Thiol-initiated photocatalytic oxidative cleavage of the C=C bond in olefins and its extension to direct production of acetals from olefins

Article abstract of DOI:10.1039/d0cy01963a

The oxidative cleavage of olefins to produce aldehydes/ketones is an important reaction in organic syntheses. In this manuscript, a mild and operationally simple protocol for the aerobic oxidation of olefins to produce carbonyl compounds was realized over ZnIn₂S₄under visible light, using air as the oxidant and a thiol as the initiator. It was proposed that the photogenerated holes over ZnIn₂S₄attack the thiol to produce thiyl radicals, which initiate the oxidative cleavage of the C=C bond in olefins to produce aldehydes/ketones. By further coupling with the condensation between the as-obtained aldehydes/ketones and alcohols, this strategy can also be applied to the production of different acetals directly from the olefins. This study demonstrates a new pathway to realize the oxidative cleavage of olefins to produce aldehydes/ketones, and also provides a new protocol for the production of acetals directly from the olefins.

Full text of DOI:10.1039/d0cy01963a

View Article Online
View Journal
Catalysis
Science &
Technology
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Wang, Y. Li and
Z. Li, Catal. Sci. Technol., 2020, DOI: 10.1039/D0CY01963A.
Volume
Number
7
2
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
21
January 2017
Pages 313-534
Catalysis
Science &
Technology
rsc.li/catalysis
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 2044-4761
PAPER
Chaoqiu Chen, Yong Qin et al.
Highly dispersed Pt nanoparticles supported on carbon
nanotubes produced by atomic layer deposition for hydrogen
generation from hydrolysis of ammonia borane
rsc.li/catalysis

Page 1 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Thiols Initiated Photocatalytic Oxidative Cleavage of
C=C Bond in Olefins and its Extension to Direct
Production of Acetals from Olefins
Xinglin Wang, Yuanyuan Li, Zhaohui Li
Research Institute of Photocatalysis, State Key Laboratory of Photocatalysis on
Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350116,
P. R. China

Author to whom all correspondences should be addressed.
E-mail: zhaohuili1969@yahoo.com, Tel (Fax): 86-591-22865855
1

Catalysis Science & Technology
Page 2 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Abstract
The oxidative cleavage of olefins to produce aldehydes/ketones is an important
reaction in organic syntheses. In this manuscript, a mild and operationally simple
protocol for the aerobic oxidation of olefins to produce carbonyl compounds was
realized over ZnIn S under visible light, using air as the oxidant and the thiol as the
2
4
initiator. It was proposed that the photo-generated holes over ZnIn S attack the thiol
2
4
to produce thiyl radicals, which initiate the oxidative cleavage of the C=C bond in
olefins to produce aldehydes/ketones. By further coupling with the condensation
between the as-obtained aldehydes/ketones and alcohols, this strategy can also be
applied to the production of different acetals directly from the olefins. This study
demonstrates a new pathway in realization of the oxidative cleavage of olefins to
produce aldehydes/ketones, and also provides a new protocol for the production of
acetals directly from the olefins.
Keywords: olefin, oxidative cleavage, thiyl radicals, aldehydes/ketones, acetal,
photocatalysis
2

