Oxidative alkylation of alkenes with carbonyl compounds through concomitant 1,2-aryl migration by photoredox catalysis

Article abstract of DOI:10.1039/d0nj03733h

Visible-light-enabled oxidative radical 1,2-alkylarylation of α-aryl allylic alcohols with carbonyl compounds has been established under mild conditions. An efficient and convenient protocol for the construction of a variety of 1,5-dicarbonyl compounds wa

Full text of DOI:10.1039/d0nj03733h

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: S. Cai, Z. Lin, M.
Lu, B. Liu, J. Gao, M. Huang and Z. Gan, New J. Chem., 2020, DOI: 10.1039/D0NJ03733H.
Volume 42
This is an Accepted Manuscript, which has been through the
Number
6
21 March 2018
Pages 3963-4776
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry
rsc.li/njc
A journal for new directions in chemistry
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 1144-2546
PAPER
Chechia Hu, Tzu-Jen Lin et al.
Yellowish and blue luminescent graphene oxide quantum dots
prepared via a microwave-assisted hydrothermal route using
H2O2 and KMnO4 as oxidizing agents
rsc.li/njc

Please do not adjust margins
Page 1 of 6
New Journal of Chemistry
1
2
3
4
5
6
7
8
9
View Article Online
DOI: 10.1039/D0NJ03733H
Journal Name
COMMUNICATION
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Oxidative alkylation of alkenes with carbonyl compounds through
concomitant 1,2-aryl migration by photoredox catalysis †
Received 00th January 20xx,
Accepted 00th January 20xx
Zhaowei Lin,a Maojian Lu,a Boyi Liu,a Jing Gao,a Mingqiang Huang,a Zhenhong Gan,a and
Shunyou Cai*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Visible-light-enabled oxidative radical 1,2-alkylarylation of α- method,8 which suffers from some limitations such as the need
aryl allylic alcohols with carbonyl compounds has been for preactivated reaction partners, narrow substrate scopes,
established under mild conditions. An efficient and and harsh reaction conditions. Some synthetic strategies for
convenient protocol for constructions of a variety of 1,5- the construction of 1,5-dicarbonyl compounds involving C-H
dicarbonyl compounds was realized in the presence of bond functionalizations have been continuously developed to
organic fluorophores 4CzIPN, hypervalent iodine(III) reagent, respond these challenges.
and visible light irradiation. An obvious kinetic isotope effect
was noticed, which helped gain insight into the mechanistic
course.
It is highly desirable in organic chemistry to design and
develop convenient, selective, efficient, and environmentally
benign synthetic methods. Within this context, considerable
catalytic processes, especially visible-light-promoted photo-
catalyzed processes,1,2 have been established and played
Scheme 1. Approaches to 1,5-diketone synthesis
significant roles in the preparations of biologically active
In 2015, Li and co-workers disclosed a practical method to
molecules and natural products.3 Recently, direct access 1,5-diketones through an alkylation/1,2-aryl migration
functionalization of the inert C-H bond has emerged as a of α-aryl allylic alcohols with α-carbonyl alkyl bromides by
cutting-edge research topic, because it meets not only the means of visible-light-enabled photoredox catalysis (Scheme
affording of a concise route to formations of diverse C-C or C- 1a).9a An alternative method to these substances is the
heteroatom bonds but also the green and efficient peroxide-promoted alkylarylation of α,α-diaryl allylic alcohols
requirement of organic transformations.4
and carbonyl compounds through direct C-H bond
As a highly versatile class of substances, 1,5-dicarbonyl functionalization (Scheme 1b).9b However, these two
compounds are known to serve as valuable structural motifs established systems require large excess amounts of
for numerous biologically natural products, such as alkaloids, potentially explosive peroxide, metal salt, or preactivation of
steroids, and terpenoids.5 Furthermore, they are also widely ketones by halogenations, under medium-to-high reaction
employed to serve as useful precursors to access various temperatures, which are not the safe and step-economical
heterocycles.6 As a result, great synthetic efforts have been processes. Therefore, developing more convenient, safe, and
made to develop efficient methods enabling their reliable and practical methods for 1,5-diketone synthesis still strongly
convenient syntheses.7 Traditionally, the conjugate addition of attract considerable attentions from the synthetic community
.
