Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis

Article abstract of DOI:10.1016/S1872-2067(19)63379-6

An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strategy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium sulfide semiconductors as heterogeneous photocatalysts and

Full text of DOI:10.1016/S1872-2067(19)63379-6

Chinese Journal of Catalysis 40 (2019) 1841–1846
a v a i l a b l e a t w w w . s c i e n c e d i r e c t . c o m
j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / c h n j c
Communication (Special Issue of the 17th Chinese National Youth Conference on Catalysis (17th CNYCC))
Practical C–P bond formation via heterogeneous photoredox and
nickel synergetic catalysis
Ernest Koranteng a,†, Yi-Yin Liu a,†, Si-Yue Liu a, Qiang-Xian Wu a, Liang-Qiu Lu a,b,*, Wen-Jing Xiao a
a CCNU-uOttawa Joint Research Centre, Hubei International Scientific and Technological Cooperation Base of Pesticide and Green Synthesis, Key Labora-
tory of Pesticides & Chemical Biology Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, Hubei, China
b State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou
730000, Gansu, China
A R T I C L E I N F O
A B S T R A C T
Article history:
An efficient C–P bond formation reaction was developed by virtue of the synergetic catalysis strate-
gy by merging heterogeneous photocatalysis and nickel catalysis. This platform utilizing cadmium
sulfide semiconductors as heterogeneous photocatalysts and nickel complexes as transition metal
catalysts provided a variety of organophosphorus compounds from readily available aryl and vinyl
halides, as well as aryl triflates, with generally a good-to-excellent reaction efficiency (31 examples,
46%-98% yields). The current protocol features mild reaction conditions, a broad substrate scope,
recyclability of photocatalysts, and inexpensive catalysts, thus defining the practical and economic
proprieties of the present catalyst system.
Received 19 April 2019
Accepted 11 May 2019
Published 5 December 2019
Keywords:
Photoredox catalysis
Nickel catalysis
Construction of carbon-phosphorus
bond
© 2019, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.
Published by Elsevier B.V. All rights reserved.
Heterogeneous
Given the fundamental significance of organophosphorus
compounds ranging from synthetic, pharmaceutical, and agri-
cultural chemistries to materials and life sciences, the construc-
tion of C–P bonds has long been an important task for genera-
tions of synthetic chemists [1–7]. Since the pioneering work
from Hirao et al., who developed the palladium-catalyzed
phosphonation of aryl iodides or bromides in the 1980s [8–10],
transition-metal-catalyzed C–P couplings have been among the
most reliable tools for synthesizing organophosphorus mole-
cules. In recent decades, many elegant protocols using aryl
halides, boronic acids, triflates, sulfonates, and other precur-
sors as coupling partners have been developed for this purpose
[11–16]. However, the requirement of expensive and
air-sensitive ligands and oxidants and the harsh reaction condi-
tions in these transition metal catalysis systems usually result-
ed in a limited substrate scope and poor functional group tol-
erance, as well as high synthetic costs. Consequently, the de-
velopment of efficient and economical methods for C–P bond
formation is still highly desirable.
Recently, a number of impressive approaches have been
reported for constructing C–P bonds following the advent of
visible photoredox catalysis as a powerful and ecofriendly syn-
thetic tool [17–32]. Particularly, the strategy of synergistic ca-
talysis by merging visible-light photoredox catalysis [33–35]
with organometallic catalysis has provided several attractive
accesses to organophosphorus molecules [29–32]. For exam-
* Corresponding author. Tel/Fax: +86-27-67862041; E-mail: luliangqiu@mail.ccnu.edu.cn
† Contributed equally to this work.
We are grateful to the National Science Foundation of China (21822103, 21820102003, 21772052, 21772053, 21572074, 21472057), the Program of
Introducing Talents of Discipline to Universities of China (111 Program, B17019), the Natural Science Foundation of Hubei Province (2017AHB047),
and the International Joint Research Center for Intelligent Biosensing Technology and Health for support of this research.
DOI: S1872-2067(19)63379-6 | http://www.sciencedirect.com/science/journal/18722067 | Chin. J. Catal., Vol. 40, No. 12, December 2019