Page 3 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Introduction
The oxidative cleavage of olefins to produce aldehydes/ketones is an important
reaction in organic syntheses since it can use inexpensive olefin feedstocks to produce
organic compounds with carbonyl functional groups.[1,2] Although traditional methods
including ozonolysis or using the Lemieux-Johnson Protocol, ie, OsO followed by
4
NaIO4,[3,4] have been used for the oxygenation of olefins, the related safety concern
limits their applications. Alternatively, metal-free reactions using equivalent oxidants
3
[5]
like m-chloroperbenzoic acid (mCPBA) and the developed aryl-λ -iodane, or the
combination of transition metal-based catalysts with peroxides, peracids and other
oxidizing reagents,[6-8] have also been applied for the C=C bond cleavage. However,
the use of either over-stoichiometric amounts of oxidants or the expensive metals not
only produces a large amount of by-products, but also increases the processing cost.
Abundant molecular O is considered to be an ideal oxidant in oxygenation
2
[9]
reactions due to its inexpensive and environmentally friendly characteristics. As an
economically attractive protocol to introduce oxygen-containing functional groups
into the organics, oxidation reactions based on different catalytic systems using O as
2
the oxidants is in particular attractive for large scale applications.[10,11] Actually,
oxidative cleavage of olefins to produce aldehydes/ketones using O as the oxidant
2
has also been demonstrated over a variety of catalytic systems.[12-15] For example,
Kroutil et al. described a simple bio-catalytic alkene cleavage to yield aldehydes.[16]
Catalyzed by Pd(OAc) in the presence of pressured O under an elevated
2
2
temperature, a wide range of olefins were oxidative cleaved, via the formation of
,2-diols or dioxo-PdII complexes as the precursors to the final carbonyl
1
compounds.[17] Alternatively, oxidative cleavage of olefins to aldehydes/ketones can
also be realized via the radical pathways.[18-21] For example, thermal activation of
Tert-butyl nitrite (TBN) under a metal free condition was found to release alkoxyl
radicals, which served as initiators to induce selective C=C cleavage to produce
aldehydes/ketones.[18] N-hydroxyphthalimide (NHPI) also served as a metal-free
catalyst for the oxidative cleavage of C=C bonds. Thermal hemolysis of NHPI led to
the formation of PINO radicals, which attacked the C=C double bond to produce
carbon radicals and further trapped by molecular O to give peroxyl radicals.[19]
2
However, these oxygenation reactions have to be carried out under high temperature
to activate either the substrates or the catalysts, and in some cases, high pressured
oxygen is also required.
3

Catalysis Science & Technology
Page 4 of 21
View Article Online
DOI: 10.1039/D0CY01963A
As compared with the traditional thermal activated processes, light initiated
reactions can be carried out in a mild condition and therefore can be more selective
since some undesirable thermally induced side reactions can be inhibited.[22-25] Since
most of the organic compounds are only responsive in the UV light region, the initial
studies in this field were carried out under UV irradiations.[26] For example, the UV
light irradiations on CBr led to the formation of Br radicals, which initiate the
4
aerobic photo-oxidative cleavage of the C=C bond of - or -substituted styrenes.[27]
However, the possible decomposition of the involved reactive peroxides under UV
irradiations lowered the yields to the desirable aldehydes/ketones.[28] By formation of
a visible light responsive charge transfer (CT) complexes between oxygen and the
olefins inside the cages of the zeolites, Frei and coworkers reported the visible light
induced oxygenations of 2,3-dimethyl-2-butene via dioxetanes as the intermediate.[29]
1
Singlet oxygen ( O ) generated by visible light irradiations on a platinum(II)
2
polypyridyl complex has also been reported to oxidative cleavage of the C=C
bonds.[30] Recently, Wang and coworkers reported an interesting protocol to realize
the aerobic oxidative cleavage of C=C bonds to produce aldehydes/ketones under
visible light, using electron-rich aromatic disulfides as the photocatalyst.[31] Both
experimental and computational studies suggest that a disulfide-olefin charge-transfer
complex formed is responsible for the facile dissociation of disulfide S-S bond under
visible light to generate thiyl radicals, which attack the C=C bonds to form the
carbon-centered radicals and further trapped by O to afford aldehyde/ketone via
2
dioxetane as the intermediates.
Considering that thiyl radicals can initiate the oxidative cleavage of C=C bonds
to produce aldehydes/ketones, and stimulated by our previous studies that thiyl
radicals can be generated when ZnIn S was irradiated under visible light in the
2
4
presence of the thiols,[32,33] herein we investigated the oxygenation of alkenes over
irradiated ZnIn S with the presence of thiols. Ternary ZnIn S is a ternary
2
4
2 4
chalcogenide with a band gap well responsive in the visible-light region, which has
been widely studied for photocatalytic H evolution and light induced organic
2
syntheses.[34-41] A successful oxidative cleavage of a variety of olefins to produce
aldehydes/ketones was found to be realized over visible light irradiated ZnIn S , with
2
4
benzyl mercaptane as the additive. Our system is the first demonstration that such a
reaction can be realized over a visible light induced semiconductor-based
4