enolates to vinyl ketones is the most frequently utilized
With particular research interest in free-radical-triggered
direct C-H bond functionalization,10 we disclose herein our
recent accomplishment in visible-light-promoted
photocatalytic radical alkylarylation of allylic alcohols,
providing a new approach for the convenient assembly of 1,5-
diketones. As illustrated in Scheme 2, a diaryliodonium salt11
carrying a strong electron-donating aromatic group appears to
aKey Laboratory of Modern Analytical Science and Separation Technology of Fujian
Province, School of Chemistry, Chemical Engineering and Environment, Minnan
Normal University, Zhangzhou, 363000, China. E-mail: caishy05@mnnu.edu.cn
bKey Laboratory of Chemical Genomics of Guangdong Province, School of Chemical
Biology and Biotechnology, Shenzhen Graduate School, Peking University,
Shenzhen, 518055, China.
†
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 2 of 6
COMMUNICATION
Journal Name
Thus, some of other similar additives (entries 3-5), including
1
2
3
4
View Article Online
), 1,3-dimethDoOxyI:b1e0.n10ze39n/eD0N( J03733H
B C), and
1,3,5-trimethylbenzene (
anisole ( ), were explored next, but all resulted in either a
D
5
lower product yield or complete inhibition in reactivities.
Gratifyingly, a good yield of anticipated product 2a was
observed through simply increasing the amount of PIFA and
1,3,5-trimethoxybenzene to 2.2 equiv (78%, entry 6). The
choice of a hypervalent iodine(III) compound was confirmed to
be critical, as the employment of PhI(OAc)2 (PIDA),
hydroxybenziodoxole (BI-OH), or acetoxybenziodoxole (BI-OAc)
led to a negative influence on the reaction efficiency (entries
7-10). Furthermore, subsequent optimizations on the reaction
demonstrated that acetone should be the optimal solvent,
because introduction of other solvents only resulted in lower
yields of 2a (entries 11 and 12). Other frequently-used
photosensitizers, such as eosin Y, rose bengal, and
Ir[dF(CF3)ppy]2(dtbpy)PF6, were also revealed to be
disadvantageous for the product yield under otherwise
identical conditions (entries 13-15). Finally, complete inhibition
of the reactivity was observed when the reaction was
conducted in the absence of visible light, an oxidant, or a
photocatalyst (entries 16-18).
6
7
8
9
Scheme 2. Visible-light-enabled diaryliodonium salt induced C-
H Functionalization
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
be ideally used as a reliable and safe single-electron oxidant,
since it is able to easily produce the relatively stable iodanyl
radical through single electron transfer (SET) process under the
synergistic interactions of visible light irradiation and
photocatalyst at room temperature. Subsequently, the in-situ
generated iodanyl radical can react with the ketones via H-
abstraction to generate the α-carbonyl alkyl radical species,12
which would undergo a sequence of radical addition, 1,2-aryl
migration, and oxidation to furnish the 1,5-diketone products.
Table 1. Screenings of the optimal reaction conditions
Scheme 3. Reactivity screenings on symmetrical allylic alcohols
This method could be readily extended to a range of other
With α,α-diphenyl allylic alcohol 1a as the model substrate,
we started to screen the reaction conditions using 1,2,3,5-
tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN)13 as the
photocatalyst under visible light irradiation (Table 1).
