Visible-Light-Driven Selective Air-Oxygenation of C?H Bond via CeCl3 Catalysis in Water

Article abstract of DOI:10.1002/cssc.202100682

Visible-light-induced C?H aerobic oxidation is an important chemical transformation that can be applied for the synthesis of aromatic ketones. High-cost catalysts and toxic solvents were generally needed in the present methodologies. Here, an efficient aqueous C?H aerobic oxidation protocol was reported. Through CeCl₃-mediated photocatalysis, a series of aromatic ketones were produced in moderate to excellent yields. With air as the oxidant, this reaction could be performed under mild conditions in water and demonstrated high activity and functional group tolerance. This method is economical, highly efficient, and environmentally friendly, and it will provide inspiration for the development of aqueous photochemical synthesis reactions.

Full text of DOI:10.1002/cssc.202100682

Communications
doi.org/10.1002/cssc.202100682
ChemSusChem
Very Important Paper
Visible-Light-Driven Selective Air-Oxygenation of CÀ H Bond
via CeCl3 Catalysis in Water
Pan Xie,*[a] Cheng Xue,[a] Sanshan Shi,[a] and Dongdong Du[a]
Visible-light-induced CÀ H aerobic oxidation is an important
chemical transformation that can be applied for the synthesis of
aromatic ketones. High-cost catalysts and toxic solvents were
generally needed in the present methodologies. Here, an
efficient aqueous CÀ H aerobic oxidation protocol was reported.
Through CeCl3-mediated photocatalysis, a series of aromatic
ketones were produced in moderate to excellent yields. With air
as the oxidant, this reaction could be performed under mild
conditions in water and demonstrated high activity and func-
tional group tolerance. This method is economical, highly
efficient, and environmentally friendly, and it will provide
inspiration for the development of aqueous photochemical
synthesis reactions.
Figure 1. Chemical structure of some commercial drugs containing the aryl
ketone motif.
As one of the most essential organic transformation processes,
oxidation has played an enormous role in production and life.[1]
Among the numerous oxidation processes, CÀ H oxygenation
would be very important due to the widespread existence of
CÀ H bond in organic compounds.[2] The importance is also
reflected in that CÀ H oxygenation can be used for the synthesis
of one highly relevant group of oxygen-containing compounds,
aryl ketones, which often demonstrate pharmacological proper-
ties and biological activities (Figure 1).[3] Thus, great efforts have
been devoted to the development of CÀ H oxygenation for the
production of aryl ketones.
In traditional CÀ H oxygenation reactions (Scheme 1),[4]
transition metals and peroxide were generally needed to be
served as the catalyst as well as the oxidant, which reduced the
atom economy significantly. Besides, the use of toxic and
dangerous oxidants would add a lot of operation risk. It is
indisputable that O2 is a cheap, clean and readily available
oxidant and is ideal for the CÀ H oxygenation.[5] Various aerobic
Scheme 1. Present methodologies of CÀ H oxygenation for the synthesis of
aryl ketones.
oxidation reactions of CÀ H bond were developed through N-
hydroxyphthalimide (NHPI) or transition-metal-based catalysis.[6]
Besides, some heterogeneous catalytic strategies were also
established to produce aryl ketones via CÀ H oxygenation.[7]
However, harsh conditions were frequently used and some
expensive catalysts or ligands also affected the practical value
of these methodologies.