Page 5 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
photocatalyst, using thiol as an initiator. In addition, the current photocatalytic system
can also be applied to the one-pot syntheses of different acetals from the reaction
between the olefins and alcohols in the presence of the thiol (benzyl mercaptane).
Results and discussion
ZnIn S was prepared through a solvothermal method from ZnCl , InCl and
2
4
2
3
thioacetamide (TAA) in
a
mixture of ethylene glycol (EG) and
N,N-dimethylformamide (DMF). The XRD diffraction patterns of the product are
[42]
indexed to hexagonal ZnIn S (JCPDS 65-2023) (Supporting Figure S1). The SEM
2
4
image shows that the product is composed of flowerlike microspheres with a
dimension of approximately 1 m, which is made up of numerous interwoven
nanoflakes (Supporting Figure S2). The N adsorption/desorption isotherms of the
2
as-obtained ZnIn S were also studied, with its BET specific surface area determined
2
4
2
to be 91.32 m /g (Supporting Figure S3). The UV-Vis diffuse reflectance spectrum
UV-vis DRS) of the product shows that it has strong absorption in the visible light
(
region, with an absorption edge extending to ca. 490 nm, corresponding to a band gap
of ca. 2.5 eV (Supporting Figure S4).
To study the performance of ZnIn S for the oxidative cleavage of olefins to
2
4
form aldehydes/ketones, styrene was first chosen as the substrate and the reaction was
initially carried out in dichloromethane (CH Cl ), in the presence of equimolar of
2
2
benzyl mercaptane (to styrene) under visible light, using air as the oxidant. It was
found that 28.1% of styrene was converted after irradiated for 15h, with a yield of
2
3% to benzaldehyde, the oxidative product (Table 1, entry 1). To study the influence
of the solvent, the reaction carried out in anisole, paraxylene, cyclohexane,
methylbenzene and acetonitrile (CH CN) was also investigated. It was found that for
3
these solvents, a conversion of styrene ranged from 25.7 to 81.2% and a yield to the
desired benzaldehyde ranged from 14.5 to 77.9% was realized (Table 1, entries 2-6).
Among all the solvents investigated, CH CN was found to be the best one for this
3
reaction, by showing the highest styrene conversion ratio of 81.2% and an optimum
yield of 77.9% to benzaldehyde after irradiated for 15 h. In the meantime, 84.5% of
benzyl mercaptane was converted, yielding disulfide (58.2%) and benzylsulfonic acid
(
19.1%).[43] The time-dependent conversion of styrene and the formation of
benzaldehyde was investigated and the result was shown in Fig. 1. Obviously the
conversion of the substrate (styrene) and the yield to the desired product
5

Catalysis Science & Technology
Page 6 of 21
View Article Online
DOI: 10.1039/D0CY01963A
(
benzaldehyde) increases with the irradiation time. No conversion of styrene was
observed either in absence of ZnIn S or in dark (Table 1, entries 7 and 8). The AQE
2
4
of the photocatalytic oxidative cleavage of styrene at 420 nm, 460 nm and 500 nm
was determined to be 0.097, 0.068 and 0.051 respectively. The AQE depends on the
wavelength in a manner that correlates with the absorption intensities of ZnIn S in
2
4
the visible light region (Supporting Figure S5), indicating that it is truly a
photocatalytic reaction. In addition, almost negligible styrene was converted in
absence of benzyl mercaptane under otherwise similar conditions (Table 1, entry 9),
indicating that benzyl mercaptane is essential for the oxidative cleavage of styrene to
produce benzaldehyde. The amount of the benzyl mercaptane also influenced the
performance. The yield to benzaldehyde decreased from 77.9% to 32.0% when only
0
.02 equimolar of benzyl mercaptane (to styrene) was used in the reaction (Table 1,
entry 10). On the contrary, a slightly increased yield to benzaldehyde (82.5%) was
observed when the amount of benzyl mercaptane was increased to 2 equimolar (to
styrene) (Table 1, entry 12).
The above results clearly indicate that benzyl mercaptane is involved in the
oxidative cleavage of C=C bond in styrene to produce benzaldehyde over irradiated
ZnIn S . Our previous studies revealed that the hydrothiolation reactions between
2
4
thiols and unsaturated alkenes/alkynes can be realized over visible light irradiated
ZnIn S , in which the photogenerated holes in ZnIn S attack the thiols to produce the
2
4
2 4
thiyl radicals and initiate the thio-ene/yne reactions.[33] Similarly, photo-generated
holes in ZnIn S can also attack the benzyl mercaptane to produce the thiyl radicals,
2
4
which is supposed to initiate the oxidative cleavage of C=C bond in styrene. To
confirm this assumption, the ESR of the reaction system, a suspension containing
ZnIn S , styrene, benzyl mercaptane and 5,5-dimethyl-1-pyrroline N-oxide (DMPO)
2
4
in CH CN, was studied. The DMPO spin-trapping ESR spectra of the reaction system
3
under visible light irradiation shows four typical signals corresponding to the
DMPO-thiyl adducts, a confirmation of the generation of thiyl radicals under visible
light (Fig. 2). In addition, control experiments were carried out in the presence of
radical trapping agents including DMPO and benzoquinone (BQ). The introduction of
either DMPO or BQ led to a significantly lower activity for the oxidative cleavage of
styrene, with only 5% and 7% of styrene converted under otherwise similar
conditions, for the system containing DMPO or BQ respectively (Supporting Table
S1), confirming that the radicals did involve in the reaction. It is proposed that the
6