Fortunately, The desired 1,5-diketone 2a was produced in 54%
yield when the reaction was carried out in acetone in the
presence of a substoichiometric amount of diaryliodonium salt,
generated in situ from the reaction of PhI(OCOCF3)2 (PIFA) with
symmetrical α,α-diaryl allylic alcohols
1 under above-defined
optimal conditions, and the results were illustrated in Scheme
3. The substrates carrying a para- or meta-alkyl substituent on
the aromatic ring proceeded successfully to afford the
expected products 2b-2d in good yields. Interesting, reaction
decomposition was observed when the electron-rich 1,1-bis(4-
methoxyphenyl)prop-2-en-1-ol 1e was employed as the
substrate. Some of the versatile functional groups, such as
1,3,5-trimethoxybenzene
(A), under a nitrogen balloon
trifluoromethyl (2f), bromo (2g), chloro (2h), and fluoro (2i
)
atmosphere at room temperature (entry 1). As a comparison,
selective removal of the additive 1,3,5-trimethoxybenzene
from the reaction system only resulted in decomposition
(entry 2), suggesting that the in-situ generated diaryliodonium
salt should be a feasible oxidant fitting this transformation.
were shown to be well accommodated in the reactions. It is
noteworthy that, compared with the previous reaction
systems,9 this technology was able to expediently prepare the
products 2j
-
2l, which contained a quaternary carbon center.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 6
New Journal of Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
1
2
3
4
5
6
7
8
9
O
O
View Article Online
DOI: 10.1039/D0NJ03733H
R3
4CzIPN (2 mol %), PIFA (2.2 equiv)
1,3,5-trimethoxybenzene (2.2 equiv)
HO
Me
R1
R3
R1
R2
O
acetone, rt, N2, 8-10 h, blue LEDs
3
4
R2
O
O
O
O
O
Me
Me
Me
Me
Me
H
H
H
Me
Ph
4a: 60% (1.6:1)
4b: 63% (2.3:1)
4c: 88%
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
O
O
O
O
O
O
Me
Me
Me
R3
H
Scheme 5. Illustrative synthetic transformations
H
MeO
CF3
R2
4g: 92%; R2 = CN
4h: 61%; R2 = CO2Me
Finally, it is worth noting that with a switch to utilization of
acetonitrile as the solvent under otherwise identical reaction
conditions, the allylic alcohol 1a could also be smoothly converted
into the anticipated cyano substituted ketone product 8, which was
able to further undergo hydrolysis to deliver ester 9 under acidic
condition. Furthermore, the 1,5-diketones, prepared by this new
method, are capable of participating in further structural
manipulations (Scheme 5). For example, the diketone 2i could be
readily converted to cyclohexenone 10 in 78% yield through an
intramolecular aldol condensation. When the diketone 2a was
treated with NH4OAc/AcOH, multisubstituted pyridine 11 could also
be conveniently obtained in 62% yield.
4e: 77%; R3 = H
4f: 80%; R3 = Me
4d: 82%
O
O
O
O
O
O
Me
Me
Me
H
H
H
Cl
MeO
Cl
R2
F
4k: 75% (1.2:1)
4l: 86% (2.0:1)
4i: 72% (5.1:1); R2 = F
4j: 87% (8.2:1); R2 = Cl
O
O
O
O
O
O
Br
Cl
F
Me
Me
Me
Me
H
H
H
F
Cl
Cl
Cl
4o: 77%
4m: 56%
4n: 91%
O
O
O
O
F
O
F
O
OMe
Me
Me
Me
H
H
H
Cl
F
Cl
O
4p: 84%
4q: 52% (1.1:1)
4r: 67%
O
O
O
O
Me
O
Cl
Me
Me
H
H
H
Cl
Cl
4s: 71%
4t: 80% (3.4:1)
4u: 82%
O
O
O
O
O
O
Me
Me
Me
H
H
S
H
F
S
4v: 79%
4w: 70%
4x: 82%
Scheme 4. Substrate scope of unsymmetrical allylic alcohols
As exemplified in Scheme 4, a range of unsymmetrical allylic
alcohols was also be able to efficiently undergo this
alkylation/1,2-aryl migration process, thus furnishing the
corresponding products . Generally, the substrates containing
an electron-donating substituent or electron-withdrawing
substituent on the aryl ring all effectively provided the
anticipated products in moderate-to-good isolated yield (56-
92%) under the optimal conditions. These collected results
showed that the electronic characteristics of the allylic alcohol
aromatic rings substituents had a crucial effect on the rate of
migration, where the electron-poor aryl group was revealed to
migrate in preference to the electron-rich aryl group. Thus, in
conjunction with previous literature,9 we envisioned that this
migration should be a radical pathway. Furthermore, we also
Scheme 6. Experiments for mechanistic study
Several control experiments were subsequently performed
to shed light on the potential reaction pathways (Scheme 6).
