Visible-light-induced tandem radical addition-cyclization of 2-aryl phenyl isocyanides catalysed by recyclable covalent organic frameworks

Article abstract of DOI:10.1039/c9gc00022d

A visible-light-induced tandem radical addition-cyclization sequence via 2-aryl phenyl isocyanides as the starting material and two-dimensional covalent organic frameworks (2D-COFs) as the photocatalyst was developed, delivering multifarious 6-substituted phenanthridines in high yields. Benefitting from the utilization of a heterogeneous photocatalyst, this protocol features easy catalyst separation and excellent recyclability. A negligible loss of the catalytic activity was observed after multiple runs. High practicability of this protocol was further demonstrated by continuous flow experiments.

Full text of DOI:10.1039/c9gc00022d

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: S. Liu, W. Pan, S.
Wu, X. Bu, S. Xin, J. Yu, H. Xu and X. Yang, Green Chem., 2019, DOI: 10.1039/C9GC00022D.
This is an Accepted Manuscript, which has been through the
Volume 18 Number
7 7 April 2016 Pages 1821–2242
Royal Society of Chemistry peer review process and has been
accepted for publication.
Green
Chemistry
Accepted Manuscripts are published online shortly after
Cutting-edge research for a greener sustainable future
www.rsc.org/greenchem
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
author guidelines.
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, outlined
in our author and reviewer resource centre, 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 1463-9262
CRITICAL REVIEW
G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
rsc.li/green-chem

Please do not adjust margins
Page 1 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C9GC00022D
Journal Name
COMMUNICATION
Visible-light-induced tandem radical addition-cyclization of 2-aryl
phenyl isocyanides catalysed by recyclable covalent organic
frameworks
Received 00th January 20xx,
Accepted 00th January 20xx
Shuyang Liu,a Wenna Pan,a Songxiao Wu,a Xiubin Bu,a Shigang Xin,a Jipan Yu, *c Hao Xu*b and
Xiaobo Yang*a
DOI: 10.1039/x0xx00000x
www.rsc.org/
A
visible-light-induced tandem radical addition-cyclization oxidation of arylboronic acids to phenols.6c Very recently, Liu
sequence via 2-aryl phenyl isocyanides as the starting material and reported a visible-light-driven reductive dehalogenation of
two-dimensional covalent organic frameworks (2D-COFs) as the phenacyl bromides and α-alkylation of aldehydes catalysed by
photocatalyst was developed, delivering multifarious 6-substituted photoactive imine-based 2D-COFs.8b These pioneering works
phenanthridines in high yields. Benefited from the utilization of have suggested the great potential catalytic ability of 2D-COFs
heterogeneous photocatalyst, this protocol features easy catalyst in heterogeneous visible-light-induced organic transformations,
separation and excellent recyclability. Negligible loss of the but their applicable organic reaction scope are still limited to
catalytic activity was observed after multiple runs. High visible-light-driven CDC reaction and simple redox reaction.
practicability of this protocol was further demonstrated by Thus, expanding the boundaries of these heterogeneous visible-
continuous flow experiments.
light-induced organic processes with 2D-COFs is highly needed.
The phenanthridine derivatives widely occur in natural
products, pharmaceuticals and materials.9 Consequently, a
Covalent organic frameworks (COFs), which are prepared from
readily available organic units, as a new type of highly ordered
porous organic crystalline materials,1 find
Homogeneous visible-light-induced tandem radical addition-cyclization:
a variety of
R2
R2
(a)
[Ru] or [Ir] complex;
organic dyes
applications such as in catalysis2 and gas storage3 due to their
large surface area and high stabilities. 2D-COFs, possessing
extended π-conjugated frameworks and eclipsed stacking,
provide ideal channels for exciton separation and charge
percolation.4 Therefore, some well-designed 2D-COFs have
proven photoactive and effective in heterogeneous
photocatalytic chemical transformations.5 For example, the
groups of Wang,6a, 6b Wu7 and Liu8a independently showed the
remarkable photocatalytic activity of hydrazone or imine-based
2D-COFs in visible-light-induced cross-dehydrogenative
coupling (CDC) reactions. In 2018, Wang and co-workers
illustrated the excellent photocatalytic performance of
benzoxazole-based COFs in the visible-light-driven aerobic
3
R1
R1
+
R
RP
Visble light
NC
N
R3
R3=Ar, Alkyl, CF3, (O)PAr2 etc.