Page 7 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
thiyl radicals can attack the C=C bond in styrene to produce the carbon-centered
radical 2 (step 2), which are further trapped by oxygen to form superoxide radical 3
step 3). Key intermediate dioxetane 4 produced, which upon heterolysis, gives the
(
final oxygenation products, with the concomitant release of the thiyl radicals to
complete the catalytic cycle (step 4). The change of air to pure O did not influence
2
the conversion of styrene obviously (81.2% in air vs. 78.3% in O , entries 6 and 13),
2
indicating that the trapping of the carbon-centered radical 2 by O to form superoxide
2
radical 3 is not the rate limiting step. However, when the intensity of the irradiation
2
2
decreased from 65 mW /cm to 32.5 mW /cm , the conversion of styrene decreased
from the original 81.2% to 59.5% (Table 1, entries 6 and 14). As shown in Table 1
(entries 6, 10 and 11), the amount of the initiator added (benzyl mercaptane) also
influenced the activity. Therefore, it is believed that the photo-generation of the thiyl
radicals is the rate limiting step in this reaction. The mechanism for the formation of
benzaldehyde from styrene over irradiated ZnIn S in the presence of benzyl
2
4
mercaptane was shown in Scheme 1.
It is obvious that the formation of benzaldehyde from styrene also follows a
radical-mediated oxidative pathway, in which thiyl radicals attack the C=C bond in
the presence of oxygen to form the dioxetane as the important intermediate, a pathway
previous proposed for the oxidative cleavage of olefins to produce
aldehydes/ketones,[44] except that the thiyl radicals in the current system are produced
by the attack of photogenerated holes on the benzyl mercaptane. The proposed
mechanism was also confirmed by the detection of 1-phenyl-1-methyl-1,2-ethanediol
by GC-MS when methionine and water was introduced into the reaction system, since
previous study has revealed that although the dioxetane, the important intermediate 4,
is not stable, it can be trapped by methionine and water to form the detectable diol
(
Supporting Figure S6).[45] A small amount of benzylsulfonic acid was also detected
in the reaction system, which may be formed due to the oxidation of the thiyl radicals
by O (step 5). The presence of this side reaction lead to slightly lower amount of the
2
photogenerated thiyl radicals and as a result, a slightly lowering of the activity was
observed after three consecutive cycling reactions even though the photocatalyst was
stable as evidenced from its similar XRD patterns (Supporting Figure S7 and S8).
Surely the coupling of the thiyl radicals to produce disulfides also occurs (step 6).
However, when irradiated, the disulfides will also be cleaved to regenerate the thiyl
radicals for the reactions.
7