Treatment of 1,3,5-trimethoxybenzene with PhI(OCOCF3)2
easily accomplished the desired ligand transfer process,
3
4
furnishing the diaryliodonium salt 13
, which could be
converted to 2-iodo-1,3,5-trimethoxybenzene 14 under the
synergistic actions of photocatalyst 4CzIPN and visible light
stimulation. Furthermore, direct employing diaryliodonium salt
13 as the oxidant, the diketone 2a could be assembled in a
slightly lower yield under otherwise identical reaction
conditions. The addition of a frequently-used radical scavenger
2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) resulted in
complete inhibition of the anticipated reactivity, pointing out
that the free radicals might be involved in this reaction. The
cleavage of the C-H bond might constitute a rate-determining
found that, in the cases of 3m-3t, migration of the 4-
substitued aryl ring was obvious faster than that of the 2-
substituted aryl rings. Notably, the alcohols possessing either
an alkyl- (3u or 3v) or a thienyl- (3w or 3x) substituent were
disclosed to be successful in the migration.
step, since a significant kinetic isotope effect (K
H
/KD = 5.6) was
noticed in this transformation. Finally, the experiments of on–
off switching of the light source revealed that continuous
irradiation of visible light is necessary to obtain a good yield.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 4 of 6
COMMUNICATION
Journal Name
1
2
3
4
5
6
7
8
9
2
(a) S. Y. Cai, Y. Tian, J. Zhang, Z. Liu, M. Lu, W. Weng and M.
View Article Online
Huang, Adv. Synth. Catal., 2018, 360D, O4I0: 8104.;10(3b9)/DY0.NJJia0n37,3M3H.
Chen, B. Huang, W. Jia, C. Yang and W. Xia, Org. Lett., 2018,
20, 5370; (c) H.-P. Deng, X.-Z. Fan, Z.-H. Chen, Q.-H. Xu and J.
Wu, J. Am. Chem. Soc., 2017, 139, 13579; (d) C. Le, Y. Liang, R.
W. Evans, X. Li and D. W. C. MacMillan, Nature, 2017, 547, 79;
(e) L. Marzo, I. Ghosh, F. Esteban and B. König, ACS Catal.
2016,
Tao and T. Murafuji, Angew. Chem. Int. Ed., 2016, 55, 9695;
(g) B. J. Shields and A. G. Doyle, J. Am. Chem. Soc., 2016, 138
12719; (h) M. S. Oderinde, M. Frenette, D. W. Robbins, B.
Aquila and J. W. Johannes, J. Am. Chem. Soc., 2016, 138
6, 6780; (f) S. Kamijo, G. Takao, K. Kamijo, M. Hirota, K.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
,
,
Scheme 7. Plausible reaction mechanism
1760; (i) W. L. Czaplyski, C. G. Na and E. J. Alexanian, J. Am.
Chem. Soc., 2016, 138, 13854; (j) D. Ravelli, S. Protti and M.
