Visible-Light-Promoted Transition-Metal-Free Approach toward Phosphoryl-Substituted Dihydroisoquinolones via Cascade Phosphorylation/Cyclization of N-Allylbenzamides

Article abstract of DOI:10.1002/adsc.201900544

A transition-metal-free visible-light-promoted radical phosphorylation/cyclization of N-allylbenzamides with phosphine oxides for the synthesis of phosphoryl-substituted dihydroisoquinolones was developed under room temperature. This protocol features mil

Full text of DOI:10.1002/adsc.201900544

Title: Visible-Light-Promoted Transition-Metal-Free Approach toward
Phosphoryl-Substituted Dihydroisoquinolones via Cascade
Phosphorylation/Cyclization of N-Allylbenzamides
Authors: Xiao-Ceng Liu, Kai Sun, Xiaolan Chen, Wen-Fei Wang, Yan
Liu, Qian-Li Li, Yuyu Peng, Lingbo Qu, and Bing Yu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900544
Link to VoR: http://dx.doi.org/10.1002/adsc.201900544

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Visible-Light-Promoted
Transition-Metal-Free
Approach
toward Phosphoryl-Substituted Dihydroisoquinolones via
Cascade Phosphorylation/Cyclization of N-Allylbenzamides
Xiao-Ceng Liu,a,# Kai Sun,a,# Xiao-Lan Chen,a,* Wen-Fei Wang,a Yan Liu,a Qian-Li
Li,b Yu-Yu Peng,c Ling-Bo Qu,a and Bing Yua,c,*
a
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China. E-mail:
chenxl@zzu.edu.cn, bingyu@zzu.edu.cn
b School of Chemistry & Chemical Engineering, Liaocheng University, Liaocheng, Shandong 252059, China
c Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation, Changsha University of
Science and Technology, Changsha 410114, China
# Xiao-Ceng Liu and Kai Sun contributed equally.
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A transition-metal-free visible-light-promoted
radical phosphorylation/cyclization of N-allylbenzamides
with phosphine oxides for the synthesis of phosphoryl-
substituted dihydroisoquinolones was developed under
room temperature. This protocol features mild reaction
conditions, simple operation, broad substrate scope as well
as scale-up ability.
Keywords: Visible-light, Cascade reaction, Transition-
metal free, Phosphorylation-cyclization
Scheme 1. Examples of dihydroisoquinolones
Dihydroisoquinolone is an important scaffold in
considered as a useful tool for the development of
green and sustainable transformations.[7] Over the
past few years, the synthesis of functionalized
many nature products, drugs and biologically active
molecules (Scheme 1).[1] Due to their excellent
pharmacological activities, dihydroisoquinolones
have attracted extensive attention and exhibited
extraordinary promising applications including anti-
nausea and anti-tumour. Therefore, considerable
efforts have been devoted to the preparation of
functionalized dihydroisoquinolones over the past
decade.[2] The traditional synthetic methods for the
construction of dihydroisoquinolones heavily relied
on the condensation of homophthalic anhydride with
imine[3] or oxidative annulations of benzamides with
alkenes.[4] However, almost all of those traditional
methods required harsh reaction conditions and thus
suffer from practical inconvenience.
dihydroisoquinolones
(e.g.
hydroxyalkyl,
difluoromethyl, trifluoromethyl, sulfonyl and
cycloalkyl substituted dihydroisoquinolones) through
radical cascade reaction has been well developed, in
which radicals were generated from thermolysis of
the corresponding precursors (Scheme 2a).[8] Despite
these significant achievements, transition-metal
reagent and/or elevated temperature (generally at 80-
120 °C) were still required in those reported
procedures. From the standpoint of green
chemistry,[9] it is highly desirable to develop
transition-metal-free and practical procedures to
construct the dihydroisoquinolone derivatives under
room termperature.
Organophosphorus compounds play important
roles in biochemistry, pharmaceutical chemistry and
material chemistry.[10] One of the strategies in
pharmaceutical research and material development is
introducing phosphorus substituents into biologically
active molecules to modify medicinal properties,
biological responses as well as material functions.[11]
On the other hand, cascade reaction (namely,
domino reaction or tandem reaction) has found to be
a powerful strategy for the rapid construction of
multiple bonds in one-pot manner.[5] Generally, it is
regarded as a step-economical process with minimal
waste production. Moreover, the time-consuming
isolation of intermediates, protection/deprotection
steps could be avoided in the cascade reactions.[6]
Consequently, the cascade reaction has been
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
In recent years, significant efforts have been directed
toward the installation of phosphorus substituents
into valuable frameworks.[12] For example, Liang and
co-workers recently reported the synthesis of 3-
phosphonoalkyl indolines form N-allyl anilines and
phosphine oxides in the presence of AgNO3 (20
mol%), K2CO3 (1 equiv) and benzoyl peroxide (BPO)
at 80 °C (Scheme 2b).[13]
the reaction of N-allylbenzamides and phosphine
oxides (Scheme 2c). To the best of our knowledge,
In the past decade, visible-light promoted reaction
has emerged as an eco-friendly and versatile tool for
organic synthesis under mild conditions,[14] in which
the conversion of light energy into chemical energy
and single electron transfer (SET) events were
involved.[15] However, the synthesis of phosphoryl-
substituted dihydroisoquinolones via convenient and
environmentally friendly photoredox catalysis is still
unexplored. During our continuing efforts in green
chemistry,[16] we herein disclose an efficient visible-
light-promoted protocol for the construction of
phosphoryl-substituted dihydroisoquinolones from
Scheme 2. Radical cascade reaction for the construction of
N-heterocycles
Table 1. Optimization of the reaction conditionsa
Entry
1
2
3
4
5
6
7
8
PC
oxidant (equiv)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
TBHP (3)
DTBP (3)
BPO (3)
K2S2O8 (3)
TBHP (1)
TBHP (2)
TBHP (2)
---
TBHP (2)
TBHP (2)
TBHP (2)
TBHP (2)
base (equiv)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
DABCO (2)
NaHCO3 (2)
K2CO3 (2)
solvent
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
EtOH
MeOH
DMF
DMSO
THF
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
yield (%)
15
42
36
39
27
N.D.
37
49
50
55
28
73
23
22
30
54
48
Eosin B
Eosin Y
Na2-Eosin Y
Na2-Eosin B
Rhodamine B
Rose Bengal
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
Eosin Y
---
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26c
27d
28e
29f
K3PO4 (2)
DBU (2)
Et3N (2)
NaHCO3 (1)
NaHCO3 (3)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
NaHCO3 (2)
69
N.D.
41
N.D.
53
83 (80)b
N.D.
N.D.
N.D.
48
Eosin Y
Eosin Y
Eosin Y
---
23 (20)b
22 (18)b
---
a Reaction conditions: 1a (0.5 mmol), 2a (1 mmol), PC (5 mol%), oxidant (2-3 equiv), solvent (3 mL)
under N2 for 24 h. PC = photocatalyst, TBHP = tert-butyl hydroperoxide, DTBP = di-tert-butyl
peroxide, BPO = benzoyl peroxide. N.D. = Not detected. Yield were determined by 31P NMR.
b
Isolated yield. c Without light. d Under air. e 60 oC in dark. f 80 oC in dark.
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
this is the first example for the photocatalytic
subsequently examined. To our delight, they also
showed good reactivity for the desired cyclization to
successfully produce the corresponding products
3n−x in good yields (52−85%) under the optimal
conditions. Among the target products obtained, the
structure of 3x was further confirmed by X-ray
crystallography (hydrogen atoms have been omitted
for clarity).[17] Unfortunately, when triethyl phosphite
was employed as substrate to react with 1a under the
standard conditions, no desired product was obtained,
suggesting that trialkyl phosphite is not suitable to
this reaction.
synthesis
of
various
phosphoryl-substituted
dihydroisoquinolones, in which the transition-metal
reagents and harsh reaction conditions were avoid.
The investigation was started by examining the
model reaction of N-allylbenzamide 1a with
diphenylphosphine oxide (2a) with organic dyes as
photocatalyst in the presence of base and oxidant
under the irradiation of 25 W white LEDs (Table 1).
Initially, several photocatalysts, such as eosin Y,
eosin B, Na2-Eosin Y, Na2-Eosin B, rhodamine B and
rose bengal were surveyed in CH3CN with TBHP and
DABCO (entries 1-6). Gratifyingly, the desired
product 3a was obtained in 42% yield when eosin Y
was employed as the catalyst (entry 2). Encouraged
by this exciting result, different solvents including
EtOH, MeOH, DMF, DMSO, and THF were further
screened (entries 7-11). The results revealed that
DMSO provided the better yield of 3a than other
solvents under the irradiation of white LEDs (55%,
entry 10). To further improve the reaction efficiency,
different bases, like NaHCO3, K2CO3, K3PO4, DBU,
and Et3N were tested (entries 12-16). To our delight,
when NaHCO3 was employed as the base, 73% yield
of 3a was detected (entry 12). For further
optimization, the influence of the amount of NaHCO3
was evaluated (entries 17 and 18). The yield
increased from 48% to 73% as the amount of
NaHCO3 increased from 1 equiv to 2 equiv, and no
improvement was observed as the amount
continuously increased up to 3 equiv. Additionally,
the oxidant such as BPO, DTBP and K2S2O8 were
evaluated (entries 19-21). However, no better
experimental results than that of TBHP were obtained.
Finally, the dosage of oxidant was further studied
(entries 22 and 23), and the results showed that 2
equiv of TBHP was the best choice for this
transformation and 3a was obtained in 83% yield
(entry 23). Further control experiments indicated that
eosin Y, oxidant, light irradiation, and N2 atmosphere
were essential for the reaction (entries 24-29). The
optimal reaction conditions were thus established as
follows: 1a (0.5 mmol), 2a (2 equiv), eosin Y (5
mol%), NaHCO3 (2 equiv) and TBHP (2 equiv) were
stirred in 3 mL DMSO under room temperature with
the irradiation of white LEDs for 24 h.
Table 2. Substrate scope for phosphoryl-substituted
dihydroisoquinolonesa
With the optimized reaction conditions in hand, we
next set out to explore the substrate scope of this
visible-light-promoted phosphorylation/cyclization of
N-allylbenzamides 1 with phosphine oxides 2. As
shown in Table 2, various N-allylbenzamides bearing
electron-donating groups (−OMe, −Me) and electron-
withdrawing substituents (−Cl, −Br, −I) reacted
smoothly with diphenylphosphine oxide (2a) under
the optimized reaction conditions, affording the
desired phosphoryl-substituted dihydroisoquinolones
3a−i in moderate to good yields (48−80%). Moreover,
N-substituted allylbenzamides, including ethyl group
(Et), isopropyl group (iPr), were also compatible with
this visible-light-promoted reaction giving the
corresponding products 3j−m in 73−84% yields.
Moreover, various phosphine oxides were
a
Reaction conditions: 1 (0.5 mmol), 2 (1 mmol), eosin Y
(5 mol%), TBHP (2 equiv), NaHCO3 (2 equiv), DMSO (3
mL), white LEDs, under N2 for 24 h, rt. Isolated yields
were given.
The scalability of this visible-light-promoted
phosphorylation/cyclization reaction was then
investigated. When the model reaction was performed
in 10 mmol scale in the simple flow reactor, we were
pleased to find that the reaction proceeded smoothly
to form the corresponding product 3a in 72% yield
(Scheme 3), suggesting this procedure is potentially
usful for preparative synthesis.
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
Several control experiments were subsequently
carried out to gain a deeper insight into the reaction
mechanism (Scheme 4). Initially, the radical
scavenger (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl
(TEMPO) was subjected to the standard reaction
conditions, the reaction process was completely
inhibited, which suggested that this visible-light-
promoted reaction might occur via a radical process.
Additionally, when another radical scavenger 2,6-di-
tert-butyl-4-methylphenol (BHT) was applied, the
reaction was also inhibited, and a radical coupling
adduct 4 was detected in the reaction mixture using
high-resolution mass spectrometry (HRMS). These
results demonstrated that phosphorus radical was
generated under the reaction conditions.
desired phosphorus radical. Moreover, the measured
quantum yield in the reaction of 1a and 2a was
determined to be 0.26, implying that a radical chains
process should not be involved in this photochemical
reaction.[18]
Based on the above-mentioned results and previous
literature reports,[19] a plausible mechanism was
proposed for this visible-light-promoted reaction
(Scheme 5). Initially, the ground state eosin Y is
excited upon irradiation of white LEDs to form eosin
Y*. Diphenylphosphine oxide 2a exists in rapid
equilibrium with tricoordinated phosphorus to form
2a’, which can be oxidized by the excited eosin Y*
giving phosphorus radical 5 and radical anion eosin
t
Y•−. The oxidation of eosin Y•− by BuOOH leads to
the regeneration of the ground state eosin Y for the
next cycle along with the formation of tert-butoxyl
radical (tBuO•). Afterward, the addition of radical 5
to the C=C bond of 1a gives radical intermediate 6,
which undergoes an intramolecular cyclization to
afford the radical intermediate 7. Finally,
intermediate 7 was further oxidized to the carbocation
intermediate 8, which was immediately converted
into the target product 3a by deprotonation.
Scheme 3. (A) Gram-scale synthesis of 3a with white
LEDs irradiation: N-allylbenzamide 1a (10 mmol, 1.89 g),
diphenylphosphine oxide 2a (20 mmol, 4.04 g), eosin Y (5
mol%), TBHP (2 equiv), NaHCO3 (2 equiv), DMSO (30
mL) under N2 for 24 h; (B) A specially designed apparatus
for gram-scale synthesis of 3a.
Scheme 5. Proposed reaction mechanism
In summary, we have developed a photocatalytic
protocol for phosphorylation/cyclization of easily
available N-allylbenzamides and phosphine oxides
under visible-light irradiation. A large variety of
phosphoryl-substituted dihydroisoquinolones were
smoothly prepared with this transition-metal-free
protocol under mild conditions. This reaction
employs an inexpensive and commercial organic
photocatalyst, which shows its eminent merits such as
mild reaction conditions, high step-economy, a
simple operation, broad substrate scope and facile
scalability. Further exploration of this strategy is
currently ongoing in our laboratory.
Scheme 4. Control experiments
Afterward, a series of Stern-Volmer fluorescence
quenching studies were conducted to further
understand the photocatalytic mechanism (for more
details see the Supporting Information). The results
showed that a significant decrease of fluorescence
intensity of eosin Y was observed along with the
increase in the concentration of diphenylphosphine
oxide 2a, which strongly implied that the
photoexcited state eosin Y* was effectively quenched
by diphenylphosphine oxide 2a to generate the
Experimental Section
A mixture of N-methyl-N-(2-methylally)benzamide (0.5
mmol, 1 equiv), phosphine oxide (2 equiv), TBHP (2
equiv), eosin Y (5 mol%) and NaHCO3 (2 equiv) were
sequentially added in a 10-mL reaction vial. Then, DMSO
(3 mL) was added. The reaction vial was sealed under N2
and stirred under white LEDs at rt for 24 h. Next, the
solvent was quenched with water (10 mL), extracted with
ethyl acetate (3 × 10 mL). The combined organic layers
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
were washed with brine (25 mL) and dried over anhydrous
Na2SO4. After filtration, the solvent was evaporated in
vacuo. The crude product was purified by silica gel
chromatography to give the desired product.
2019, 7, 8798; e) C. Wu, L.-H. Lu, A.-Z. Peng, G.-K. Jia, C.
Peng, Z. Cao, Z. Tang, W.-M. He, X. Xu, Green Chem.
2018, 20, 3683; f) C. Wu, X. Xin, Z.-M. Fu, L.-Y. Xie, K.-J.
Liu, Z. Wang, W. Li, Z.-H. Yuan, W.-M. He, Green Chem.
2017, 19, 1983; g) L.-Y. Xie, Y.-J. Li, J. Qu, Y. Duan, J.
Hu, K.-J. Liu, Z. Cao, W.-M. He, Green Chem. 2017, 19,
5642.
Acknowledgements
[8] a) W. Zhou, S. Ni, H. Mei, J. Han, Y. Pan, Org. Lett. 2015,
17, 2724; b) J. Zheng, Z. Deng, Y. Zhang, S. Cui, Adv.
Synth. Catal. 2016, 358, 746; c) D. Xia, Y. Li, T. Miao, P.
Li, L. Wang, Chem. Commun. 2016, 52, 11559; d) Z.-Q.
Xu, C. Wang, L. Li, L. Duan, Y.-M. Li, J. Org. Chem.
2018, 83, 9718; e) J. Wang, K. Sun, X. Chen, T. Chen, Y.
Liu, L. Qu, Y. Zhao, B. Yu, Org. Lett. 2019, 21, 1863; f) J.
Hu, T.-J. Pu, Z.-W. Xu, W.-Y. Xu, Y.-S. Feng, Adv. Synth.
Catal. 2019, 361, 708; g) P. Qian, B. Du, W. Jiao, H. Mei, J.
Han, Y. Pan, Beilstein J. Org. Chem. 2016, 12, 301; h) W.
Zhou, P. Qian, J. C. Zhao, H. Fang, J. L. Han, Y. Pan, Org.
Lett. 2015, 17, 1160.
[9] a) G.-P. Yang, X. Wu, B. Yu, C.-W. Hu, ACS Sustainable
Chem. Eng. 2019, 7, 3727; b) L.-H. Lu, S.-J. Zhou, M. Sun,
J.-L. Chen, W. Xia, X. Yu, X. Xu, W.-M. He, ACS
Sustainable Chem. Eng. 2019, 7, 1574; c) C. Wu, H.-J.
Xiao, S.-W. Wang, M.-S. Tang, Z.-L. Tang, W. Xia, W.-F.
Li, Z. Cao, W.-M. He, ACS Sustainable Chem. Eng. 2019,
7, 2169.
We acknowledge the Centre of Advanced Analysis
&
Computational Science (Zhengzhou University) for the
characterization and financial support from NSFC (21501010),
China Postdoctoral Science Foundation (2019M652561), and
Hunan Provincial Key Laboratory of Materials Protection for
Electric Power and Transportation (2019CL03).
References
[1] a) S.-S. Zhang, J.-Q. Wu, X. Liu, H. Wang, ACS Catal.
2015, 5, 210; b) W. H. Moser, J. Zhang, C. S. Lecher, T. L.
Frazier, M. Pink, Org. Lett. 2002, 4, 1981; c) S. Cui, Y.
Zhang, Q. Wu, Chem. Sci. 2013, 4, 3421; d) Y. You, K.
Zhou, B. Guo, Q. Liu, Z. Cao, L. Liu, H.-C. Wu, ACS Sens.
2019, 4, 774.
[2] a) T. K. Hyster, D. M. Dalton, T. Rovis, Chem. Sci. 2015, 6,
254; b) F. Pan, C. Shu, L.-W. Ye, Org. Biomol. Chem.
2016, 14, 9456.
[10] a) M. H. Muhammad, X.-L. Chen, B. Yu, L.-B. Qu, Y.-F.
Zhao, Pure Appl. Chem. 2019, 91, 33; b) C. Jing, X. Chen,
K. Sun, Y. Yang, T. Chen, Y. Liu, L. Qu, Y. Zhao, B. Yu,
Org. Lett. 2019, 21, 486.
[11] a) Y. Liu, X.-L. Chen, F.-L. Zeng, K. Sun, C. Qu, L.-L. Fan,
Z.-L. An, R. Li, C.-F. Jing, S.-K. Wei, L.-B. Qu, B. Yu, Y.-
Q. Sun, Y.-F. Zhao, J. Org. Chem. 2018, 83, 11727; b) L.
Peng, Z. Hu, Z. Tang, Y. Jiao, X. Xu, Chin. Chem. Lett.
2019, DOI: 10.1016/j.cclet.2019.04.008.
[12] a) K. Luo, W.-C. Yang, L. Wu, Asian J. Org. Chem. 2017,
6, 350; b) B.-G. Cai, J. Xuan, W.-J. Xiao, Sci. Bull. 2019,
64, 337.
[13] D. Liang, D. Ge, Y. Lv, W. Huang, B. Wang, W. Li, J. Org.
Chem. 2018, 83, 4681.
[14] a) L. Niu, J. Liu, X. A. Liang, S. Wang, A. Lei, Nat.
Commun. 2019, 10, 467; b) T.-Y. Shang, L.-H. Lu, Z. Cao,
Y. Liu, W.-M. He, B. Yu, Chem. Commun. 2019, 55, 5408;
c) Q. Liu, L. Wang, H. Yue, J.-S. Li, Z. Luo, W. Wei,
Green Chem. 2019, 21, 1609; d) L. Wang, M. Zhang, Y.
Zhang, Q. Liu, X. Zhao, J.-S. Li, Z. Luo, W. Wei, Chin.
Chem. Lett. 2019, DOI: 10.1016/j.cclet.2019.05.041; e) Y.
Liu, X.-L. Chen, K. Sun, X.-Y. Li, F.-L. Zeng, X.-C. Liu,
L.-B. Qu, Y. Zhao, B. Yu, Org. Lett. 2019,
10.1021/acs.orglett.9b01175; f) W. Wei, L. Wang, P. Bao,
Y. Shao, H. Yue, D. Yang, X. Yang, X. Zhao, H. Wang,
Org. Lett. 2018, 20, 7125.
[15] a) Q.-Q. Zhou, Y.-Q. Zou, L.-Q. Lu, W.-J. Xiao, Angew.
Chem. Int. Ed. 2019, 58, 1586; b) J.-R. Chen, X.-Q. Hu, L.-
Q. Lu, W.-J. Xiao, Chem. Soc. Rev. 2016, 45, 2044; c) R.
Li, X. Chen, S. Wei, K. Sun, L. Fan, Y. Liu, L. Qu, Y.
Zhao, B. Yu, Adv. Synth. Catal. 2018, 360, 4807.
[16] a) G.-P. Yang, N. Jiang, X.-Q. Huang, B. Yu, C.-W. Hu,
Mol. Catal. 2019, 468, 80; b) B. Yu, B. Zou, C.-W. Hu, J.
CO2 Util. 2018, 26, 314; c) X. Feng, T. Yang, X. He, B.
Yu, C.-W. Hu, Appl. Organomet. Chem. 2018, 32, e4314;
d) X.-L. Chen, X. Li, L.-B. Qu, Y.-C. Tang, W.-P. Mai, D.-
H. Wei, W.-Z. Bi, L.-K. Duan, K. Sun, J.-Y. Chen, D.-D.
Ke, Y.-F. Zhao, J. Org. Chem. 2014, 79, 8407.
[3] a) Y. Vara, T. Bello, E. Aldaba, A. Arrieta, J. L. Pizarro, M.
I. Arriortua, X. Lopez, F. P. Cossío, Org. Lett. 2008, 10,
4759; b) L. Wang, J. Liu, H. Tian, C. Qian, J. Sun, Adv.
Synth. Catal. 2005, 347, 689; c) J. Azizian, A. A.
Mohammadi, A. R. Karimi, M. R. Mohammadizadeh, J.
Org. Chem. 2005, 70, 350.
[4] a) Q. Tang, D. Xia, X. Jin, Q. Zhang, X.-Q. Sun, C. Wang,
J. Am. Chem. Soc. 2013, 135, 4628; b) S. Rakshit, C.
Grohmann, T. Besset, F. Glorius, J. Am. Chem. Soc. 2011,
133, 2350; c) N. Guimond, S. I. Gorelsky, K. Fagnou, J.
Am. Chem. Soc. 2011, 133, 6449; d) M. Yamauchi, M.
Morimoto, T. Miura, M. Murakami, J. Am. Chem. Soc.
2010, 132, 54; e) B. Li, J. Ma, N. Wang, H. Feng, S. Xu, B.
Wang, Org. Lett. 2012, 14, 736; f) L. Grigorjeva, O.
Daugulis, Org. Lett. 2014, 16, 4684.
[5] a) B. Yu, B.-B. Cheng, W.-Q. Liu, W. Li, S.-S. Wang, J.
Cao, C.-W. Hu, Adv. Synth. Catal. 2016, 358, 90; b) F.-L.
Zeng, X. Chen, S.-Q. He, K. Sun, Y. Liu, R. Fu, L. Qu, Y.
Zhao, B. Yu, Org. Chem. Front. 2019, 6, 1476; c) X.
Huang, N. Rong, P. Li, G. Shen, Q. Li, N. Xin, C. Cui, J.
Cui, B. Yang, D. Li, C. Zhao, J. Dou, B. Wang, Org. Lett.
2018, 20, 3332; d) K. Sun, S. Wang, R. Feng, Y. Zhang, X.
Wang, Z. Zhang, B. Zhang, Org. Lett. 2019, 21, 2052; e) X.
Gao, L. Tang, L. Huang, Z.-S. Huang, Y. Ma, G. Wu, Org.
Lett. 2019, 21, 745.
[6] a) K. Sun, X.-L. Chen, S.-J. Li, D.-H. Wei, X.-C. Liu, Y.-L.
Zhang, Y. Liu, L.-L. Fan, L.-B. Qu, B. Yu, K. Li, Y.-Q.
Sun, Y.-F. Zhao, J. Org. Chem. 2018, 83, 14419; b) Y.
Zhang, K. Sun, Q. Lv, X. Chen, L. Qu, B. Yu, Chin. Chem.
Lett. 2019, DOI: 10.1016/j.cclet.2019.03.034; c) K. Sun,
S.-J. Li, X. Chen, Y. Liu, X. Huang, D. Wei, L. Qu, Y.
Zhao, B. Yu, Chem. Commun. 2019, 55, 2861; d) H. Hu, X.
Chen, K. Sun, J. Wang, Y. Liu, H. Liu, L. Fan, B. Yu, Y.
Sun, L. Qu, Y. Zhao, Org. Lett. 2018, 20, 6157; e) H. Hu,
X. Chen, K. Sun, J. Wang, Y. Liu, H. Liu, B. Yu, Y. Sun, L.
Qu, Y. Zhao, Org. Chem. Front. 2018, 5, 2925.
[7] a) J. Sun, J.-K. Qiu, Y.-N. Wu, W.-J. Hao, C. Guo, G. Li,
S.-J. Tu, B. Jiang, Org. Lett. 2017, 19, 754; b) X.-T. Zhu, Q.
Zhao, F. Liu, A.-F. Wang, P.-J. Cai, W.-J. Hao, S.-J. Tu, B.
Jiang, Chem. Commun. 2017, 53, 6828; c) J. Zheng, Y.
Zhang, D. Wang, S. Cui, Org. Lett. 2016, 18, 1768; d) C.
Wu, L. Hong, H. Shu, Q.-H. Zhou, Y. Wang, N. Su, S.
Jiang, Z. Cao, W.-M. He, ACS Sustainable Chem. Eng.
[17] CCDC
1906760
contains
the
supplementary
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
[18] M. A. Cismesia, T. P. Yoon, Chem. Sci. 2015, 6, 5426.
[19] a) D. Liu, J.-Q. Chen, X.-Z. Wang, P.-F. Xu, Adv. Synth.
Catal. 2017, 359, 2773; b) Y. Chen, L.-Q. Lu, D.-G. Yu,
C.-J. Zhu, W.-J. Xiao, Sci. China Chem. 2019, 62, 24; c)
D.-M. Yan, J.-R. Chen, W.-J. Xiao, Angew. Chem. Int. Ed.
2019, 58, 378; d) D.-M. Yan, Q.-Q. Zhao, L. Rao, J.-R.
Chen, W.-J. Xiao, Chem. Eur. J. 2018, 24, 16895; e) Z.-J.
Shen, H.-N. Shi, W.-J. Hao, S.-J. Tu, B. Jiang, Chem.
Commun. 2018, 54, 11542.
6
This article is protected by copyright. All rights reserved.

10.1002/adsc.201900544
Advanced Synthesis & Catalysis
COMMUNICATION
Visible-Light-Promoted Transition-
Metal-Free Approach Toward
Phosphoryl-Substituted
Dihydroisoquinolones via Cascade
Phosphorylation/Cyclization of N-
Allylbenzamides
Adv. Synth. Catal. Year, Volume, Page
– Page
An operationally simple, scalable, and transition-metal-free
visible-light-promoted radical phosphorylation/cyclization
reaction for the synthesis of phosphoryl-substituted
dihydroisoquinolones under mild reaction conditions was
developed.
Xiao-Ceng Liu,# Kai Sun,# Xiao-Lan
Chen,* Wen-Fei Wang, Yan Liu,
Qian-Li Li, Yu-Yu Peng, Ling-Bo Qu,
and Bing Yu*
7
This article is protected by copyright. All rights reserved.