Catalysis Science & Technology
Page 8 of 21
View Article Online
DOI: 10. 21 03 49 /D0CY01963A
The photo-oxidative cleavage of olefins over visible light irradiated ZnIn S
using benzyl mercaptane as the initiator can also be applied to a wide scope of
substrates (Table 2). Styrenes with different functional groups in the benzene ring,
including both electron-withdrawing substituents (p-F, p-Cl and o-Cl) as well as
electron-donating groups (p-OCH and p-CH ) can all be converted to their
3
3
corresponding aldehydes in yields of 65.2-80.5% (Table 2, entries 1-5). No obvious
electronic effect was observed in this reaction. In addition, the reactions using either
α-methylstyrene or 1,1-diphenylethylene as the substrate led to the formation of
acetophenone (81.2%) and benzophenone (73.4%), the ketone products (Table 2,
entries 6,7).
Acetals are important intermediates in organic syntheses and found wide
applications in chemical and medicinal industry.[46,47] Acetals are usually obtained
from aldehydes/ketones. Considering that the oxidative cleavage of the olefins to
produce aldehydes/ketones can be realized over the current catalytic system under
visible light, it would be an ideal protocol to couple it with the condensation between
aldehydes/ketones and alcohols to directly produce acetals from olefins. Therefore,
the reactions between different olefins and several alcohols were investigated in the
presence of benzyl mercaptane over visible light irradiated ZnIn S . To our
2
4
expectation, all the investigated reactions occur smoothly, leading to corresponding
acetals with yields ranged from 38% to 81% (Table 3). In addition, the photocatalytic
system showed high stability during the reaction, as evidenced from the cycling
reactions as well as its unchanged XRD patterns after the reaction (Fig. 3 and 4).
Conclusion
In summary, the oxidative cleavage of olefins to produce aldehydes/ketones was
realized over ZnIn S under visible light, using air as the oxidant and the benzyl
2
4
mercaptane as the initiator. The holes photogenerated over ZnIn S attack the thiols to
2
4
produce thiyl radicals, which are added to the C=C bond in olefins and are oxidized to
produce aldehydes/ketones. This strategy not only can be applied to a broad scope of
olefins, but also can be coupled with the further condensation between the as-obtained
aldehydes/ketones and alcohols to yield acetals directly from the olefins. This study
demonstrates a new pathway in realization of the oxidative cleavage of olefins to
produce aldehydes/ketones, and also provides a new protocol for the production of
acetals directly from the olefins.
Acknowledgements
8

Page 9 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
This work was supported by NSFC (21872031 and U1705251). Z. Li
acknowledges the Award Program for Minjiang Scholar Professorship for financial
support.
9

Catalysis Science & Technology
Page 10 of 21
View Article Online
DOI: 10.1039/D0CY01963A
References
[1] G. Urgoitia, R. SanMartin, M. T. Herrero, E. Domínguez, ACS Catal. 2017, 7,
3
050-3060.
[2] J. Wan, Y. Gao, L. Wei, Chem. Asian J. 2016, 11, 2092-2102.
[3] S. G. Van Ornum, R. M. Champeau, R. Pariza, Chem. Rev. 2006, 106,
2
990-3001.
4] R. Pappo, D. S. Allen Jr, R. U. Lemieux, W. S. Johnson, J. Org. Chem. 1956, 21,
78-479.
5] K. Miyamoto, Y. Sei, K. Yamaguchi, M. Ochiai, J. Am. Chem. Soc. 2009, 131,
382-1383.
[
[
4
1
[6] A. Rajagopalan, M. Lara, W. Kroutil, Adv. Synth. Catal. 2013, 355, 3321-3335.
[7] D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang, Z. Shi, Org. Lett. 2006, 8, 693-696.
[8] S. T. Liu, K. V. Reddy, R. Y. Lai, Tetrahedron 2007, 63, 1821-1825.
[9] R. Mei, U. Dhawa, R.C. Samanta, W. Ma, J. Wencel-Delord, L. Ackermann,
ChemSusChem 2020, 13, 3306-3356.
[10]Y. Liang, N. Jiao, Acc. Chem. Res. 2017, 50, 1640-1653.
[11]H. Sterckx, B. Morel, B. U. W. Maes, Angew. Chem. Int. Ed. 2019, 58,
7
946-7970.
[
[
[
12]M. Hu, W. Wu, H. Jiang, ChemSusChem 2019, 12, 2911-2935.
13]A. Gonzalez-de-Castro, J. Xiao, J. Am. Chem. Soc. 2015, 137, 8206-8218.
14]I. Hajnal, K. Faber, H. Schwab, M. Hall, K. Steiner, Adv. Synth. Catal. 2015, 357,
3
309-3316.
[15]A. Bhowmik, R. A. Fernandes, Org. Lett. 2019, 21, 9203-9207.
[16]M. Lara, F. G. Mutti, S. M. Glueck, W. Kroutil, J. Am. Chem. Soc. 2009, 131,
5
368-5369.
[
[
[
[
[
17]A. Wang, H. Jiang, Org. Chem. 2010, 75, 2321-2326.
18]C. Miao, B. Yu, L. He, Green Chem. 2011, 13, 541-544.
19]R. Lin, F. Chen, N. Jiao, Org. Lett. 2012, 14, 4158-4161.
20]G. Wang, X. Li, J. Dai, H. Xu, J. Org. Chem. 2014, 79, 7220-7225.
21]A. Fujiya, A. Kariya, T. Nobuta, N. Tada, T. Miura, A. Itoh, Synlett 2014, 25,
8
84-888.
[22]X. Lang, X. Chen, J. Zhao, Chem. Soc. Rev. 2014, 43, 473-486.
[23]X. Deng, Z. Li, H. Garcia, Chem. Eur. J. 2017, 23, 11189-11209.
[24]G. Chen, G.I.N. Waterhouse, R. Shi, J. Zhao, Z. Li, L. Wu, C. Tung, T. Zhang,
Angew. Chem. Int. Ed. 2019, 58, 17528-17551.
[25]C. Wang, P. H. Dixneuf, J. F. Soulé, Chem. Rev. 2018, 118, 7532-7585.
[26]A. C. Hernandez-Perez, S. K. Collins, Acc. Chem. Res. 2016, 49, 1557-1565.
[27]S. Hirashima, Y. Kudo, T. Nobuta, N. Tada, A. Itoh, Tetrahedron Lett. 2009, 50,
4
328.
[28]E. L. Clennan, G. L. Pan, Org. Lett. 2003, 5, 4979-4982.
1
0