Fagnoni, Acc. Chem. Res., 2016, 49, 2232; (k) V. P. Ananikov,
The observed reactivities, with the addition of the above
investigations, point to a plausible reaction pathway outlined
in Scheme 7. Initially, the diaryliodonium salt 13, generated in
situ from the PhI(OCOCF3)2 and 1,3,5-trimethoxybenzene,
could readily react with the excited 4CzIPN, thus converting to
ACS Catal., 2015, 5, 1964; (l) M. Louillat-Habermeyer, R. Jin
and F. Patureau, W. Angew. Chem., Int. Ed., 2015, 54, 4102;
(m) S. J. Hwang, D. C. Powers, A. G. Maher, B. L. Anderson, R.
G. Hadt, S. L. Zheng, S. Chen and D. G. Nocera, J. Am. Chem.
Soc., 2015, 137, 6472; (n) H. Jiang, X. An, K. Tong, T. Zheng, Y.
Zhang and S. Yu, Angew. Chem., Int. Ed., 2015, 54, 4055; (o) J.
Davies, S. G. Booth, S. Essafi, R. A. W. Dryfe and D. Leonori,
Angew. Chem., Int. Ed., 2015, 127, 14223; (p) X. Hu, J. Chen
and W. Xiao, Angew. Chem., Int. Ed., 2017, 56, 1960.
the key stable iodanyl radical species E. Then, an event of
iodanyl-radical-enabled C-H bond abstraction would be
triggered on acetone to generate α-carbonyl alkyl radical as
well as the 2-iodo-1,3,5-trimethoxybenzene 14. Subsequently,
the newly generated α-carbonyl alkyl radical could participate
in the radical addition to the C=C double bonds of allylic
3
4
(a) C. Sun, B. Li and Z. Shi, Chem. Rev., 2011, 111, 1293; (b) L.
Ackermann, R. Vicente and A. R. Kapdi, Angew. Chem., Int.
Ed., 2009, 48, 9792; (c) C. Liu, H. Zhang, W. Shi and A. Lei,
Chem. Rev., 2011, 111, 1780.
alcohols to furnish the intermediate
events that involved 1,2-aryl migration,14 oxidation, and
deprotonation would take place on the intermediate
resulting in the formation of final 1,5-diketone, 2a
F. Finally, a sequence of
(a) T. W. Lyons and M. S. Sanford, Chem. Rev., 2010, 110
,
F
,
1147; (b) C.-J. Li, Acc. Chem. Res., 2009, 42, 335; (c) R. G.
Bergman, Nature, 2007, 446, 391; (d) K. Godula and D.
Sames, Science, 2006, 312, 67; (e) C. S. Yeung and V. M. Dong,
Chem. Rev., 2011, 111, 1215.
.
In summary, we develop a reliable and practical method for
synthesis of 1,5-diketones directly from readily available
acetone and α-aryl allylic alcohols through the strategy of C-H
bond functionalization by means of photoredox catalysis. It
merits attention that the established method, compared with
the previous protocols, refrains from employing potentially
explosive peroxide and operates efficiently at room
temperature without prefunctionalization. Given the broadly
appreciated significance of 1,5-diketone substances in
chemical and biological contexts, it is envisioned these
discoveries would find applications and motivate further
studies in due course.
5
(a) R. B. Mitra and G. B. Reddy, Synthesis, 1989, 694; (b) M. E.
Jung, Tetrahedron, 1976, 32, 3; (c) R. E. Gawley, Synthesis,
1976, 777; (d) S. Ramachandran and M. S. Newman, Org.
Synth., 1973, 5, 486.
6
7
(a) W. M. Owton, P. T. Gallagher and M. Brunavs, Synth.
Commun., 1992, 22, 351; (b) C. Seoane, J. L. Soto and M.
Quintéro, Heterocycles, 1980, 14, 337.
(a) J.-H. Fan, W.-T. Wei, M.-B. Zhou, R.-J. Song and J.-H. Li,
Angew. Chem., Int. Ed., 2014, 53, 6650; (b) L. Debien and S. Z.
Zard, J. Am. Chem. Soc., 2013, 135, 3808; (c) K. K. Goh, S. Kim
and S. Z. Zard, Org. Lett., 2013, 15, 4818; (d) T. Nishikata, Y.
