y. Chen, X. Liu, C. Wu,
P. J. Dyson, R. Scopelliti, G. Laurenczy, M. Beller, Z. Liu, New J. Chem. 2017, 41, 2869–2872.
Angew. Chem. Int. Ed. 2010, 49, 9777–9780; b) C. [22] G. Wang, M. Jiang, G. Ji, Z. Sun, C. Li, L. Yan, Y. Ding,
Ziebart, C. Federsel, P. Anbarasan, R. Jackstell, W. ACS Sustainable Chem. Eng. 2020, 8, 5576–5583.
Baumann, A. Spannenberg, M. Beller, J. Am. Chem. Soc. [23] W. Wang, C. Li, L. Yan, Y. Wang, M. Jiang, Y. Ding,
2012, 134, 20701–20704; c) U. Jayarathne, N. Hazari,
W. H. Bernskoetter, ACS Catal. 2018, 8, 1338–1345.
[8] P. Daw, S. Chakraborty, G. Leitus, Y. Diskin-Posner, Y.
Ben-David, D. Milstein, ACS Catal. 2017, 7, 2500–2504.
ACS Catal. 2016, 6, 6091–6100.
[24] C. L. Mathis, J. Geary, Y. Ardon, M. S. Reese, M. A.
Philliber, R. T. VanderLinden, C. T. Saouma, J. Am.
Chem. Soc. 2019, 141, 14317–14328.
[9] K. Kiyoshi, P. Heng, S. Nobuyuki, T. Yoshimasa, Chem. [25] L. W. Daasch, D. C. Smith, Anal. Chem. 1951, 23, 853–
Lett. 1977, 6, 1495–1496. 868.
[10] S. Schreiner, J. Y. Yu, L. Vaska, J. Chem. Soc. Chem. [26] X. K. Chen, H. J. Zhu, X. G. Song, H. Du, T. Wang,
Commun. 1988, 9, 602–603.
Z. A. Zhao, Y. J. Ding, React. Kinet. Mech. Catal. 2017,
120, 637–649.
Adv. Synth. Catal. 2021, 363, 1335–1340
1340
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