Page 11 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
[29]F. Blatter, H. Frei, J. Am. Chem. Soc. 1993, 115, 7501-7502.
[
30]Q. Meng, T. Lei, L. Zhao, C. Wu, J. Zhong, X. Gao, C. Tung, L. Wu, Org. Lett.
014, 16, 5968-5971.
31]Y. Deng, X. Wei, H. Wang, Y. Sun, T. Noël, X. Wang, Angew. Chem. Int. Ed.
017, 56, 832-836.
2
[
2
[
[
[
[
[
[
[
32]L. Xu, X. Deng, Z. Li, Appl. Catal. B: Environ. 2018, 234, 50-55.
33]Y. Li, J. Cai, M. Hao, Z. Li, Green Chem. 2019, 21, 2345-2351.
34]B. Wang, Z. Deng, X. Fu, Z. Li, J. Mater. Chem. A 2018, 6, 19735-19742.
35]H. Hao, X. Lang. ChemCatChem. 2019, 11, 1378-1393.
36]B. Wang, Y. Ding, Z. Deng, Z. Li, Chin. J. Catal. 2019, 40, 335-342.
37]M. Hao, X. Deng, L. Xu, Z. Li, Appl. Catal. B: Environ. 2019, 252, 18-23.
38]B. Xu, P. He, H. Liu, P. Wang, G. Zhou, X. Wang, Angew. Chem. Int. Ed. 2014,
5
3, 2339-2343.
39]B. Wang, Z. Deng, X. Fu, C. Xu, Z. Li, Appl. Catal. B: Environ. 2018, 237,
70-975.
[
[
9
40]W. Yang, L. Zhang, J. Xie, X. Zhang, Q. Liu, T. Yao, S. Wei, Q. Zhang, Y. Xie,
Angew. Chem. Int. Ed. 2016, 55, 6716-6720.
[
[
[
41]X. Wang, Y. Li, Z. Li, Chin. J. Catal. 2021, 42, 409-416.
42]B. Wang, Z. Deng, Z. Li, J. Catal. 2020, 389, 241-246.
43]A. Mardyukov, P. R. Schreiner, Phys. Chem. Chem. Phys. 2016, 18,
2
6161-26165.
44]B. Xiong, X. Zeng, S. Geng, S. Chen, Y. He, Z. Feng, Green Chem. 2018, 20,
521-4527.
45]W. Adam, S. G. Bosio, N. J. Turro, B. T. Wolff, J. Org. Chem. 2004, 69,
704-1715.
[
[
4
1
[
46]B. T. Gregg, K. C. Golden, J. F. Quinn, J. Org. Chem. 2007, 72, 5890-5893.
47]O. Diebolt, C. Cruzeuil, C. Müller, D. Vogt, Adv. Synth. Catal. 2012, 354,
[
6
70-677.
1
1

Catalysis Science & Technology
Page 12 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Captions for Figures
Fig. 1 Time-dependent changes in the amounts of styrene and benzaldehyde under
visible-light irradiation over ZnIn2S4
Fig. 2 DMPO spin-trapping ESR spectra of the reaction system containing ZnIn S ,
2
4
styrene, benzyl mercaptan and CH CN (a) in the dark and (b) under visible light
3
irradiation
Fig. 3 Cycling of ZnIn S for the reaction between styrene and methanol in the
2
4
presence of benzyl mercaptane under visible-light irradiation
Fig. 4 XRD diffraction patterns of (a) fresh ZnIn S and (b) used ZnIn S (after three
2
4
2 4
cycling reactions between styrene and methanol)
Captions for Tables
Table 1 Light induced catalytic performance for the oxidative cleavage of styrene in
the presence of benzyl mercaptane over ZnIn S under different conditions
2
4
Table 2 Investigations of the substrate scope of the oxidative cleavage of olefins in
the presence of benzyl mercaptane over ZnIn2S4
Table 3 Light induced production of acetals from olefins in the presence of benzyl
mercaptane over ZnIn2S4
Caption for Scheme
Scheme 1 Proposed mechanism for the oxidative cleavage of olefins in the presence
of benzyl mercaptane over ZnIn S under visible light
2
4
1
2

Page 13 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Fig. 1
1
3

Catalysis Science & Technology
Page 14 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Fig. 2
1
4

Page 15 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Fig. 3
1
5

Catalysis Science & Technology
Page 16 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Fig. 4
1
6

Page 17 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Table 1
Entry
PhCH SH
Styrene/
Benzaldehyde/
2
Solvent
e
/
mmol
Conv.
28.1%
25.7%
26.3%
29.0%
30.1%
81.2%
-
Yield
1
2
0.1
Dichloromethane
Anisole
23.0%
14.5%
23.5%
24.6%
27.8%
77.9%
-
0.1
3
0.1
Paraxylene
4
0.1
Cyclohexane
Methylbenzene
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
Acetonitrile
5
0.1
6
0.1
7a
8b
9c
0.1
0.1
-
-
0.1
-
-
1
1
1
0
1
2
0.02
0.06
0.2
46.1%
55.2%
88.6%
78.3%
59.5%
32.0%
42.9%
82.5%
75.1%
55.4%
1
3d
4f
0.1
1
0.1
Conditions: styrene (0.1 mmol), benzyl mercaptane, ZnIn S (10 mg), solvent (4 mL),
2
4
under air, visible light irradiation for 15 h. a. without ZnIn S ; b. without light; c.
2
4
without benzyl mercaptane; d.in pure O ; f. irradiation for 15 h with lower light
2
2
intensity (32.5 mW/cm ); e. The amount of the products was calculated based on GC
and GC-MS.
1
7

Catalysis Science & Technology
Page 18 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Table 2
Aromatic olefin
Products
(yield/%)
Entry
a
(conv./%)
1
1
a (81.7)
2a (75.7)
2
3
4
5
1
b (83.4)
2b (79.8)
2c (80.5)
2d (66.1)
2e (65.2)
1
c (84.1)
1
d (74.4)
1
e (71.1)
6
7
1
f (89.4)
2f (81.2)
2g (73.4)
1
g (79.0)
Conditions: Aromatic olefins (0.1 mmol), benzyl mercaptane (0.1 mmol),
ZnIn S (10 mg), CH CN (4 mL), under air, visible light irradiation for
2
4
3
1
5 h; a. The amount of the products was calculated based on GC and
GC-MS.
1
8

Page 19 of 21
Catalysis Science & Technology
View Article Online
DOI: 10.1039/D0CY01963A
Table 3
Entry
Styrene
Alcohol
Aromatic acetals
Yield (%)a, b
1
CH OH
81
56
3
2
3
C H OH
2
5
C H OH
38
3
7
4
5
6
7
CH OH
71
78
75
70
3
CH OH
3
CH OH
3
CH OH
3
Conditions: Aromatic olefins (0.1 mmol), benzyl mercaptane (0.1 mmol), ZnIn S (10
2
4
mg), alcohols (4 mL), under air, visible light irradiation for 15h; a. conv. was
calculated based on olefins; b. The amount of the products was calculated based on
GC and GC-MS.
1
9

Catalysis Science & Technology
Page 20 of 21
View Article Online
DOI: 10.1039/D0CY01963A
Scheme 1
2
0

Page 21 of 21
Catalysis Science & Technology
View Article Online
Graphical Abstract
DOI: 10.1039/D0CY01963A