This work:
R1
R2
R2
(b)
R3
2D-COF-1
3
+
R
RP
R1
Blue LED, rt
NC
N
R3=Ar, Alkyl, CF3, ArS, (O)PAr2
O
O
H
N
N
N
N
H
O
O
N
N
NH
O
O
NH
O
O
O
O
O
HN
N
HN
N
O
2D-COF-1
N
O
NH
aInstitute of Catalysis for Energy and Environment, College of Chemistry & Chemical
Engineering, Shenyang Normal University, Shenyang, Liaoning, 110034, P. R.
China.
N
O
NH
O
O
O
O
HN
N
O
O
bCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng,
475004, P. R. China.
HN
N
O
O
H
N
N
N
N
H
c Laboratory of Nuclear Energy Chemistry, Institute of High Energy Physics, Chinese
Academy of Sciences, Beijing, 100049, China.
O
O
E-mail: bxy1223@gmail.com; yangxb@synu.edu.cn; xuhao@henu.edu.cn;
yujipan@ihep.ac.cn.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Scheme 1 Visible-light-induced tandem radical addition-cyclization of 2-aryl
†
phenyl isocyanides
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
Green Chemistry
Page 2 of 7
COMMUNICATION
Journal Name
wide range of efficient methods have been developed for the Table 1 Visible-light-induced tandem radical addition-cyclization of 2-aryl phenyl
View Article Online
synthesis of these scaffolds in the past decades.10 Among them, isocyanides (1) with hydrazines (2) by using 2D-COF-1 as the photosensitizer
a,b
DOI: 10.1039/C9GC00022D
visible-light-induced tandem radical addition-cyclization of 2-
aryl phenyl isocyanides is the most attractive and facile strategy
R2
2D-COF-1
R2
R3NHNH2
or
because of its high efficiency and green features.11 Numerous
homogeneous photosensitizers including [Ru] or [Ir] complex12
and organic dyes13 have been reported to realize this
photocatalytic transformation successfully (Scheme 1a), but the
drawbacks of homogeneous photocatalysts, for example,
difficult to separate and recycle impairs their practical
applications,14 especially in industrialized synthesis. To address
the above practicability issues and maximize the application
K2CO3, DMSO
air, Blue LED, rt
R1
+
R1
R3NHNH2·HCl
N
R3
R3=Ar, Alkyl
NC
1
2
3
OMe
OMe
R1
N
N
N
potentials
of
2D-COFs
in
photocatalytic
organic
1
3aa
3ba
R =H,
, 77%
3ca
3ab
, 87%
, 64%
transformations, in the continuation of our interests on
photoinduced reactions and construction of N-heterocycles,15
herein, we wish to report a heterogeneous visible-light-induced
tandem radical addition-cyclization process from 2-aryl
phenylisocyanides to synthesize diverse 6-substituted
phenanthridines, in which hydrazone-based two-dimensional
covalent organic frameworks (2D-COF-1) are utilized as the
recyclable and reusable heterogeneous photosensitizers
(Scheme 1b).
1
R =F,
, 76%
OMe
F
R1
N
N
N
1
c
3ac
3bc
R =H,
, 91%
c
c
3cc
3dc
, 91%
, 96%
1
c
R =F,
, 81%
Me
R2
At the outset of our study, the 2D-COF-1 was prepared by the
condensation of 2,5-dimethoxyterephthalohydrazide with
1,3,5-triformylbenzene according to a previously reported
R1
Cl
N
N
N
(a)
2
c
3hc
R =Ph,
, 93%
1
c
3ec
R =F,
, 90%
c
2
c
3gc
3ic
, 89%
, 86%
R =H,
1
c
3fc
R =Me,
, 95%
2
c
3jc
R =Cl,
, 93%
a1 (0.1 mmol), 2 (0.3 mmol), 2D-COF-1 (0.001 mmol, 4 mg), K2CO3 (0.3 mmol), DMSO (1 mL),
5
W
Blue LEDs, under air for 20
h
at room temperature. bIsolated yield. cHydrazine
hydrochlorides were used.
protocol6 (Scheme S1, see details in ESI). Its structure, porosity
and thermostability were confirmed and characterized by FT-IR
spectra, 13C CP/MAS NMR spectra, powder X-ray diffraction,
thermogravimetric analysis, nitrogen adsorption-desorption
experiments and scanning electron microscopy respectively
(Figure S1-S6, Table S1, see details in ESI). The results indicate
that the synthesized 2D-COF-1 possesses high crystallinity and
good thermostability which are the key features of the suitable
heterogeneous catalyst. Subsequently, to verify the feasibility
of the above visible-light-induced organic transformation with
this 2D-COF, the comparison of UV/Vis absorption and redox
potential between 2D-COF-1 and reported homogeneous
photosensitizers16 were conducted (Figure 1, S7, S8), and the
potential photocatalytic activity of this 2D-COF material was
investigated by electrochemical impedance spectroscopy (EIS)
and the photocurrent tests (Figure S9, S10, see details in ESI).
All of these results demonstrate that it is qualified to be an
effective photocatalyst in the tandem radical addition-
cyclization of 2-aryl phenyl isocyanides under blue LED light
irradiation.
(b)
Motivated by the remarkable suitability of 2D-COF-1 in
photocatalytic reactions, we further investigated the
application of 2D-COF-1 as the heterogeneous photosensitizers
for the installation of various radical precursors onto 2-aryl
phenyl isocyanides, delivering a wide range of 6-substituted
phenanthridines.
Figure 1 (a) Normalized UV/Vis absorption spectra of 2D-COF-1 (red line),
-
[Acr+-Mes]ClO4 (blue line), Eosin B (purple line) and Ir[(ppy)2(dtbpy)]PF6
(green line). (b) Redox potentials (in V vs. SCE) of 2D-COF-1 and reported
homogeneous photosensitizers.
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 7
Green Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
OMe
Initially, we chose phenylhydrazine 2a as the phenyl radical
precursor to synthesize 6-aryl phenanthridines under visible-
light irradiation in the presence of 10 mol% 2D-COF-1. To our
delight, after the optimization and adjustments of the reaction
conditions (Table S2, see details in ESI), the desired product 3aa
was obtained in 77% yield. Then we examined the generality of
this photocatalytic transformation by using different 2-aryl
phenyl isocyanides and hydrazines. As shown in the Table 1, all
of the selected 2-aryl phenyl isocyanides participated the
reactions well regardless of the position or type of the
substituted group. Halogenated aryl isocyanides also gave the
corresponding products in high yield, providing a chance for
further derivatization and modification (3ba, 3bc, 3dc, 3ec, 3gc,
3jc). Apart from phenylhydrazines, tert-butyl hydrazine 2c is
also compatible with this reaction, producing the target
molecules in excellent yields (3ac-3jc). Compared with previous
work using the homogeneous photosensitizer, there is no
OMe
View Article Online
2D-COF-1
DTBP, EA
DOI: 10.1039/C9GC00022D
R1
R1
(PhS)2
+
N2, Blue LED, rt
N
SPh
NC
1
6
9
1
a,b
R1=H or F
9a
R =H, , 66%
1
a,b
9b
R =F, , 66%
a1 (0.1 mmol), 6 (0.2 mmol), 2D-COF-1 (0.001 mmol, 4 mg), DTBP (0.2 mmol), EA (1 mL), 5 W Blue LEDs,
under N2 for 24h at room temperature. bIsolated yield.
Scheme 2 Visible-light-induced tandem radical addition-cyclization of 2-aryl
phenyl isocyanides (1) with diphenyl disulfide (6) by using 2D-COF-1 as the
photosensitizer
(a)
OMe
OMe
2D-COF-1
NHNH2·HCl
+
N
NC
1a
2c
3ac
Table 2 Visible-light-induced tandem radical addition-cyclization of 2-aryl phenyl
isocyanides (1) with CF3SO2Na (4) a,c, diphenylphosphine oxide (5)b,c by using 2D-
COF-1 as the photosensitizer
R2
2D-COF-1
K2S2O8, Na2CO3, EA
R1
CF3SO2Na
N2, Blue LED, rt
N
7
CF3
R2
4
+
R1
R2
2D-COF-1
NC
O
K2S2O8, CsF, EA
N2, Blue LED, rt
R1
H
P
Ph
1
O
Ph
N
P
Ph
Ph
5
8
R2
CF3SO2Na:
OMe
F
(b)
OMe
OMe
+
2D-COF-1
N
CF3
N
CF3
N
CF3
(PhS)2
2
7c
R =H, , 77%
N
SPh
7a
7d
, 79%
, 79%
NC
1a
2
7f
R =Me, , 73%
R2
6
9a
1.0g
, 79% ( )
Cl
Scheme 3 (a) Recycling experiments (b) Reactions in continuous flow
N
CF3
N
CF3
N
CF3
obvious diminishing reaction efficiency.5a
2
7j
R =Cl, , 60%
7g
7i
, 73%
, 75%
Next, the scope of this strategy was expanded by installing
trifluoromethyl radical and P-centered radical onto 2-aryl
phenyl isocyanides (Table 2). Under the modified reaction
conditions (Table S3, S4, see details in ESI), CF3SO2Na and
diphenylphosphine oxide were both smoothly converted to the
corresponding radicals respectively under the blue LED light
irradiation with the photocatalyst 2D-COF-1, producing a series
of 6-trifluoromethyl phenanthridines and 6-phosphorylated
phenanthridines in good to excellent yields. The electronic
effect and substituent type are not the key factors of this
reaction. Notably, in the reactions towards the above two types
of phenanthridines, ethyl acetate (EA), as a greener solvent, was
employed instead of environmental-unfriendly DMF, which was
used in previous works.10c More importantly, because of the
excellent porosity and photoactivity of the 2D-COF-1, the
corresponding product yields of these two heterogeneous
photocatalytic transformations are comparable with reported
2
, 7k
R =Me
, 73%
Diphenylphosphine oxide:
OMe
F
O
O
O
N
P
N
P
N
P
Ph
Ph
Ph
Ph
Ph
Ph
8a
8c
8d
, 86%
, 86%
, 87%
Cl
Ph
R1
R1
O
O
O
N
P
N
P
N
P
Ph
Ph
Ph
Ph
Ph
8i
Ph
1
1
8h
R =H, , 73%
R =H, , 87%
8j
, 80%
1
1
8l
8m
, 40%
R =Me, , 66%
R =F,
a1 (0.1 mmol), 4 (0.2 mmol), 2D-COF-1 (0.001 mmol, 4 mg), K2S2O8 (0.2 mmol), Na2CO3 (0.2
mmol), EA (1 mL), 34 W Blue LED, under N2 for 36 h at room temperature. b1 (0.1 mmol), 5
(0.3 mmol), 2D-COF-1 (0.001 mmol, 4 mg), K2S2O8 (0.3 mmol), CsF (0.2 mmol), EA (1 mL), 34
W Blue LED, under N2 for 12 h at room temperature. cIsolated 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
Green Chemistry
Page 4 of 7
COMMUNICATION
Journal Name
homogeneous photocatalysis. In some cases, it is even higher
than previous protocols.
Based on the above experiments, the measurement of the redox
View Article Online
12-13
potential for the 2D-COF-1 and previous DrOepI:o1r0t.s1039/,C9aGpCl0a0u0s2ib2lDe
Sulfur-containing compounds, as an important class of reaction mechanism was proposed as depicted in Scheme 5. Initially,
chemicals, play the key role in the pharmaceutical industry and under the visible-light irradiation, the excited-state 2D-COF-1*
materials science.17 Although a number of excellent methods reduces the oxidant with the formation of radical anion A. It abstracts
for their synthesis have been reported,18 there is still extremely one electron from the radical precursor to generate the key radical
necessary for the development of more practical and B. Then, intermediate I is formed via the intermolecular addition
environmentally benign methods to construct them. Hence, from B and the substrate 1. Subsequently, the intramolecular
diphenyl disulfide was introduced to generate the S-radical with cyclization delivers a cyclohexadienyl-type radical II, which is
the 2D-COF-1 via a visible-light- enabled process. As depicted in oxidized by 2D-COF-1+ to afford the cation intermediate III with the
Scheme 2, two sulfur contained phenylhydrazines were regeneration of the photocatalyst 2D-COF-1. Finally, in the presence
synthesized in moderated yields under the established reaction of base, the deprotonation of intermediate III produces the desired
conditions (Table S5, see details in ESI). To the best of our 6-substituted phenanthridine.
knowledge, the present approach illustrates the first method to
prepare 6-phenylthiophenanthridines via visible-light-induced
tandem radical addition-cyclization, avoiding the high reaction
temperature in the previous report.10f
2D-COF-1*
2D-COF-1
H
Ar
N
R
O
O
O
O
III
As a heterogeneous photosensitizer, the recyclability and
reusability are crucial features in practical process. In this context,
the recycling experiment was performed using 2-isocyano-4'-
methoxy-1,1'-biphenyl (1a) and tert-butyl hydrazine (2c) as the
substrates with 10 mol% 2D-COF-1 under the standard conditions. As
shown in Scheme 3a, it displays almost unchanged reaction efficiency
after six runs. Furthermore, inspired by the pioneer work on
heterogeneous transformations19, the reaction between 2-isocyano-
Ar
2D-COF-1
Ar
Ar
A
N
R
3, 7, 8, 9
H
R
N
II
RP
Ar
Ar
4'-methoxy-1,1'-biphenyl (1a) and diphenyl disulfide
6 was
R
N
I
R
conducted and scaled-up in continuous flow by using a modified
continuous-flow photoreactor (see details in ESI), giving the desired
product 9a in 79% yield (Scheme 3b). All of these experiments
suggest the great potential of 2D-COF-1 as the photocatalyst to
generate radicals with visible light as the driving force.
B
1
Scheme 5 A plausible mechanism
To gain the mechanistic insights of this photoinduced reaction,
several trapping experiments were conducted. As shown in Scheme
4a, in the four model reaction systems, the radical addition-
cyclization reactions were significantly suppressed with the addition
of TEMPO (common radical scavenger), suggesting that a radical
process should be involved. Furthermore, in Scheme 4b, the
apparent quantum efficiency (450 nm) values for the four model
reactions were calculated to be 9.5%, 5.4%, 17.6% and 6.8%
respectively (see details in ESI, part VIII), which indicate that this
radical process should present a closed photoredox cycle without
chain propagation.
Conclusions
Overall, we have described a practical protocol toward the
synthesis of diverse 6-substituted-phenanthridines from 2-aryl
phenyl isocyanides via visible-light-induced tandem radical
addition-cyclization under very mild conditions, in which the
hydrazone-based 2D-COF-1 was employed as the
heterogeneous photosensitizer. The reaction shows good
functional-group compatibility and efficiency. The recycling
experiments and continuous flow experiments suggest that the
use of heterogeneous photosensitizer 2D-COF-1 exhibits
excellent recyclability and practicability. Studies on other
visible-light-induced organic transformations with photoactive
2D-COFs are currently ongoing.
(a) Radical trapping experiments:
"Standard conditions"
3aa
(1)
(trace)
1a
2a
+
TEMPO (3 equiv)
"Standard conditions"
TEMPO (2 equiv)
7a
(0%)
(trace)
(0%)
(2)
(3)
(4)
CF3SO2Na
O
1a
1a
1a
+
+
+
Acknowledgements
"Standard conditions"
TEMPO (3 equiv)
8a
9a
H
PPh2
We acknowledge funding from the National Natural Science
Foundation of China (Grant No. 21402126, 21502042,
21806167), Natural Science Foundation of Liaoning Province
(20180550882), the Program for Creative Talents in University
of Liaoning Province, the Basic Scientific Project of the
Universities in Liaoning Province (LFW201701), the Program for
Young Creative Talents in Shenyang City (RC170189), the
Engineering Technology Research Centre of Catalysis for Energy
and Environment-Major Platform for Science and Technology of
"Standard conditions"
TEMPO (2 equiv)
(PhS)2
(b) The apparent quantum efficiency values:
Model reaction
A. Q. E. (%)
1
2
3
4
9.5
5.4
17.6
6.8
Scheme 4 (a) Radical trapping experiments (b) The apparent quantum
efficiency values
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 7
Green Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
H. Xia, G. Li, X. Feng, X. Chen, Z. Shi and X. Liu, Appl. Catal. B,
the Universities in Liaoning Province. We acknowledge Dr.
Wenbo Liu, Dr. Minghua Bai, Dr. Ling Zhang and Dr. Lijing Zhou
for valuable suggestions and experimental assistance.
View Article Online
2019, 245, 334.
DOI: 10.1039/C9GC00022D
9
(a) T. Nakanishi, M. Suzuki, A. Saimoto and T. Kabasawa, J.
Nat. Prod., 1999, 62, 864; (b) I. Kock, D. Heber, M. Weide, U.
Wolschendorf and B. Clement, J. Med. Chem., 2005, 48, 2772;
(c) N. Stevens, N. O’Connor, H. Vishwasrao, D. Samaroo, E. R.
Kandel, D. L. Akins, C. M. Drain and N. J. Turro, J. Am. Chem.
Soc., 2008, 130, 7182.
Conflicts of interest
There are no conflicts to declare.
10 For selected examples and reviews: (a) D. A. Candito and M.
Lautens, Angew. Chem. Int. Ed., 2009, 48, 6713; (b) M. Tobisu,
K. Koh, T. Furukawa and N. Chatani, Angew. Chem. Int. Ed.,
2012, 51, 11363; (c) B. Zhang, C. G. Daniliuc and A. Studer,
Org. Lett., 2014, 16, 250; (d) J.-J. Cao, T.-H. Zhu, S.-Y. Wang, Z.-
Y. Gu, X. Wang and S.-J. Ji, Chem. Commun., 2014, 50, 6439;
(e) J. Liu, C. Fan, H. Yin, C. Qin, G. Zhang, X. Zhang, H. Yi and A.
Lei, Chem. Commun., 2014, 50, 2145; (f) H. Fang, J. Zhao, P.
Qian, J. Han and Y. Pan, Asian J. Org. Chem., 2014, 3, 1266; (g)
C. Pan, H. Zhang, J. Han, Y. Cheng and C. Zhu, Chem.Commun.,
2015, 51, 3786; (h) B. Zhang and A. Studer, Chem. Soc. Rev.,
2015, 44, 3505; (i) W.-L. Chen, C.-Y. Chen, Y.-F. Chen and J.-C.
Hsieh, Org. Lett., 2015, 17, 1613; (j) X. Tang, S. Song, C. Liu, R.
Zhu and B. Zhang, RSC Adv., 2015, 5, 76363; (k) J. Lei, J. Huang
and Q. Zhu, Org. Biomol. Chem., 2016, 14, 2593; (l) J.-T. Yu and
C. Pan, Chem. Commun., 2016, 52, 2220; (m) H.-B. Zhao, Z.-J.
Liu, J. Song and H.-C. Xu, Angew. Chem. Int. Ed., 2017, 56,
12732; (n) Q. Yao, X. Zhou, X. Zhang, C. Wang, P. Wang and M.
Li, Org. Biomol. Chem., 2017, 15, 957; (o) J. Li, C. A. D. Caiuby,
M. W. Paixão and C.-J. Li, Eur. J. Org. Chem., 2018, 20-21, 2498.
11 (a) M. H. Shaw, J. Twilton and D. W. C. MacMillan, J. Org.
Chem., 2016, 81, 6898; (b) N. A. Romero and D. A. Nicewicz,
Chem. Rev., 2016, 116, 10075; (c) Q. Liu and L.-Z. Wu, Natl. Sci.
Rev., 2017, 4, 359; (d) C. Michelin and N. Hoffmann, ACS Catal.,
2018, 8, 12046; (e) I. K. Sideri, E. Voutyritsa and C. G. Kokotos,
Org. Biomol. Chem., 2018, 16, 4596.
12 For the synthesis of phenanthridine derivatives using [Ru] or
[Ir] complex as photoredox catalysts, see: (a) H. Jiang, Y.
Cheng, R. Wang, M. Zheng, Y. Zhang and S. Yu, Angew. Chem.
Int. Ed., 2013, 52, 13289; (b) X. Sun and S. Yu, Org. Lett., 2014,
16, 2938; (c) S. Wang, W.-L. Jia, L. Wang and Q. Liu, Eur. J. Org.
Chem., 2015, 31 6817; (d) Z. Zhang, X. Tang and W. R. Dolbier,
Org. Lett., 2015, 17, 4401; (f) J. Rong, L. Deng, P. Tan, C. Ni, Y.
Gu and J. Hu, Angew. Chem. Int. Ed., 2016, 55, 2743; (g) H.
Zhou, X. Z. Deng, A. H. Zhang and R. X. Tan, Org. Biomol.
Chem., 2016, 14, 10407; (h) C.-X. Li, D.-S. Tu, R. Yao, H. Yan
and C.-S. Lu, Org. Lett., 2016, 18, 4928.
13 For the synthesis of phenanthridine derivatives using organic
dyes as photoredox catalysts, see: (a) T. Xiao, L. Li, G. Lin, Q.
Wang, P. Zhang, Z.-w. Mao and L. Zhou, Green Chem., 2014,
16, 2418; (b) J. Fang, W.-G. Shen, G.-Z. Ao and F. Liu, Org.
Chem. Front., 2017, 4, 2049; (c) M. Singh, A. K. Yadav, L. D. S.
Yadav and R. K. P. Singh, Synlett, 2018, 29, 176.
14 (a) X. Lang, X. Chen and J. Zhao, Chem. Soc. Rev., 2014, 43,
473; (b) J. Chen, J. Cen, X. Xu and X. Li, Catal. Sci. Technol.,
2016, 6, 349; (c) D. Friedmann, A. Hakki, H. Kim, W. Choi and
D. Bahnemann, Green Chem., 2016, 18, 5391; (d) J. Z. Bloh and
R. Marschall, Eur. J. Org. Chem., 2017, 15, 2085.
15 (a) H. Xu, S. Ma, Y. Xu, L. Bian, T. Ding, X. Fang, W. Zhang and
Y. Ren, J. Org. Chem., 2015, 80, 1789; (b) X. Yang, W. Liu, L. Li,
W. Wei and C.-J. Li, Chem. -Eur J., 2016, 22, 15252; (c) W. Liu,
X. Yang, Y. Gao and C.-J. Li, J. Am. Chem. Soc., 2017, 139, 8621;
(d) L. Pan, Z. Li, T. Ding, X. Fang, W. Zhang, H. Xu and Y. Xu, J.
Org. Chem., 2017, 82, 10043; (e) W. Liu, X. Yang, Z.-Z. Zhou
and C.-J. Li, Chem, 2017, 2, 688; (f) S. Liu, J. Jie, J. Yu and X.
Yang, Adv. Syn. Catal., 2018, 360, 267; (g) Z. Lai, Z. Li, Y. Liu, P.
Yang, X. Fang, W. Zhang, B. Liu, H. Chang, H. Xu and Y. Xu, J.
Org. Chem., 2018, 83, 145.
Notes and references
1
(a) A. P. Côté, A. I. Benin, N. W. Ockwig, M. O'Keeffe, A. J.
Matzger and O. M. Yaghi, Science, 2005, 310, 1166; (b) X. Feng,
X. Ding and D. Jiang, Chem. Soc. Rev., 2012, 41, 6010; (c) S.-Y.
Ding and W. Wang, Chem. Soc. Rev., 2013, 42, 548; (d) S. Das,
P. Heasman, T. Ben and S. Qiu, Chem. Rev., 2017, 117, 1515;
(e) S. M. J. Rogge, A. Bavykina, J. Hajek, H. Garcia, A. I. Olivos-
Suarez, A. Sepúlveda-Escribano, A. Vimont, G. Clet, P. Bazin, F.
Kapteijn, M. Daturi, E. V. Ramos-Fernandez, F. X. Llabrés i
Xamena, V. Van Speybroeck and J. Gascon, Chem. Soc. Rev.,
2017, 46, 3134; (f) Y. Jin, Y. Hu and W. Zhang, Nat. Rev. Chem.,
2017, 1, 0056; (g) C. S. Diercks and O. M. Yaghi, Science, 2017,
355, eaal1585; (h) W. Zhao, L. Xia and X. Liu, CrystEngComm,
2018, 20, 1613.
For selected examples: (a) S.-Y. Ding, J. Gao, Q. Wang, Y. Zhang,
W.-G. Song, C.-Y. Su and W. Wang, J. Am. Chem. Soc. 2011,
133, 19816; (b) H. Xu, J. Gao and D. Jiang, Nat. Chem., 2015,
7, 905; (c) X. Wang, X. Han, J. Zhang, X. Wu, Y. Liu and Y. Cui,
J. Am. Chem. Soc., 2016, 138, 12332; (d) Z.-F. Pang, S.-Q. Xu,
T.-Y. Zhou, R.-R. Liang, T.-G. Zhan and X. Zhao, J. Am. Chem.
Soc., 2016, 138, 4710; (e) Q. Sun, B. Aguila, J. Perman, N.
Nguyen and S. Ma, J. Am. Chem. Soc., 2016, 138, 15790.
For selected examples: (a) S. S. Han, H. Furukawa, O. M. Yaghi
and W. A. Goddard, J. Am. Chem. Soc., 2008, 130, 11580; (b)
H. Furukawa and O. M. Yaghi, J. Am. Chem. Soc., 2009, 131,
8875; (c) C. J. Doonan, D. J. Tranchemontagne, T. G. Glover, J.
R. Hunt and O. M. Yaghi, Nat. Chem., 2010, 2, 235.
(a) X. Ding, L. Chen, Y. Honsho, X. Feng, O. Saengsawang, J.
Guo, A. Saeki, S. Seki, S. Irle, S. Nagase, V. Parasuk and D. Jiang,
J. Am. Chem. Soc., 2011, 133, 14510; (b) S. Patwardhan, A. A.
Kocherzhenko, F. C. Grozema and L. D. A. Siebbeles, J. Phy.
Chem. C, 2011, 115, 11768; (c) L. Chen, K. Furukawa, J. Gao, A.
Nagai, T. Nakamura, Y. Dong and D. Jiang, J. Am. Chem. Soc.,
2014, 136, 9806.
For selected examples: (a) L. Stegbauer, K. Schwinghammer
and B. V. Lotsch, Chem. Sci., 2014, 5, 2789; (b) V. S. Vyas, F.
Haase, L. Stegbauer, G. Savasci, F. Podjaski, C. Ochsenfeld and
B. V. Lotsch, Nat.Commun., 2015, 6, 8508; (c) R. K. Yadav, A.
Kumar, N.-J. Park, K.-J. Kong and J.-O. Baeg, J. Mater. Chem. A,
2016, 4, 9413; (d) T. Banerjee, F. Haase, G. Savasci, K.
Gottschling, C. Ochsenfeld and B. V. Lotsch, J. Am. Chem. Soc.,
2017, 139, 16228; (e) X. Wang, L. Chen, S. Y. Chong, M. A. Little,
Y. Wu, W.-H. Zhu, R. Clowes, Y. Yan, M. A. Zwijnenburg, R. S.
Sprick and A. I. Cooper, Nat. Chem., 2018, 10, 1180; (f) L.
Stegbauer, S. Zech, G. Savasci, T. Banerjee, F. Podjaski, K.
Schwinghammer, C. Ochsenfeld and B. V. Lotsch, Adv. Energy
Mater., 2018, 8, 1703278.
2
3
4
5
6
(a) H.-Z. Wang, M.S. Thesis, Lanzhou University, Lanzhou,
China, 2014; (b) Chinese Patent Application 201410010008.6,
2014; (c) P.-F. Wei, M.-Z. Qi, Z.-P. Wang, S.-Y. Ding, W. Yu, Q.
Liu, L.-K. Wang, H.-Z. Wang, W.-K. An and W. Wang, J. Am.
Chem. Soc., 2018, 140, 4623.
7
8
W. Liu, Q. Su, P. Ju, B. Guo, H. Zhou, G. Li and Q. Wu,
ChemSusChem, 2017, 10, 664.
(a) Y. Zhi, Z. Li, X. Feng, H. Xia, Y. Zhang, Z. Shi, Y. Mu and X.
Liu, J. Mater. Chem. A, 2017, 5, 22933; (b) Z. Li, Y. Zhi, P. Shao,
16 (a) S. Fukuzumi, H. Kotani, K. Ohkubo, S. Ogo, N. V. Tkachenko
and H. Lemmetyinen, J. Am. Chem. Soc., 2004, 126, 1600; (b)
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
Green Chemistry
Page 6 of 7
COMMUNICATION
Journal Name
K. Ohkubo, K. Mizushima, R. Iwata, K. Souma, N. Suzuki
and S. Fukuzumi, Chem. Commun., 2010, 46, 601; (c) C. K.
Prier, D. A. Rankic and D. W. C. MacMillan, Chem. Rev., 2013,
113, 5322; (d) V. Srivastava and P. P. Singh, RSC Adv., 2017, 7,
31377.
View Article Online
DOI: 10.1039/C9GC00022D
17 (a) E. G. Hope and W. Levason, Coord. Chem. Rev., 1993, 122,
109; (b) N. V. Zyk, E. K. Beloglazkina, M. A. Belova and N. S.
Dubinina, Russ. Chem. Rev., 2003, 72, 769; (c) M. D.
McReynolds, J. M. Dougherty and P. R. Hanson, Chem. Rev.,
2004, 104, 2239; (d) H. Cui, W. Wei, D. Yang, J. Zhang, Z. Xu, J.
Wen and H. Wang, RSC Adv., 2015, 5, 84657; (e) X. Liu, H. Cui,
D. Yang, S. Dai, T. Zhang, J. Sun, W. Wei and H. Wang, RSC Adv.,
2016, 6, 51830; (f) H. Cui, W. Wei, D. Yang, Y. Zhang, H. Zhao,
L. Wang and H. Wang, Green Chem., 2017, 19, 3520.
18 (a) P.-C. Qian, Y. Liu, R.-J. Song, J.-N. Xiang and J.-H. Li, Synlett,
2015, 1213; (b) D.-P. Jin, P. Gao, D.-Q. Chen, S. Chen, J. Wang,
X.-Y. Liu and Y.-M. Liang, Org. Lett., 2016, 18, 3486; (c) W. Wei,
H. Cui, D. Yang, H. Yue, C. He, Y. Zhang and H. Wang, Green
Chem., 2017, 19, 5608; (d) M.-H. Huang, W.-J. Hao, G. Li, S.-J.
Tu and B. Jiang, Chem. Commun. 2018, 54, 1079; (e) M.-H.
Huang, W.-J. Hao and B. Jiang, Chem. Asian J. 2018, 13, 2958;
(f) W. Wei, P. Bao, H. Yue, S. Liu, L. Wang, Y. Li and D. Yang,
Org. Lett., 2018, 20, 5291.
19 Y. Cai, Y. Tang, L. Fan, Q. Lefebvre, H. Hou and M. Rueping,
ACS Catal., 2018, 8, 9471.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 7
Green Chemistry
View Article Online
DOI: 10.1039/C9GC00022D
Graphics abstract
Visible-light-induced tandem radical addition-cyclization of 2-aryl
phenyl isocyanides catalysed by recyclable covalent organic
frameworks
Shuyang Liu,a Wenna Pan,a Songxiao Wu,a Xiubin Bu,a Shigang Xin,a Jipan Yu,*c Hao Xu*b
and Xiaobo Yang*a
A heterogeneous visible-light-induced tandem radical addition-cyclization of isocyanides by
photoactive covalent organic frameworks was developed, delivering diverse phenanthridines
with high reaction efficiency and easy catalyst recyclability.