Noda, R. Fujimoto and T. Sakashita, J. Am. Chem. Soc., 2013,
135, 16372; (e) C. Liu, S. Tang, D. Liu, J. Yuan, L. Zheng, L.
Meng and A. Lei, Angew. Chem., Int. Ed., 2012, 51, 3638; (f)
H. Jiang, Y. Cheng, R. Wang, M. Zheng, Y. Zhang and S. Yu,
Angew. Chem., Int. Ed., 2013, 52, 13289.
Acknowledgements
The work is supported by the National Natural Science
Foundation of China (No. 21502086 and No. 41575118),
Natural Science Foundation of Fujian Province (No.
2019J01744), Outstanding Youth Science Foundation of Fujian
Province (No. 2015J06009), and Program for Excellent Talents
of Fujian Province.
8
9
(a) W. S. Rapson and R. Robinson, J. Chem. Soc., 1935, 1285;
(b) O. Wichterle, J. Procházka and J. Hofman, Coll. Czech.
Chem. Commun., 1948, 13, 300.
(a) Y. Li, B. Liu, X. Ouyang,; R.-J. Song and J.-H. Li, Org. Chem.
Front. 2015, 2, 1457; (b) X. Chu, H. Meng, Y. Zi, X. Xu and S.-J.
Ji, Chem. Eur. J., 2014, 20, 17198.
10 (a) T. L. Yang, M. Lu, Z. Lin, M. Huang and S. Y. Cai, Org.
Biomol. Chem., 2019, 17, 449; (b) M. Lu, Z. Lin, S. Chen, H.
Chen, M. Huang, and S. Y. Cai, Org. Lett., 2019, 21, 9929; (c)
M. Lu, H. Qin, Z. Lin, H. Huang, W. Weng and S. Y. Cai, Org.
Lett., 2018, 20, 7611; (d) S. Y. Cai, Y. Xu, D. Chen, L. Li, Q.
Chen, M. Huang, W. Weng, Org. Lett., 2016, 18, 2990; (e) S. Y.
Cai, X. Y. Zhao, X. B. Wang, Q. S. Liu, Z. G. Li and D. Z. Wang,
Angew. Chem., Int. Ed., 2012, 51, 8050.
11 For selected reviews on hypervalent iodine chemistry: (a) X.
Wang and A. Studer, Acc. Chem. Res., 2017, 50, 1712; (b) A.
Yoshimura and V. V. Zhdankin, Chem. Rev., 2016, 116, 3328;
(c) Y. Li, P. Hari, M. V. Vita and J. Waser, Angew. Chem., Int.
Ed., 2016, 55, 4436.
Notes and references
1
For selected reviews on photo-redox catalysis, see: (a) J. K.
Matsui, S. B. Lang, D. R. Heitz and G. A. Molander, ACS Catal.,
2017, 7, 2563; (b) N. A. Romero and D. A. Nicewicz, Chem.
Rev., 2016, 116, 10075; (c) M. D. Karkas, J. A. Jr. Porco, C. R. J.
Stephenson, Chem. Rev., 2016, 116, 9683; (d) J. Xuan, Z.-G.
Zhang and W.-J. Xiao, Angew. Chem., Int. Ed., 2015, 54
15632; (e) D. M. Schultz and T. P. Yoon, Science, 2014, 343
1239176; (f) C. K. Prier, D. A. Rankic and D. W. C. MacMillan,
Chem. Rev., 2013, 113, 5322; (g) X. Yu, Q. Zhao, J. Chen, W.
Xiao and J. Chen, Acc. Chem. Res., 2020, 53, 1066.
,
,
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 6
New Journal of Chemistry
Please do not adjust margins
Journal Name
12 (a) Shang, T.; Lu, L.; Cao, Z.; Liu, Y.; He, W. and Yu, B. Chem.
COMMUNICATION
1
2
3
4
5
6
7
8
View Article Online
DOI: 10.1039/D0NJ03733H
Commun., 2019, 55, 5408; (b) W.-T. Wei, M.-B. Zhou, J.-H.