Recently, visible-light-driven chemical transformation has
emerged as a powerful tool in today‘s synthetic chemistry
landscape,[8] which was also applied in the field of the aerobic
oxygenation. Hosseini-Sarvari et al. designed two heteroge-
neous catalysts: nano Ni/g-C3N4 and ternary Ag/AgBr/TiO2
nanotube.[9] By using these catalytic systems, they realized
the oxidation of CÀ H Bonds via heterogeneous photocatal-
ysis. We know that both catalysts should be prepared at quite
high temperature. In addition, high cost and preparation
difficulty also made these processes not conducive to large-
scale industrial productions. Jiang and co-workers developed
a new kind of iron photocatalyst, tetrahalogenoferrate (III)
[a] Prof. P. Xie, C. Xue, S. Shi, D. Du
College of Chemistry and Chemistry Engineering
Shaanxi Key Laboratory of Chemistry Additives for Industry
Shaanxi University of Science & Technology
Xi’an, 710021 (P. R. China)
E-mail: pan.xie@sust.edu.cn
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/cssc.202100682
ChemSusChem 2021, 14, 1–6
1
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cssc.202100682
ChemSusChem
complexes, which demonstrated a good and tunable photo-
sensitivity in the light-induced CÀ H oxygenation reactions.[10]
Most recently, Fu and co-workers first established a novel
light and oxygen-enabled CF3SO2Na-mediated strategy for
the selective oxidation of CÀ H bonds to produce aromatic
ketones.[11] Both reactions allowed the CÀ H oxygenation to
proceed with high atomic economy under mild conditions;
however, the application of toxic solvent still produced an
enormous amount of hazardous waste. In light of the
increasing attention towards environmental protection today,
further development of green and efficient methodology to
realize the CÀ H oxygenation with an environmentally friendly
solvent would be highly desired.[12]
which revealed the O2 in air participated in the reaction and
oxygen in the product might be from the dioxygen. The
investigation of different commercial photosensitizer did not
improve the reaction yield, suggesting CeCl3 was still the best
choice. Then the catalyst loading was decreased from 10 to
5 mol%, and slightly lower yield was obtained. Furthermore,
some other phase-transfer catalysts, such as tetrabutylammo-
nium bromide (TBAB), 18-Crown-6 and PEG 2000 were inves-
tigated. All of them cause the yield to decrease to a certain
degree.
After establishing the optimized conditions for the CÀ H
oxygenation of diphenylmethane, we first examined the scope
of diarylmethanes. As shown in Figure 2, the reaction tolerated
electron-donating and electron-withdrawing groups, such as
methyl and chloride on the different positions of the of the
phenyl ring, generating the corresponding ketone in good
yields. Then, cyclic ketones, such as fluorenone and xanthone
could be also produced in the valuable yield by this method-
ology when fluorene and xanthene were used as the starting
materials.
A range of aryl alkanes were next investigated to further
test the synthetic potential of our protocol (Figure 3). Various
substrates, including neutral (3a, 3k, 3l, 65–85% yields),
electron-rich (3b, 3c, 3j, 50–86% yields) and electron-deficient
(3d-3i, 65–80% yields) ethyl arenes could be compatible in this
transformation. A slight steric hindrance effect for the reaction
was observed, which was demonstrated by the reactivities of
ortho- and para-bromide, or ortho- and para-nitro substituted
ethylbenzene (3f vs. 3g, 3h vs. 3i). It is worth noting that a
series of functional groups could be tolerated in the CÀ H
oxidation, giving the desired product in moderate to good
yields. Also, this supplied a potential possibility for the further
derivation. Finally, cyclohexane was also served as the starting
material, but unfortunately, no cyclohexanone was obtained as
the product.
As the most abundant rare earth element,[13] cerium has
long been used in the light-induced organic synthesis due to its
unique photophysical properties.[14] Zuo and co-workers devel-
oped a series of cerium(III)-promoted photocatalytic organic
transformations via ligand-to-metal charge transfer (LMCT)
process,[15] which also inspired us to explore more possibilities
of cerium catalysis. Herein, we reported an efficient aqueous
CÀ H aerobic oxidation protocol to generate aryl ketones via
CeCl3-mediated photocatalysis process.
At the outset of our studies, we examined the aerobic
oxidation of 1,1-diphenylethylene (1a) under different condi-
tions (Table 1, see the Supporting Information for details). To
our delight, we found that the conditions using 10 mol% of
CeCl3 as the photosensitizer, 2 mol% of polyethylene glycol
4000 (PEG 4000) as the additive and water as the solvent with
irradiation of a 5 W blue light under air atmosphere achieved
the desired product, benzophenone in 82% yield. Then we
found both Ce catalyst and light are indispensable because the
exclusion of eithrt led to the complete inhibition of this
oxygenation reaction. The absence of PEG 4000 caused the
yield to decrease obviously, demonstrating the importance of a
phase-transfer catalyst for the process. When the reaction
proceeded under N2 atmosphere, no product was observed,
Additionally, the catalyst loading could be reduced to
0.5 mol% in the reaction of 1a, furnishing the product 2a in
73% yield when the reaction time was prolonged to 48 h
(Scheme 2). We are also pleased to find that the reaction can be
Table 1. Parameters for CÀ H oxygenation of diphenylmethane.[a]
Entry
Variation of the standard conditions
Yield[b]
[%]
1
2
3
4
5
6
7
8
none
without CeCl3
without light
without PEG 4000
N2 atmosphere instead of air
CeBr3 instead of CeCl3
Eosin Y instead of CeCl3
fac-Ir(ppy)3 instead of CeCl3
CeCl3 (5 mol%) instead of CeCl3 (10 mol%)
TBAB instead of PEG 4000
18-Crown-6 instead of PEG 4000
PEG 2000 instead of PEG 4000
82
n.r.
n.r.
40
n.r.
57
34
21
71
54
60
70
9
10
11
12
Figure 2. Substrate scope of diarylmethanes. Reaction conditions: 1a
(0.2 mmol), CeCl3 (10 mol%), PEG 4000 (2 mol%) in H2O (1.0 mL) at room
[a] 1a (0.2 mmol), CeCl3 (10 mol%), PEG 4000 (2 mol%) in H2O (1.0 mL) at
°
°
room temperature (25 C), irradiation under Blue LED (405–410 nm, 5 W)
for 24 h. [b] Isolated yield. n.r.=no reaction.
temperature (25 C), irradiation under Blue LED (405–410 nm, 5 W) for 24 h.
Isolated yield.
ChemSusChem 2021, 14, 1–6
www.chemsuschem.org
2
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cssc.202100682
ChemSusChem
Scheme 3. Control experiments.
Figure 3. Substrate scope of aryl alkanes. Reaction conditions: 1 a
(0.2 mmol), CeCl3 (10 mol%), PEG 4000 (2 mol%) in H2O (1.0 mL) at room
that the oxygen of carbonyl group originated from dioxygen in
the air.
°
temperature (25 C), irradiation under blue LED (405–410 nm, 5 W) for
24 h. Isolated yield.
Combining all the information obtained above and
previous reports,[18] a plausible mechanism of this trans-
formation was proposed and illustrated in Scheme 4. The
excited-state species, [CeIII]* was first obtained via the
irradiation of CeCl3, which was oxidized to [CeIV] by O2 along
with the generation of superoxide radical anion. Then, the
treatment of [CeIV] species with ethylbenzene 3a would
deliver the radical cation A. Meanwhile, [CeIII] was recovered
to close the photocatalytic cycle. On the other hand, radical
species A would react with superoxide radical anion to
furnished intermediate B. The following dehydration would
provide the target ketone product 4a.
In summary, we have developed an aqueous photocatalytic
system through CeCl3 catalysis, and a series of aromatic ketones
were synthesized in moderate to excellent yields via selective
air-oxygenation of CÀ H bonds by using readily available diaryl-
methanes or aryl alkanes as the starting materials. A variety of
functional groups, such as methoxy, fluorine, chlorine, bromine,
hydroxy and nitro group, were tolerated in this methodology.
We believed this protocol should provide some inspiration for
the development of environmentally friendly organic trans-
formation processes. The investigations on the mechanism and
Scheme 2. Reaction practicability.
effectively scaled up with good efficiency. For instance, the
oxygenation of 1a could be directly run at a 20 mmol scale by
using 2 mol% of CeCl3 for 40 h, to produce benzophenone in
77% yield.
To gain further information of the reaction mechanism,
some control experiments were carried out (Scheme 3). Radical
scavengers, such as 2,6-di-tertbutyl-4-methyl phenol (BHT) and
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) were first sub-
jected to the standard reaction. As a result, the reaction was
almost completely inhibited, demonstrating a radical pathway
might be involved in the oxidation process. Then, we found
when CuCl2 was added, the yield decreased dramatically, which
proved the involvement of single-electron processes.[16] Further-
more, the addition of benzoquinone led to obviously lower
yield, suggesting the presence of superoxide radical anion.[17]
Finally, H218O was used as the solvent to show the actual source
of oxygen in the ketone product. Just like what we imagined
above, no 18O-labelled product was observed, which indicated
Scheme 4. Plausible mechanism for CÀ H oxygenation reaction.
ChemSusChem 2021, 14, 1–6
www.chemsuschem.org
3
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cssc.202100682
ChemSusChem
e) W. A. A. Arafa, J. Heterocycl. Chem. 2019, 56, 1403–1412; f) A. M.
Pandey, S. G. Agalave, C. P. Vinod, B. Gnanaprakasam, Chem. Asian J.
2019, 14, 3414–3423; g) H. Yu, Q. Zhao, Z. Wei, Z. Wu, Q. Li, S. Han, Y.
Wei, Chem. Commun. 2019, 55, 7840–7843; h) D. P. Lubov, E. P. Talsi,
K. P. Bryliakov, Russ. Chem. Rev. 2020, 89, 587–628; i) M. Oliva, G. A.
Coppola, E. V. Van der Eycken, U. K. Sharma, Adv. Synth. Catal. 2021,
363, 1810–1834.
further application of our strategy are still ongoing in our
laboratory.
Acknowledgements
[5] a) M. S. Sigman, D. R. Jensen, Acc. Chem. Res. 2006, 39, 221–229; b) T.
Tsukuda, H. Tsunoyama, H. Sakurai, Chem. Asian J. 2011, 6, 736–748;
c) C. Parmeggiani, F. Cardona, Green Chem. 2012, 14, 547–564; d) S.
Wertz, A. Studer, Green Chem. 2013, 15, 3116–3134; e) X. Lang, W.
Ma, C. Chen, H. Ji, J. Zhao, Acc. Chem. Res. 2014, 47, 355–363;
f) K. V. N. Esguerra, J.-P. Lumb, Synthesis 2019, 51, 334–358; g) J. Liu,
A. Gudmundsson, J.-E. Backvall, Angew. Chem. Int. Ed. 2021,
DOI: 10.1002/anie.202012707; Angew. Chem. 2021, DOI: 10.1002/
ange.202012707.
This work was supported financially by the Shaanxi University of
Science & Technology and Education Foundation of Shaanxi
Province (No. 18JK0105).
Conflict of Interest
[6] a) G. Urgoitia, A. Maiztegi, R. SanMartin, M. T. Herrero, E. Dominguez,
RSC Adv. 2015, 5, 103210–103217; b) R. D. Patil, B. Fuchs, N. Taha, Y.
Sasson, ChemistrySelect 2016, 1, 3791–3796; c) A. Rezaeifard, A.
Khoshyan, M. Jafarpour, M. Pourtahmasb, RSC Adv. 2017, 7, 15754–
15761; d) B. Chandra, P. De, S. Sen Gupta, Chem. Commun. 2020, 56,
8484–8487.
[7] a) M. Mahyari, M. S. Laeini, A. Shaabani, Chem. Commun. 2014, 50,
7855–7857; b) M. Jafarpour, A. Rezaeifard, V. Yasinzadeh, H. Kargar, RSC
Adv. 2015, 5, 38460–38469; c) M. Jafarpour, F. Feizpour, A. Rezaeifard,
RSC Adv. 2016, 6, 54649–54660; d) S. Li, L. Zhang, S. Jie, Z. Liu, New J.
Chem. 2020, 44, 5404–5409.
[8] a) C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113,
5322–5363; b) M. N. Hopkinson, A. Tlahuext-Aca, F. Glorius, Acc.
Chem. Res. 2016, 49, 2261–2272; c) K. L. Skubi, T. R. Blum, T. P. Yoon,
Chem. Rev. 2016, 116, 10035–10074; d) M. D. Kärkäs, J. A. Porco,
C. R. J. Stephenson, Chem. Rev. 2016, 116, 9683–9747; e) D. Ravelli, S.
Protti, M. Fagnoni, Chem. Rev. 2016, 116, 9850–9913; f) J. Twilton, C.
Le, P. Zhang, M. H. Shaw, R. W. Evans, D. W. C. MacMillan, Nat. Rev.
Chem. 2017, 1, 52–70; g) S. Roslin, L. R. Odell, Eur. J. Org. Chem. 2017,
1993–2007; h) I. K. Sideri, E. Voutyritsa, C. G. Kokotos, Org. Biomol.
Chem. 2018, 16, 4596–4614; i) Q. Xia, J. Dong, H. Song, Q. Wang,
Chem. Eur. J. 2019, 25, 2949–2961; j) L. Marzo, S. K. Pagire, O. Reiser,
B. König, Angew. Chem. Int. Ed. 2018, 57, 10034–10072; Angew. Chem.
2018, 130, 10188–10228; k) T. Rigotti, J. Aleman, Chem. Commun.
2020, 56, 11169–11190; l) R. Cannalire, S. Pelliccia, L. Sancineto, E.
Novellino, G. C. Tron, M. Giustiniano, Chem. Soc. Rev. 2021, 50, 766–
897; m) S. Singh, V. J. Roy, N. Dagar, P. P. Sen, S. R. Roy, Adv. Synth.
Catal. 2021, 363, 937–979.
The authors declare no conflict of interest.
Keywords: aqueous reaction · aromatic ketones · CeCl3 · CÀ H
oxygenation · photocatalysis
[1] a) B. L. Ryland, S. S. Stahl, Angew. Chem. Int. Ed. 2014, 53, 8824–8838;
Angew. Chem. 2014, 126, 8968–8983; b) S. D. McCann, S. S. Stahl, Acc.
Chem. Res. 2015, 48, 1756–1766; c) X. Engelmann, I. Monte-Perez, K. Ray,
Angew. Chem. Int. Ed. 2016, 55, 7632–7649; Angew. Chem. 2016, 128,
7760–7778; d) M. Ravi, M. Ranocchiari, J. A. van Bokhoven, Angew.
Chem. Int. Ed. 2017, 56, 16464–16483; Angew. Chem. 2017, 129, 16684–
16704; e) X. Duan, H. Sun, S. Wang, Acc. Chem. Res. 2018, 51, 678–687;
f) D. Wang, A. B. Weinstein, P. B. White, S. S. Stahl, Chem. Rev. 2018, 118,
2636–2679; g) P. Pal, S. Saravanamurugan, ChemSusChem 2019, 12,
145–163; h) J. C. Vedrine, ChemSusChem 2019, 12, 577–588; i) H. Sterckx,
B. Morel, B. U. W. Maes, Angew. Chem. Int. Ed. 2019, 58, 7946–7970;
Angew. Chem. 2019, 131, 8028–8055; j) M. Hu, W. Wu, H. Jiang,
ChemSusChem 2019, 12, 2911–2935; k) K. Yamamoto, M. Kuriyama, O.
Onomura, Acc. Chem. Res. 2020, 53, 105–120.
[2] a) M. Zhou, R. H. Crabtree, Chem. Soc. Rev. 2011, 40, 1875–1884; b) T.
Newhouse, P. S. Baran, Angew. Chem. Int. Ed. 2011, 50, 3362–3374;
Angew. Chem. 2011, 123, 3422–3435; c) A. R. Lippert, G. C. V. De Bittner,
C. J. Chang, Acc. Chem. Res. 2011, 44, 793–804; d) J. L. Roizen, M. E.
Harvey, J. Du Bois, Acc. Chem. Res. 2012, 45, 911–922; e) S. Chiba, H.
Chen, Org. Biomol. Chem. 2014, 12, 4051–4060; f) L. Ren, S. Gao, Chinese
J. Org. Chem. 2017, 37, 1338–1351; g) D. Vidal, G. Olivo, M. Costas,
Chem. Eur. J. 2018, 24, 5042–5054; h) M. C. White, J. Zhao, J. Am. Chem.
Soc. 2018, 140, 13988–14009; i) G. Urgoitia, R. SanMartin, M. T. Herrero,
E. Dominguez, Catalysis 2018, 8, 640–660; j) F. Yang, H. Zhang, X. Liu, B.
Wang, A. Lutz, Chin. J. Org. Chem. 2019, 39, 59–73; k) F. Kakiuchi, T.
Kochi, Chem. Lett. 2020, 49, 1256–1269.
[3] a) J. R. DoAmaral, E. J. Jr. Blanz, F. A. French, J. Med. Chem. 1969, 12, 21–
25; b) J. R. DoAmaral, F. A. French, E. J. Blanz, Jr., D. A. French, J. Med.
Chem. 1971, 14, 862–866; c) Y. Nishizuka, Nature 1988, 334, 661–665;
d) X.-Q. Ding, E. Lindstrom, R. Hakanson, Pharmacol. Toxicol. 1997, 81,
232–237; e) P. J. Masson, D. Coup, J. Millet, N. L. Brown, J. Biol. Chem.
1994, 270, 2662–2668; f) T. Ukita, Y. Nakamura, A. Kubo, Y. Yamamoto,
Y. Moritani, K. Saruta, T. Higashijima, J. Kotera, M. Takagi, K. Kikkawa, K.
Omori, J. Med. Chem. 2001, 44, 2204–2218; g) H. Surburg, J. Panten,
Common Fragrance and Flavor Materials, Wiley, Weinheim, Germany,
2006; h) Y. Deng, Y.-W. Chin, H. Chai, W. J. Keller, A. D. Kinghorn, J. Nat.
Prod. 2007, 70, 2049–2052; i) M. Fukuda, R. Sekiya, R. Kuroda, Angew.
Chem. Int. Ed. 2008, 47, 706–710; Angew. Chem. 2008, 120, 718–722;
j) H.-B. Yang, K. Ghosh, Y. Zhao, B. H. Northrop, M. M. Lyndon, D. C.
Muddiman, H. S. White, P. J. Stang, J. Am. Chem. Soc. 2008, 130, 839–
841; k) H. Kim, S. M. So, C. P.-H. Yen, E. Vinhato, A. J. Lough, J.-I. Hong,
H.-J. Kim, J. Chin, Angew. Chem. Int. Ed. 2008, 47, 8657–8660; Angew.
Chem. 2008, 120, 8785–8788; l) K. Albrecht, K. Yamamoto, J. Am. Chem.
Soc. 2009, 131, 2244–2251; m) S. K. Vooturi, C. M. Cheung, M. J. Rybak,
S. M. Firestine, J. Med. Chem. 2009, 52, 5020–5031; n) J. R. Luque-Ortega,
P. Reuther, L. Rivas, C. Dardonville, J. Med. Chem. 2010, 53, 1788–1798.
[4] a) Y. Xu, Z. Yang, J. Hu, J. Yan, Synthesis 2013, 45, 370–374; b) Y.
Zhou, J. Long, Y. Li, Chin. J. Catal. 2016, 37, 955–962; c) M. M. Hossain,
S. G. Shyu, Tetrahedron 2016, 72, 4252–4257; d) D. Tu, Y. Li, J. Li, Y.
Gu, B. Wang, Z. Liu, Z. Liu, J. Lu, Catal. Commun. 2017, 97, 130–133;
[9] a) M. Hosseini-Sarvari, Z. Akrami, J. Organomet. Chem. 2020, 928,
121549–121560; b) M. Hosseini-Sarvari, A. Dehghani, New J. Chem. 2020,
44, 16776–16785.
[10] S. Li, B. Zhu, R. Lee, B. Qiao, Z. Jiang, Org. Chem. Front. 2018, 5, 380–385.
[11] X. Zhu, Y. Liu, C. Liu, H. Yang, H. Fu, Green Chem. 2020, 22, 4357–4363.
[12] a) B. Wang, H.-X. Sun, B. Chen, Z. Sun, Green Chem. 2009, 11, 1112–
1114; b) B.-L. Su, Q. Zhang, D. Bonifazi, J. Li, ChemSusChem 2011, 4,
1327–1331; c) R. Luque, S. Obare, ChemSusChem 2015, 8, 1632–1633;
d) A. M. Rather, N. Jana, S. Begum, H. K. Srivastava, U. Manna, Green
Chem. 2017, 19, 4527–4532; e) J.-F. Qin, B. Wang, G.-Q. Lin, Green Chem.
2019, 21, 4656–4661; f) E. A. Saverina, V. Sivasankaran, R. R. Kapaev, A. S.
Galushko, V. P. Ananikov, M. P. Egorov, V. V. Jouikov, P. A. Troshin, M. A.
Syroeshkin, Green Chem. 2020, 22, 359–367.
[13] G. B. Haxel, J. B. Hedrick, G. J. Orris, Rare Earth Elements-Critical Resources
for High Technology, U. S. Geological Survey, 2002.
[14] a) H. Yin, P. J. Carroll, J. M. Anna, E. J. Schelter, J. Am. Chem. Soc. 2015,
137, 9234–9237; b) H. Yin, P. J. Carroll, B. C. Manor, J. M. Anna, E. J.
Schelter, J. Am. Chem. Soc. 2016, 138, 5984–5993; c) H. Yin, Y. Jin, J. E.
Hertzog, Mullane, K. C. Carroll, P. J. Manor, B. C. Anna, J. M. E. J. Schelter,
J. Am. Chem. Soc. 2016, 138, 16266–16273; d) Y. Qiao, Q. Yang, E. J.
Schelter, Angew. Chem. Int. Ed. 2018, 57, 10999–11003; Angew. Chem.
2018, 130, 11165–11169; e) Y. Qiao, E. J. Schelter, Acc. Chem. Res. 2018,
51, 2926–2936; f) Y. Chen, X. Ji, B. Paul, S. Vadivel, Mater. Lett. 2019, 237,
113–117; g) J. Schwarz, B. König, Chem. Commun. 2019, 55, 486–488;
h) Y. Qiao, T. Cheisson, B. C. Manor, P. J. Carroll, E. J. Schelter, Chem.
Commun. 2019, 55, 4067–4070; i) K. Wadekar, S. Aswale, V. R. Yatham,
Org. Biomol. Chem. 2020, 18, 983–987.
[15] a) J.-J. Guo, A. Hu, Y. Chen, J. Sun, H. Tang, Z. Zuo, Angew. Chem. Int. Ed.
2016, 55, 15319–15322; Angew. Chem. 2016, 128, 15545–15548; b) A.
Hu, J.-J. Guo, H. Pan, Z. Zuo, Science 2018, 361, 668–672; c) A. Hu, J.-J.
Guo, H. Pan, H. Tang, Z. Gao, Z. Zuo, J. Am. Chem. Soc. 2018, 140, 1612–
ChemSusChem 2021, 14, 1–6
www.chemsuschem.org
4
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

Communications
doi.org/10.1002/cssc.202100682
ChemSusChem
1616; d) Y. Chen, J. Du, Z. Zuo, Chem 2020, 6, 266–279; e) Q. An, Z.
Wang, Y. Chen, X. Wang, K. Zhang, H. Pan, W. Liu, Z. Zuo, J. Am. Chem.
[18] a) X. Cheng, X. Hu, Z. Lu, Chin. J. Org. Chem. 2017, 37, 251–266; b) X.
Zhang, K. P. Rakesh, L. Ravindar, H.-L. Qin, Green Chem. 2018, 20, 4790–
4833.
Soc. 2020, 142, 6216–6226.
[16] a) W. Huang, B.-C. Ma, H. Lu, R. Li, L. Wang, K. Landfester, K. A. I. Zhang,
ACS Catal. 2017, 7, 5438–5442; b) J. Kollmann, Y. Zhang, W. Schilling, T.
Zhang, D. Riemer, S. Das, Green Chem. 2019, 21, 1916–1920; c) W.
Schilling, Y. Zhang, D. Riemer, S. Das, Chem. Eur. J. 2020, 26, 390–395.
[17] a) Y. Zhang, W. Schilling, D. Rieme, S. Das, Nat. Protoc. 2019, 15, 822–
839; b) Y. Zhang, W. Schilling, S. Das, ChemSusChem 2019, 12, 2898–
2910.
Manuscript received: April 1, 2021
Revised manuscript received: April 20, 2021
Accepted manuscript online: April 20, 2021
Version of record online: ■■■, ■■■■
ChemSusChem 2021, 14, 1–6
www.chemsuschem.org
5
© 2021 Wiley-VCH GmbH
��
These are not the final page numbers!

COMMUNICATIONS
Prof. P. Xie*, C. Xue, S. Shi, D. Du
1 – 6
Visible-Light-Driven Selective Air-
Oxygenation of CÀ H Bond via
CeCl3 Catalysis in Water
Mild conditions: A mild and efficient
aqueous photocatalytic strategy is es-
tablished for the synthesis of aromatic
ketones via CeCl3-catalyzed selective
air-oxygenation of CÀ H bonds. With
air as the oxidant and water as the
solvent, this methodology demon-
strates good economy, high efficiency,
and environmental friendliness.