Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling

Article abstract of DOI:10.1039/c8gc00971f

A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO₂ catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.

Full text of DOI:10.1039/c8gc00971f

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DOI: 10.1039/C8GC00971F
Hydrofunctionalization of olefins to value-added chemicals via
†
photocatalytic coupling
a,b
a,c
a,b
a,b
a,d
Yonghui Fan, Shenggang Li, Jingxian Bao, Lei Shi, Yanzhang Yang, Fei
a,d
a
a
,a,c
,a,c
Yu, Peng Gao, Hui Wang, Liangshu Zhong,* and Yuhan Sun*
a
Key Laboratory of LowꢀCarbon Conversion Science and Engineering, Shanghai Advanced
Research Institute, Chinese Academy of Sciences, Shanghai 201203, China
b
Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China
c
School of physical Science and Technology, ShanghaiTech University, Shanghai 201210, China
d
University of the Chinese Academy of Sciences, Beijing 100049, China
*
Eꢀmail: zhongls@sari.ac.cn; sunyh@sari.ac.cn
†
Electronic Supplementary Information (ESI) available. See DOI:10.1039/x0xx00000x
A green strategy was developed for synthesis of various value-added chemicals
using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the
hydrogen source by coupling them with olefins over heterogeneous
photocatalysts. A radical coupling mechanism was proposed for the
hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over
2
the Pt/TiO catalyst as the model reaction. C-H bond cleavage and C-C bond
formation between photogenerated radicals and terminal olefins were
accomplished in a single reaction at high efficiency. Our approach is atomically
economical with high anti-Markovnikov regioselectivity and promising
application potential under mild reaction conditions.
Olefins are commonly used as the feedstock for the production of various
valueꢀadded chemicals including alcohols, acids, esters and nitriles via
1
ꢀ3
hydrofunctionalization in industry . For example, the conventional synthesis method
for higher aliphatic alcohols is through the hydrogenation of aldehydes, whereas
aldehydes are produced via homogeneous hydroformylation of terminal olefins with
4
ꢀ8
syngas under high pressure (Scheme 1a) . The oxidation of aldehydes yields
aliphatic acids, which can be further converted into esters via esterification. Although
significant progress has been made in catalyst development for the hydroformylation
9
reaction , expensive Rhꢀbased homogeneous catalysts are still usually required. In
1

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DOI: 10.1039/C8GC00971F
addition, both limited product selectivity and difficulty in catalyst recovery make the
1
0, 11
process less economically viable and environmentally friendly. Yang’s group
reported a CeO −Pt@mSiO heterogeneous catalyst to convert methanol and ethylene
2
2
into propanal via tandem hydroformylation, where methanol served as both the C1
feedstock and the hydrogen source to replace syngas with the additional benefit of
facile catalyst recycle. However, it remains difficult to avoid byꢀproducts such as
isoꢀaldehydes and alkanes, limiting the yield of the nꢀaldehydes target product. As for
1
2
another valueꢀadded olefinꢀderived chemicals, nitriles are widely used in industry .
The present industrial route for the antiꢀMarkovnikov hydrocyanation of olefins to
13
nitriles is the DuPont adiponitrile process using nickel triarylphosphite catalyst .
However, such a route is impractical for routine chemical synthesis for the severe
safety concern of HCN, which is extremely toxic and explosive (Scheme 1b). To
14
avoid using HCN, Fang et al. reported a nickelꢀcatalyzed transfer hydrocyanation
reaction between alkyl nitriles and olefins. However, other olefins were also
generated as byꢀproducts in this process. Obviously, it is highly desirable yet
challenging to develop a singleꢀstep olefin hydrofunctionalization process for
synthesizing valueꢀadded chemicals with an inexpensive and safe
hydrofunctionalization source under mild reaction conditions.
The realization of CꢀH bond cleavage and CꢀC or CꢀN bond formation through
photocatalytic coupling has been extensively studied in organic synthesis over the last
15ꢀ20
15
decade
. Recently, Wu et al. reported that aromatic photocatalytic benzene
amination and hydroxylation over cobaltꢀcatalyst under unusually mild conditions in
17
excellent yields and selectivities. And Li et al. built new CꢀC bond by
photoꢀinduced methylation of heteroarenes with MeOH as both the solvent and the
methylation source. In addition, numerous photoꢀcatalyzed homogeneous systems
2
1ꢀ23
have been developed to realize the functionalization of olefins
. Compared with
conventional thermal reactions, photochemical reactions occur under unparalleled
24
25, 26
mild conditions and, in many case, have a high product selectivity
. In recently
years, radical hydroxyalkylation of olefins with alcohol or nitrile have also been
27, 28
reported
. However, the focus on the approach of synthesis valueꢀadded chemicals
via heterogeneous photocatalysis from olefins and cheap, readily available, and
abundant small molecules is yet not enough.
2

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In order to develop a green and atomic economic olefin hydrofunctionalization
process for synthesizing valueꢀadded chemicals, herein, a route for synthesizing
various fine chemicals including alcohols, acids, esters, ketones and nitriles from
olefins was developed by hydrofunctionalization with high atomic economy and
antiꢀMarkovnikov regioselectivity via heterogeneous photocatalytic coupling (Scheme
1c). CꢀH bond cleavage and CꢀC bond formation between photogenerated radicals and
terminal olefins were accomplished in a single reaction at high efficiency. Our
catalytic strategy is simple and effective with high atomic economy and promising
application potential.
Scheme 1. Development of the protocol for hydrofunctionalization of olefins and our strategy for
hydrofunctionalization of olefins via photocatalytic coupling.
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Table 1. Hydrofunctionalization of olefins with methanol, acetonitrile, acetic acid, acetone or
ethyl acetate.
a
Reaction condition: 1 mmol of olefin substrates，50 mg of photocatalyst in 50 mL of methanol,
acetonitrile, acetic acid, acetone, ethyl acetate, respectively. The reaction were conducted under
argon atmosphere at 60 °C (Entry 1ꢀ7) or 50 °C (Entry 8ꢀ17) under Xe lamp irradiation (200ꢀ400
2
nm) with light intensity of 100 mW/cm . The reaction time was 15 h. TON and TOF were
calculated based on the target product.
4

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Pt/TiO
2
was used as the model photocatalyst (Figure S1) for the
hydrofunctionalization of olefins via photocatalytic coupling with methanol,
acetonitrile, acetic acid, acetone and ethyl acetate. Various valueꢀadded chemicals
including longꢀchain alcohols, nitriles, carboxylic acids, ketones, and esters were
produced in oneꢀstep with high selectivity (Table 1). For the coupling of methanol and
olefins to yield higher aliphatic alcohols, the antiꢀMarkovnikov regioselectivity was
up to 90% (Entry 1ꢀ7), and the main byproducts were acetal and alkane (Figure S2).
Acetonitrile is an excellent substrate for producing nitriles, and our synthetic route not
only avoids the use of the lethal HCN but also achieves nearly perfect
chemoselectivity and regioselectivity (Entry 8ꢀ11). In addition, acetic acid (Entry
12ꢀ15), acetone (Entry 16) and ethyl acetate (Entry 17) can also be utilized to generate
the desired products with very high antiꢀMarkovnikov regioselectivity and atomic
economy. Meanwhile, a broad range of olefins with different carbon chain lengths
were examined and showed excellent catalytic performance. And the catalytic activity
based on TON and TOF showed to be improved with the increase in the carbon
number of olefin. Besides, substituted olefins such as 1,9ꢀdecadiene, 10ꢀundecenꢀ1ꢀol,
4ꢀphenylꢀ1ꢀbutene were also successfully converted into the desired higher aliphatic
alcohols with 100% regioselectivity (Entry 5ꢀ7).
To further investigate the factors affecting the photocatalytic performance,
coupling between 1ꢀdecene and methanol was chosen as the model reaction. The
control experiment clearly indicated that the desired reaction required both light and
the photocatalyst, because no desired reaction occurred without either light or the
photocatalyst. Under typical conditions, only trace amount of higher aliphatic alcohol
ꢀ
3
(
C H OH) was obtained at much lower TON of 10.3 × 10 for the sole TiO catalyst.
1
1
2
3
2
Increasing TON and TOF with the addition of Pt nanoparticles was attributed to the
reduced probability for the recombination of photogenerated electrons and holes due
29
to the transfer of the photoelectrons to Pt (Table 2, Entries 3ꢀ6). However, the TON
and TOF decreased with the further increasing the Pt loading as the higher loading of
Pt enhanced the hydrogenation of olefin to alkane (Table 2, Entries 7 and 8). Other
noble metals were explored (Table 2, Entries 9ꢀ11), which also significantly improved
the catalytic activity. We also investigated the effect of reaction temperature on the
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catalytic performance. The result showed that there was no product at 20℃. As shown
in Figure S3, both the TON and the selectivity to higher aliphatic alcohol increased
with the increase of reaction temperature. When certain amount of water was added to
the reaction system, the selectivity of the higher aliphatic alcohol increased. This is
likely due to the enhanced production of the ·OH radical from water, which can
17, 30ꢀ32
activate methanol to form stable intermediates
(Table S1), as discussed below.
A wide range of alcohols were found to be effective as the hydrofunctionalization
source for the coupling reaction and all the obtained higher aliphatic alcohols
possessed perfect antiꢀMarkovnikov regioselectivity (Table 3). In addition, with the
sequence of ethanol, propanol and isopropanol, the TON and TOF of the desired
product increased markedly, suggesting the trend in the catalytic activity to coincide
with the stability of the αꢀC free radical intermediates (tertiary > secondary >
3
3
primary)
Table 2. Catalytic performance of controlled experiment for synthesis higher aliphatic alcohol via
a
photocatalysis
Selectivity to higher AntiꢀMarkovnikov
Noble metal
TON
ꢀ
1
3
Entry
Catalyst
TOF (h ) ×10
aliphatic alcohol
regioselectivity
3
loading (wt%)
×10
(%)
(%)
b
1
-
-
-
-
-
-
c
2
Pt/TiO
TiO
Pt/TiO2
2
0.44
ꢀ
-
-
-
-
3
4
5
6
7
8
9
2
10.3
23.9
24.2
45.3
22.5
0
0.7
1.6
1.6
3.0
1.5
0
85.3
42.6
43.3
62.3
64.2
0
94
95
95
93
94
-
0.14
0.29
0.44
0.70
1.22
0.48
0.48
0.48
Pt/TiO
2
2
Pt/TiO
Pt/TiO2
Pt/TiO
Pd/TiO
Ru/TiO
Au/TiO
2
2
89.7
94.9
31.9
6.0
6.3
2.1
36.3
52.5
42.8
85
90
85
1
1
0
1
2
2
a
Reaction condition: 1 mmol of 1ꢀdecene，50 mg of photocatalyst in 50 mL of methanol. The
reaction were conducted under argon atomsphere at 60 °C under Xe lamp irradiation (200ꢀ400 nm)
2
with light intensity of 100 mW/cm . The reaction time was 15 h. TON and TOF were calculated
c
b
based on the target product. Entry 1: no photocatalyst under illumination. Entry 2: at dark
condition
6

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Table 3.Investigation of the scope of alcohol substrates.
∗
The reaction time was 15 h (Entry 1ꢀ3) or 10 h (Entry 4). TON and TOF were calculated based
on the target product.
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Fig. 1. Photocatalytic performance with timeꢀonꢀstream and Xꢀray photoelectron spectra of
Pt/TiO at different stages. a, Formation rates of higher aliphatic alcohol and alkane and selectivity
to higher aliphatic alcohols with timeꢀonꢀstream. b, O 1s XPS spectrum of Pt/TiO catalysts. XPS
O1s spectra for the sample can be deꢀconvoluted into three distinct peaks: the main oxide peak at
30.3 eV (‘Olattice’) and two additional peaks at 531.2 eV and 532.5 eV, which were assigned to O
atoms next to defects (‘Odefect’) and surface hydroxyls (‘OH’), respectively. c, Ti 2p3/2 XPS
spectrum of Pt/TiO catalysts. XPS Ti 2p3/2 spectra for the sample can be deꢀconvoluted into two
2
2
5
2
4
+
3+
distinct peaks: the Ti peak at 459.0 eV and Ti peak at 457.9 eV, respectively.
We further examined the photocatalytic performance with timeꢀonꢀstream. The
formation rate of higher aliphatic alcohol increased first and then stabilized with
timeꢀonꢀstream while the production rate of alkane declined rapidly. Additionally, the
selectivity to higher aliphatic alcohols increased quickly with timeꢀonꢀstream
especially during the first three hours (Fig. 1a). It suggested that defects on the
3
4
3+
photocatalyst surface generated by UV irradiation promoted the coupling . The Ti
surface defect was previously proposed as one of the most important surface species,
35
playing an essential role in the photocatalytic process . Indeed, the photogenerated
electrons and holes were produced by UV radiation in Pt/TiO
2
and some of the
4+
3+
photogenerated electrons were trapped, which reduced the Ti cations into the Ti
36
3+
state . Based on the XPS experiments (Figure 1b, 1c), the relative amount of Ti and
defect increased after the reaction (Table S3), which may benefit the separation of
O
electrons and holes and the formation of higher aliphatic alcohols.
Fig. 2. Proposed photocatalytic mechanism for the photocatalytic coupling reaction between
methanol and olefins. (i), Electron and hole pairs were generated by photoexcitation of the
electrons from the valence band into the conduction band. (ii), The photogenerated electrons were
8

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transferred to the Pt nanoparticles. (iii), The hole direct oxidized the absorbed alcohols into the
corresponding αꢀC free hydroxyalkyl radicals. (iv) and (v), The holes oxidized H O to yield ·OH
2
and ·OH radicals abstracted the H from αꢀC of the absorbed alcohols to form hydroxyalkyl
radicals. (vi), Terminal olefins coupled with the hydroxyalkyl radicals to form a new CꢀC bond in
the more stable secondary carbonꢀcentred radicals. (vii), The carbonꢀcentred radicals combined
+
with electron and H to form higher aliphatic alcohols. (viii), Terminal olefins were hydrogenated
into alkanes as byꢀproducts.
Based on the above results, we proposed the following mechanism as shown in
Fig. 2 for the photocatalytic coupling reaction between methanol and olefins over
Pt/TiO
2
. Under UV illumination, electrons were excited from the valence band to the
, leading to the production of photogenerated electron and
conduction band of TiO
2
hole pairs (Step i). Next, the electron would transfer to Pt (Step ii) while the hole
direct oxidized the absorbed alcohols into the corresponding αꢀC free hydroxyalkyl
radicals. Meanwhile, the absorbed alcohols was also indirect oxidized by
photogenerated ·OH radicals produced by oxidation of surface −OH groups or
2
9,37
adsorbed water by the photogenerated holes (Step iv&v)
paramagnetic resonance (EPR) studies were performed to probe the intermediate
radical species and DMPOꢀCH OH spin adduct was detected under illumination (Fig.
. In situ electron
2
3
2
S4) . Upon the formation of the ·CH OH radical, it was trapped immediately by the
2
terminal carbon of olefins to generate a relatively stable carbonꢀcentred radical
intermediate (Step vi). This step was suggested to be the rateꢀlimiting step during the
alcohol/olefin coupling reaction. As secondary carbonꢀcentred radicals were more
38
stable than primary carbonꢀcentred radicals for synthesis of higher aliphatic alcohol ,
the former were formed and further been reduced to alkyl anion, which protonated by
+
H to give the desired product with high antiꢀMarkovnikov regioselectivity (Step vii).
Furthermore, we also carried out first principles calculations using molecular density
functional theory to further couple radical intermediates with terminal olefin
(1ꢀheptene as an example). The formation of secondary carbonꢀcentred radical
intermediates is thermodynamically favorable to that of primary carbonꢀcentred
radicals (Fig. 3). The coupling reaction is also exothermic due to stabilization of the
carbonꢀcentred radical, and should also have a relatively low energy barrier. Upon
further reaction of the secondary radical intermediates with surfaceꢀadsorbed H*,
antiꢀMarkovnikov products are formed. In addition, there was a competitive pathway
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for direct hydrogenation of the olefin to form alkane by absorbed H* (Step viii).
Similar mechanisms were also proposed for the coupling reactions between other
substrates and olefins (Scheme S1).
Fig. 3. First principles studies on the photocatalytic coupling reaction. The primary
carbonꢀcentered radicals which were formed by abstracting a H from the αꢀC of methanol,
acetonitrile, acetic acid, acetone, and ethyl acetate are coupled with terminal olefin (1ꢀheptene) to
form secondary or primary carbonꢀcentered radicals with energies shown in blue and black,
respectively. Upon further hydrogenation, antiꢀMarkovnikov and Markovnikov products are
produced, and the latter are unfavorable. Energies at 0 K are given in kcal/mol. Spin density for
the radicals is shown to illustrate the nature of the radical. Colors of the atoms: blue for Ti, red for
O, black for C, green for N, and white for H.
For the photocatalytic hydrofunctionalization of olefins, the light absorption
wavelength of the photocatalyst can be tuned through band gap engineering by doping
2 2
TiO with metal cations and anions, surface sensitization of TiO with visible light
absorbing dyes, molecular complexes, quantum dots, etc29. And visibleꢀlightꢀdriven
photocatalysts are under development for this approach. In addition, suitable junction
structures should also lead to enhanced catalytic activity by improving the separation
39
efficiency of photogenerated electrons and holes .
Conclusions
10

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In summary, photocatalytic hydrofunctionalization of olefins provides a green
and atomꢀefficient strategy for the synthesis of a great range of valueꢀadded chemicals
all with nearly 100% antiꢀMarkovnikov regioselectivity. Excellent performance was
observed in the photocatalytic coupling reaction of olefins with methanol, acetonitrile,
acetic acid, acetone and ethyl acetate. Experimental and computational studies were
also performed to investigate the possible photocatalytic mechanism, which involved
αꢀCꢀH cleavage and CꢀC bond formation via the coupling of photogenerated radical
intermediates and terminal olefins. Our green strategy provides a promising route for
synthesizing various fine chemicals by the photocatalytic coupling of olefins, and can
be expected to have a broad impact in the field of chemical synthesis.
Conflicts of interest
There are no conflicts to declare.
Acknowledgement
This work has been supported by the National Key R&D Program of China
(2017YFB0602202), the Natural Science Foundation of China (21573271, 91545112),
and the Chinese Academy of Sciences (QYZDBꢀSSWꢀSLH035, XDA21020600).
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Green Chemistry
Page 14 of 14
View Article Online
DOI: 10.1039/C8GC00971F
TOC
A sustainable strategy for hydrofunctionalization of olefins to value-added chemicals
via photocatalytic cross-coupling was developed with high atomic economy.