Fan, W. Liu, R.-J. Song, Y. Liu, M. Hu, P. Xie and J.-H. Li,
Angew. Chem., Int. Ed., 2013, 52, 3638; (c) Y. Li, B. Liu, H. Li,
Q. Wang and J.-H. Li, Chem. Commun., 2015, 51, 1024; (d) Y.-
Y. Liu, X.-H. Yang, R.-J. Song, S. Luo and J.-H. Li, Nat.
Commun., 2017, 8, 14720; (e) A. Bunescu, T. M. Ha, Q. Wang
and J. Zhu, Angew. Chem., Int. Ed., 2017, 56, 10555; (f) X.
Ouyang, M. Hu, R. Song and J.-H. Li, Chem. Commun., 2018,
54, 12345; (g) W.-Z. Weng and B. Zhang, Chem. Eur. J., 2018,
24, 10934.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
13 (a) H. Uoyama, K. Goushi, K. Shizu, H. Nomura and C. Adachi,
Nature, 2012, 492, 234; (b) J. Luo and J. Zhang, ACS Catal.,
2016, 6, 873; (c) R. Zhou, Y. Goh, H. Liu, H. Tao, L. Li and J.
Wu, Angew. Chem., Int. Ed., 2017, 56, 16621; (d) S. B. Lang, R.
J. Wiles, C. B. Kelly and G. A. Molander, Angew. Chem., Int.
Ed., 2017, 56, 15073.
14 For selected examples, see: (a) P. Sivaguru, Z. Wang, G.
Zanoni and X. Bi, Chem. Soc. Rev., 2019, 48, 2615; (b) X. Chu,
H. Meng, Y. Zi, X.-P. Xu and S.-J. Ji, Org. Chem. Front., 2015,
216. (c) Z.-M. Chen, Q.-W. Zhang, Z.-H. Chen, H. Li, Y.-Q. Tu,
F.-M. Zhang and J.-M. Tian, J. Am. Chem. Soc., 2011, 133
2,
,
8818; (d) Q. Yin and S.-L. You, Org. Lett., 2014, 16, 1810; (e) A.
Bunescu, Q. Wang and J. Zhu, Angew. Chem., Int. Ed., 2015,
54, 3132; (f) C. Pan, Q. Ni, Y. Fu and J.-T. Yu, J. Org. Chem.,
2017, 82, 7683; (g) W. Hu, S. Sun and J. Cheng, J. Org. Chem.,
2016, 81, 4399; (h) R.-J. Song, Y.-Q. Tu, D.-Y. Zhu, F.-M. Zhang
and S.-H. Wang, Chem. Commun., 2015, 51, 749; (i) L. Zheng,
H. Huang, C. Yang and W. Xia, Org. Lett., 2015, 17, 1034; (j)
X.-Q. Chu, Y. Zi, H. Meng, X.-P. Xu and S.-J. Ji, Chem.
Commun., 2014, 50, 7642; (k) Q. Wang, Z. Chen, C. Zhou, B.
Xiong, P. Zhang, C. Yang, Y. Liu and Q. Zhou, Tetrahedron
Lett., 2018, 59, 4551; (l) Z. Chen, X. Zhang and Y. Tu, Chem.
Soc. Rev., 2015, 44, 5220.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
New Journal of Chemistry
Page 6 of 6
COMMUNICATION
Journal Name
1
2
3
4
Graphical Abstract
View Article Online
DOI: 10.1039/D0NJ03733H
5
6
7
8
9
visible light
O
O
R3
Cz
Cz
O
OCOCF3
OMe
HO
NC
Cz
CN
I
R4
MeO
+
R2
H2C
H
C
R4
R1
R3
Cz
R1
OMe
R2
Photoredox Catalysis
All carbon quaternary center
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
36 examples
up to 92% yield
C-H bond functionalization
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins