Linear-selective hydroformylation of vinyl ether using Rh (acac)(2,2′-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,1′-binaphthalene) – Possible way to synthesize 1,3-propanediol

Article abstract of DOI:10.1002/aoc.5863

Three bidentate phosphoramidite ligands were synthesized, characterized, and employed in Rh-catalyzed hydroformylation of vinyl ethers. The complex Rh(acac)(2,2′-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,1′-binaphthalene} (acac = acetylacetone) (Rh-L4) was also synthesized and characterized. Rh-L4 showed good regioselectivity for the hydroformylation of vinyl ethers under mild reaction conditions: 2 MPa of syngas, 1:1 (H₂/CO) substrate/catalyst molar ratio 1000:1, and 60 °C. The linear selectivity was up to 98%, and in most cases was about 80%, with no hydrogenation product formation observed, which could be a potential way to synthesize 1,3-propanediol. A mechanism study including density functional theory computational analysis showed that both Rh–H and CO insertion steps in the hydroformylation of vinyl ether were linear-preferred in our catalyst system.

Full text of DOI:10.1002/aoc.5863

Received: 11 March 2020
DOI: 10.1002/aoc.5863
Revised: 30 April 2020
Accepted: 16 May 2020
F U L L P A P E R
Linear-selective hydroformylation of vinyl ether using Rh
(acac)(2,20-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,10-
binaphthalene) – Possible way to synthesize 1,3-propanediol
Kefeng Wan1
Ruixiang Li1 | Hua Chen1
| Jiangui Zhao1 | Song Qin1 | Xueli Zheng1
| Haiyan Fu1
|
| Jijun Yang2 | Chunji Yang3
1Key Laboratory of Green Chemistry &
Technology, Ministry of Education
College of Chemistry, Sichuan University,
Chengdu, 610064, P. R. China
2Key Laboratory of Radiation Physics and
Technology, Ministry of Education,
Institute of Nuclear Science and
Technology, Sichuan University,
Chengdu, 610064, P. R. China
Three bidentate phosphoramidite ligands were synthesized, characterized, and
employed in Rh-catalyzed hydroformylation of vinyl ethers. The complex
Rh(acac)(2,20-bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,10-binaphthalene}
(acac = acetylacetone) (Rh-L4) was also synthesized and characterized. Rh-L4
showed good regioselectivity for the hydroformylation of vinyl ethers under
mild reaction conditions: 2 MPa of syngas, 1:1 (H2/CO) substrate/catalyst
molar ratio 1000:1, and 60 ꢀC. The linear selectivity was up to 98%, and in most
cases was about 80%, with no hydrogenation product formation observed,
which could be a potential way to synthesize 1,3-propanediol. A mechanism
study including density functional theory computational analysis showed that
both Rh–H and CO insertion steps in the hydroformylation of vinyl ether were
linear-preferred in our catalyst system.
3Petrochemical research institute QaQing
petrochemical research center, Daqing,
163000, P. R. China
Correspondence
Xueli Zheng and Hua Chen, Key
Laboratory of Green Chemistry &
Technology, Ministry of Education
College of Chemistry, Sichuan University,
Chengdu 610064, P. R. China.
Email: zhengxueli@scu.edu.cn;
scuhchen@163.com
K E Y W O R D S
linear selectivity, mechanism study, Rh-catalyzed hydroformylation, vinyl ether
Funding information
Sichuan Science and Technology program,
Grant/Award Number: 2019YFG0146;
National Natural Science Foundation of
China, Grant/Award Number: 21871187;
Sichuan University Innovation Spark
Research Fund, Grant/Award Number:
2018SCUH0079
1 | INTRODUCTION
Although chemical methods,[1] using acrolein or ethylene
oxide as starting materials, and biological methods,[2]
1,3-Propanediol (1,3-PDO) is the raw material for the
production of polytrimethylene terephthalate (PTT), a
kind of polyester which could be applied in textile and
carpet manufacturing owing to its superior properties
such as stain resistance, elastic recovery, chromaticity.
The production of PTT resin and its downstream
products is seriously affected by the synthesis of 1,3-PDO.
using glucose or glycerol as starting materials, have been
developed to synthesize 1,3-PDO, acrolein is difficult to
obtain and quite expensive; besides, high temperature
and high pressure are required for the reaction of
ethylene oxide with syngas, and the overall efficiency of
the biological method needs be increased to meet the
industrial requirement. Therefore, identifying a potential
Appl Organomet Chem. 2020;e5863.
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© 2020 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.5863

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WAN ET AL.
method for the synthesis of 1,3-PDO is quite important to
meet the globally increased demand for PTT.
Vinyl acetate is cheap and readily available, and is one
of the best candidates for synthesizing 1,3-PDO, because
its linear hydroformylation product linear aldehyde could
be hydrolyzed and then be hydrogenated to 1,3-PDO.
However, preliminary work[3] on the hydroformylation of
vinyl acetate is frustrating, with the branched aldehyde
dominating the products. Asymmetric hydroformylation
focused on branched aldehyde formation from vinyl ace-
tate was widely reported.[4] The best linear-to-branched
aldehyde ratio (l/b) achieved so far is 0.8.[5] It is likely that
due to the chelation of carbonyl group with rhodium,
branched alkyl rhodium complexes might form relatively
stable intramolecular five-membered rings (Scheme 1).[6]
Therefore, branched aldehydes are the main products in
the hydroformylation of vinyl acetate. It is speculated that
the ratio of linear to branched aldehyde should be
improved if the carbonyl group is removed. With this con-
sideration in mind, vinyl ether was selected as the
hydroformylation substrate with the purpose of affording
linear aldehyde as the dominant product.
SCHEME 2 Phosphine ligands applied in hydroformylation
Recently, functionalized olefins such as styrene, acry-
late, vinyl acetate, and other vinyl and allyl derivatives
have been widely studied in hydroformylation to produce
linear or branched aldehydes, because the aldehyde itself
and its derivatives are versatile building blocks in organic
synthesis and industries.[7] So far, there are only a few
systematic reports about hydroformylation of vinyl ether
to linear aldehyde.[8]
To guarantee the hydroformylation of vinyl ether in
terms of both reactivity and regioselectivity, satisfactory
phosphorus ligands are required. Phosphorus ligands
usually play a vital role in controlling Rh-catalyzed
hydroformylation. It is believed that phosphorus
ligands possessing strong π-acceptors were able to make
rhodium more electron deficient so that rhodium
would readily coordinate to alkene, thus enhancing the
reactivity[9]; additionally, the Rh–diphosphorus ligand
complex with a large bite angle could promote the
formation of rhodium complexes with equatorial–
equatorial (ee) configuration, which is the linear
aldehyde-preferred configuration, compared with its
apical–equatorial (ea) isomer, in hydroformylation.[10]
We applied the typical linear aldehyde-preferred
diphosphorus ligand BISBI (L1) in hydroformylation as
a model ligand[11] and on this basis, a pyrrolyl substitu-
ent was applied to enhance the π-acceptor properties of
phosphorus atom and indolyl substituents to enhance
both π-acceptor properties and steric hindrance of the
ligand. According to the literature, the dihedral angle
between the two moieties of binaphthol is about 104ꢀ in
the steady state.[12] We wonder whether the binaphthol
SCHEME 1 Hydroformylation of vinyl acetate
and ethyl vinyl ether

WAN ET AL.
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backbone will be beneficial to the Rh–phosphorus com-
plex with a large bite angle to achieve high linear-
aldehyde ratio. Ligands BISBI (L1), L2, L3 based on
biphenol, and L4 (Scheme 2) based on the binaphthol
skeleton were synthesized and used in the Rh-catalyzed
hydroformylation of vinyl ether.[13]
2.4 | Preparation of 2,20-bis{(di[1H-pyrrol-
1-yl]phosphanyl)oxy}-1,10binaphthalene
(L3)
Under an argon atmosphere, a solution of 2,20-dihydroxy-
1,10-( )binaphthyl (1.4 g, 4.6 mmol) and triethylamine
(1.6 mL, 12.0 mmol) in 30 mL THF was added dropwise
to a solution of chlorodipyrrolylphosphine (2.3 g,
11.4 mmol) in 20 mL THF at 0 ꢀC. The Et3NꢁHCl salt was
filtered off after 12 hr of stirring at room temperature and
the solvent was removed under vacuum to obtain a yel-
low oily product. The crude product was recrystallized
with ethyl alcohol to obtain a white solid (yield: 45.7%).
2 | EXPERIMENTAL
2.1 | General
All solvents were purified by standard methods. Reagents
were purchased from commercial suppliers and used as
received, and moisture-sensitive compounds were stored
in a glovebox. 1H, 13C, and 31P{1H} nuclear magnetic
resonance (NMR) spectra were recorded on the Bruker
AVANCE III HD-400 MHz in CDCl3 or toluene-d8
(Bruker, Beijing, P.R. China). GC analysis was performed
with Agilent 7890B (KB-1; 30 m × 0.32 mm × 0.25 μm)
(Agilent, Shanghai, P. R. China). High-resolution mass
spectroscopy was measured on SHIMADZU LCMS-IT-TOF
mass spectrometer (SHIMADZU, Kyoto, Japan).
2.5 | Preparation of 2,20-bis{(di[1H-indol-
1-yl]phosphanyl)oxy}-1,10binaphthalene
(L4)
Under an argon atmosphere, a solution of 2,20-dihydroxy-
1,10-( )binaphthyl (1.4 g, 4.6 mmol) and triethylamine
(1.6 mL, 12.0 mmol) in 30 mL THF was added dropwise
to
a solution of chlorodiindolylphosphine (3.45 g,
11.4 mmol) in 20 mL THF at 0 ꢀC. The Et3NꢁHCl salt was
filtered off after 12 hr of stirring at room temperature and
the solvent was removed under vacuum to obtain a
yellow oily product. The crude product was separated by
flash column chromatography with CH2Cl2:PE = 3:1
(yield: 35.7%).
2.2 | Procedure for the catalytic
experiments
Hydroformylation studies were conducted in a 25-mL
autoclave. In a typical experiment, the reactor was
charged with toluene (2 mL), ethyl vinyl ether (10 mmol)
and Rh(acac)(CO)2 (0.01 mmol), biphosphorus ligand
(0.02 mmol), and monophosphorus ligand (0.04 mmol).
The reactor was purged with syngas (H2/CO = 1/1) three
times and pressurized to 2 MPa. The mixture was then
heated up to the appropriate temperature. Samples
were analyzed after 2 hr by GC or 1H NMR with
dibromomethane (700 μL) as the internal standard.
2.6 | Preparation of Rh(acac)(2,20-
bis{(di[1H-indol-1-yl]phosphanyl)oxy}-1,10-
binaphthalene) (Rh [acac][L4])
Rh(acac)(CO)2 (25.8 mg, 0.1 mmol) and L4 (89 mg,
0.11 mmol) were added into 20 mL toluene, stirred in
room temperature for 10 min. Many bubbles are
produced in this process. Then, the solvent was removed
under vacuum and the bright yellow complex was dried
at 60 ꢀC. The yield was 99%.
2.3 | Preparation of 2,20-bis{(di[1H-pyrrol-
1-yl]phosphanyl)oxy}-1,10biphenyl (L2)
Under an argon atmosphere, a solution of 2,20-dihydroxy-
1,10-biphenyl (1.7 g, 9.0 mmol) in 25 mL of tetrahydrofu-
ran (THF) was added dropwise to a solution of
chlorodipyrrolylphosphine (3 mL, 18.0 mmol) and
triethylamine (6.0 mL, 43.0 mmol) in 30 mL of THF at
0 ꢀC. The Et3NꢁHCl salt was filtered off after 12 hr of stir-
ring at room temperature and the solvent was removed
under vacuum to obtain a yellow oily crude product,
which was recrystallized in ethanol to give the desired
product as a white solid in 62.4% yield.
3 | RESULTS AND DISCUSSION
3.1 | Ligand effect on the
hydroformylation of ethyl vinyl ether
Ethyl vinyl ether was selected as a model substrate for the
hydroformylation. In the presence of rhodium dicarbonyl-
2,4-pentanedionate (Rh[acac][CO]2) (0.1 mol%) and
diphosphorus ligand (0.2 mol%) or monophosphorus
ligand (0.4 mol%), 2 MPa syngas (H2/CO = 1/1) was added

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WAN ET AL.
TABLE 1 Ligand effect on the hydroformylation of ethyl vinyl ether
Entry
Ligand
PPh3
Conversion (%)
l. (%)a
29
b. (%)b
71
Hydrogenation product (%)
1
2
3
4
5
6
7
8
9
41
98
83
19
39
36
96
70
41
–
–
–
–
–
–
–
–
–
P(N-pyrrolyl)3
P (OPh)3
P(N-indolyl)3
DIPHOS
L1
26
74
33
66
9
91
43
57
52
48
L2
60
40
L3
73
27
L4
82
18
Conditions: ethyl vinyl ether, 1 mL (10 mmol); Rh(acac)(CO)2, 2.6 mg (0.01 mmol);
Toluene, 2 mL. Selectivity was determined by 1H NMR (supporting information, part VI).
al represents linear aldehyde.
bb represents branched aldehyde.
to the solution of ethyl vinyl ether in toluene at 60 ꢀC for
2 hr. Two products were detected by 1H NMR:
3-ethoxypropanal (l) and 2-ethoxypropanal (b); no diethyl
ether was detected. As shown in Table 1, for
monophosphorus ligands (Entries 1–4), the excellent and
good π-accepting phosphorus ligand P(N-pyrrolyl)3,
P(OPh)3, achieved high conversion under this mild
condition as expected. PPh3 was a σ-donor ligand, com-
pared with O- and N-substituted phosphorus ligands,
which are π-accepting phosphorus ligand, as mentioned
previously,[9] and therefore its activity was poor. In the
case of P(N-indolyl)3, the conversion was determined to be
19% and only 9% linear aldehyde could be detected, which
may be caused by significant steric hindrance of the indole
substituent. Although the conversion was not satisfactory
with the diphosphorus ligand DIPHOS, an increase of
regioselectivity was observed (43%). Possessing a larger
bite angle than DIPHOS (85ꢀ), L1 (113ꢀ) further improved
the regioselectivity (Table 1, Entry 6). Subsequently, the
diphosphorus ligand L2 with a structure similar to L1 was
TABLE 2 Optimizations of the reaction conditions based on L4
Entry
P/Rh
T (ꢀC)
60
P (MPa)
Conversion (%)
l (%)
n.d.
33
b (%)
/
Hydrogenation product (%)
1
0
2
Trace
60
/
2
1
60
2
66
20
18
19
30
/
–
–
–
–
–
/
3
2
60
2
39
80
4
4
60
2
41
82
5
6
60
2
35
81
6
10
20
4
60
2
13
70
7
60
2
Trace
29
n.d.
67
8
60
8
33
27
25
30
35
28
48
–
–
–
–
–
4
14
9
4
60
4
39
73
10
11
12
13
14
4
60
1
25
75
4
60
0.5
2
16
70
4
40
15
65
4
80
2
80
72
4
100
2
98
52
Conditions: ethyl vinyl ether, 1 mL (10 mmol); toluene, 2 mL; t = 2 hr. Dibromomethane (700 μL) was added after the reaction as internal
standard. Selectivity was determined by GC.
al represents linear aldehyde.
bb represents branched aldehyde.

WAN ET AL.
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TABLE 3 Substrates scope for the hydroformylation of vinyl ethers using Rh/L4
Entry
3a
Substrate
Conversion (%)
l (%)
82
b (%)
18
Hydrogenation product (%)
Ethyl vinyl ether
74
89
77
78
75
90
83
–
–
–
–
–
–
–
3b
2-Chloroethyl vinyl ether
Butyl vinyl ether
68
32
3c
82
18
3d
Iso-butyl vinyl ether
Tertiary-butyl vinyl ether
Cyclohexyl vinyl ether
Phenyl vinyl ether
82
18
3e
98
2
3f
90
10
3g
50
50
Conditions: vinyl ether, 10 mmol; Rh(acac)(CO)2, 2.6 mg (0.01 mmol); L4, 16 mg (0.02 mmol); toluene, 2 mL; t = 4 hr. Selectivity was
determined by 1H NMR.
al represents linear aldehyde.
bb represents branched aldehyde.
used in the hydroformylation. To our delight, this
biphenol skeleton with pyrrolyl-substituted diphosphorus
ligand showed remarkable reactivity (96%) and slightly
improved regioselectivity (60%). Because the reactivity is
guaranteed, the regioselectivity was further improved by
increasing the rigidity of backbone (L3) and replacing pyr-
rolyl with indolyl which has a larger steric hindrance (L4).
In particular, L4 showed the highest regioselectivity for
linear aldehyde (82%) at a little expense of reactivity com-
pared with L2 and L3 (Entry 9).
(Table 2, Entry 1); however, a big jump in the conversion
and regioselectivity was observed once a small amount of
ligand was introduced. The selectivity of linear aldehyde
was slightly improved when the P/Rh ratio increased
from 1/1 to 4/1 (Entries 2 and 4); however, further
increasing the P/Rh ratio resulted in a sharp drop in reac-
tivity. An optimal P/Rh ratio of 4 was preferred to
achieve high selectivity to linear aldehyde. The syngas
(CO/H2 = 1/1) pressure also influenced the reaction. Rel-
atively low pressure benefited linear aldehyde (Entries
4 and 8), because the CO-insertion of branched Rh-alkyl
species was not favored in the low-pressure syngas condi-
tion. However, when the syngas pressure was pretty low,
the reactivity dropped sharply and the linear selectivity
was slightly decreased (Entries 10 and 11). The effect of
temperature on selectivity was not obvious. Moderate
temperature was in favor of linear aldehyde. The
3.2 | Optimization of reaction conditions
We applied L4 as the model diphosphorus ligand to
explore how the reaction condition influenced this reac-
tion. The reaction hardly occurred without the ligand
SCHEME 3 Stacked 31P{1H} NMR spectra
of Rh(acac)(CO)2 and L4 mixed in different
molar ratios

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WAN ET AL.
hydrogenation product can only be detected at high
found in the supporting information, Part IV, Intermedi-
ates [IMs] S1 and S2). Further increasing the amount of
L4 to 2 equiv. of Rh(acac)(CO)2 (P/Rh = 4) would not
generate new species (Scheme 3d); instead, only Rh
(acac)(L4) and excess L4 were observed, indicating that
the 1:1 complex was the IM of the reaction.
temperature (80–100 ꢀC)
3.3 | Hydroformylation of other vinyl
ethers
The substrate scope was investigated under the optimized
reaction conditions of using 0.1 mol% of Rh(acac)(CO)2
and 0.2 mol% of L4 (Table 3) and we prolonged the reac-
tion time to 4 hr. In all cases, no hydrogenation product
was detected in the hydroformylation of substituted vinyl
ethers under 60 ꢀC. The regioselectivity for tertiary butyl-
substituted vinyl ether was the highest among all the
alkyl-substituted vinyl ethers (3e; l:b ratio of up to 49).
This could be attributed to the large steric hindrance
between the tertiary butyl group in substrate and the
indolyl group in phosphorus ligand, causing branched
Rh-alkyl species to be extremely unstable, which will be
explained in the “Computational Study” section.
Although the reactivity for the phenyl-substituted vinyl
ether was comparable with that of cyclohexyl vinyl ether,
the regioselectivity for the former (3g) was significantly
lower than the latter (3f). We could not figure out the
exact reason for this phenomenon, but this might be
related to the entire conjugation system involved in the
hydroformylation of styrene.[14]
3.5 | Computational study
As the entire hydroformylation involves the addition of
alkene to rhodium hydride (Rh–H insertion) and CO-
insertion steps, hydroformylation IMs are produced with
certain configuration. Therefore, the formation and evo-
lution of Rh–alkyl IMs in these two steps remain vital to
3.4 | Confirmation of catalytic precursor
To understand the origin of the reactivity, diphosphorus
ligand L4 and its complexes with Rh(acac)(CO)2 were
characterized by 31P{1H} NMR. In toluene-d8, ligand L4
showed a singlet at 104.57 ppm (Scheme 3a). Compared
with BISBI (at −10 ppm), L4 was more electron deficient.
The rigidity of binaphthol skeleton and the bulky indolyl
reduced reactivity compared with L2 to some extent, but
it was still superior to that of BISBI. When Rh(acac)(CO)2
and L4 were mixed in the molar ratio of 2:1 at ambient
temperature, a doublet at 124.88 ppm (1JP-Rh = 258.7 Hz)
in 31P{1H} NMR spectra was observed, which cor-
responded to the structure Rh2(acac)2(CO)2(L4)
(Scheme 3b). When Rh(acac)(CO)2 and L4 were mixed in
the molar ratio of 1:1, Rh2(acac)2(CO)2(L4) could not be
detected and a new doublet resonance at 127.44 ppm (1JP-
= 267.5 Hz) appeared (Scheme 3c), which cor-
Rh
responded to Rh(acac)(L4). When mixing Rh(acac)(CO)2
and L4, many bubbles were generated, so we suspected
that it was CO, not acetylacetone, which was replaced by
the ligand. Both Rh2(acac)2(CO)2(L4) and Rh(acac)(L4)
were further confirmed by high-resolution mass spectros-
copy and NMR as expected (characterization can be
SCHEME 4 3D model and the energies of Rh-alkyl species;
the energies are in kJ/mol. Upper figure corresponds to the ethyl
vinyl ether system and the lower figure corresponds to the tertiary
butyl vinyl ether system. IM, intermediate

WAN ET AL.
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the regioselectivity, based on the density function
theory method applied on the Rh/L4 system at the
B3LYP/6-31G(d), LANL2DZ level (the computational
details and the optimized structures are available in sup-
plementary information, Part VII). This part focused on
the structures and the relative energies of these IMs
(Scheme 4). The upper figure in Scheme 4 displays the
Rh–H insertion and CO-insertion IMs for the ethyl vinyl
ethyl system, and the lower figure displays these for the
tertiary butyl vinyl ether system.
branched Rh-alkyl species as a result of the structure
rigidity of binaphthol backbone and the large steric
hindrance of indolyl substituent on L4. Besides, to
some extent, the CO insertion of the branched Rh-alkyl
was more difficult to occur in comparison with the linear
one. This was also confirmed by the result that linear
aldehyde was the main product under relatively low
syngas pressure.
As shown in Scheme 4, the calculation places the lin-
ear IMs lower than branched IMs in relative energies
when ethyl or t-butyl vinyl ether was used as substrates.
The energy gap between l and b is predicted to be 2.7 and
15.3 kJ/mol for Rh–H and CO-insertion IMs, respec-
tively, indicating that the linear IMs of ethyl vinyl ether
should be more thermodynamically stable in both Rh–H
insertion and CO-insertion steps. It should be noted that
the calculation predicts that the branched IMs suffer
from the distinguished steric hindrance between the alkyl
group of the substrate and the indole moiety of the
ligand. Such a steric hindrance is even more pronounced
in the tertiary butyl vinyl ether system. As expected, the
energy gap between l0 and b0 is calculated to be 8.4 and
25.6 kJ/mol for Rh–H and CO-insertion IMs, which is
remarkably larger than that in the ethyl vinyl ether
system. Therefore, the high selectivity could be achieved
in tertiary butyl vinyl ether, which is consistent with the
experimental observation. Rh/L4 achieved higher
regioselectivity than L1, L2, and L3, which could be
attributed to the increase in the steric hindrance effect of
4 | CONCLUSION
In conclusion, we have presented the hydroformylation
of vinyl ether with high regioselectivity (up to 98% linear
selectivity) through Rh-L4, with branched aldehyde as
the only by-product. The π-accepting diphosphorus
ligand showed significantly improved reactivity (L1 to
L2) due to the N and O atoms. Study on the reaction
mechanism revealed that the rigidity of backbone and
substituent made the linear IM more thermodynamically
stable in the Rh/L4 system. Corresponding to the circula-
tion (Scheme 5), both Rh–H insertion and CO-insertion
steps are dominant than those of branched circulation in
most cases, especially for tertiary butyl vinyl ether.
Further investigation on more effective ligands and the
conversion of linear aldehyde to 1,3-PDO is ongoing. This
strategy may provide a new idea for the production of
1,3-PDO.
ACKNOWLEDGMENTS
The authors thank the financial support from the Sichuan
Science and Technology program (No. 2019YFG0146),
the National Natural Science Foundation of China
(No. 21871187), and the Sichuan University Innovation
Spark Research Fund (No. 2018SCUH0079). We are grate-
ful to the Centre of Testing & Analysis and the comprehen-
sive raining platform of specialized laboratory, College of
Chemistry, Sichuan University for the analysis work. We
also thank Dr Qin for the great contribution to the calcula-
tions performed in this work.
ORCID
Kefeng Wan https://orcid.org/0000-0001-8498-143X
Xueli Zheng https://orcid.org/0000-0001-8394-0310
Hua Chen https://orcid.org/0000-0003-1159-3780
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SCHEME 5 Linear circulation of hydroformylation of
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How to cite this article: Wan K, Zhao J, Qin S,
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