1842
Ernest Koranteng et al. / Chinese Journal of Catalysis 40 (2019) 1841–1846
ple, in 2015, Toste et al. [29] disclosed an elegant C–P coupling
reaction of aryldiazonium salts and H-phosphonates in the
presence of gold catalysts and ruthenium-based photocatalysts.
In the same year, a dual catalytic C(sp2)−P formation reaction of
diphenylphosphine oxides with aryl iodides by using nickel
catalysts and ruthenium-based photosensitizers was reported
[30]. In 2017, Lei et al. [31] reported a visible-light-induced
oxidant-free oxidative phosphonylation of a C(sp2)–H bond of
arenes via a dual photoredox and cobalt catalysis. Despite these
important advances in the field of photocatalytic C–P bond
formation, regardless of whether single photoredox catalysis or
the synergistic photoredox and organometallic catalysis is
used, homogeneous photocatalysts, including ruthenium or
iridium complexes and organic dyes, are widely applied. This
leads to the problem of the inability to separate, recover, and
reuse compared with heterogeneous photocatalysts (Fig. 1(a))
[36–44]. In this work, because of continuing interest in visi-
ble-light photocatalysis [45–50], this C–P formation reaction is
updated by the joint use of Ni catalysts and heterogeneous
cadmium sulfide (CdS, 2.4-eV bandgap) photocatalysts (Fig.
1(b)) [51]. Compared with previous endeavors, this protocol
should attract wide interest from the synthetic community
because of the recyclable photocatalysts, a less expensive cata-
lyst system, and a broad substrate scope.
Table 1
Condition optimization a.
Entry
1
2
Solvent
Base
DBU
Cs2CO3
DABCO
Et3N
Et3N
Et3N
Et3N
Yield b (%)
MeCN
MeCN
MeCN
MeCN
DMF
DMA
DMSO
THF
21
54
73
80
79
90
51
54
29
57
3
4
5
6
7
8
Et3N
9
10 c
Toluene
DMA
Et3N
Et3N
a Reaction conditions: 1a (1.0 mmol), 2a (1.5 mmol, 1.5 equiv), base (2.0
mmol, 2.0 equiv.), NiCl2•6H2O (0.05 mmol, 5 mol%), dtbbpy (0.05 mmol,
5 mol%), CdS (0.2 mmol, 20 mol%), and solvent (3.0 mL) under irradia-
tion by 2 × 3 W blue LEDs. b Isolated yield of 3aa. c Room temperature
for 24 h. LEDs, light-emitting diodes; DBU, 1,5-diazabicyclo[4.3.0]non-
5-ene; dtbbpy, 4,4'-di-tert-butyl-2,2'-bipyridine; DMA, dimethyla-
cetamide.
ality of this catalyst system for the C–P coupling was then in-
vestigated. Different aryl bromides bearing a variety of func-
tional groups can be utilized in this protocol to deliver the cou-
pled product with a good-to-excellent yield (Scheme 1). For
instance, aryl bromides containing electron-withdrawing
groups, such as ester, ketone, nitrile, trifluoromethyl, and fluo-
ride, at the para- or meta-position were adequate coupling
The study began with ethyl 4-bromobenzoate and diphe-
nylphosphine oxide as substrates. Exposure of these two
chemicals in CH3CN to blue light-emitting diodes (LEDs) in the
presence of 20-mol% CdS, 5-mol% NiCl2•6H2O, 5-mol% dtbbpy,
and 2.0 equiv. DBU under an Ar atmosphere at 55 °C resulted in
the desired product 3aa in 21% yield after 24 h. Because of this
result, different parameters were evaluated to improve the
reaction efficiency. First, it was found that organic base Et3N
gave the best yield of the product (Table 1, entry 4, 80% yield)
among all the screened bases. Second, after other reaction me-
dia were screened, DMA stood out as the optimal one (Table 1,
entry 6), and the best substrate ratio of 1a to 2a was 1:2 (Table
S2). Third, the reaction, when performed at room temperature,
gave a low reaction efficiency (Table 1, entry 10). Finally, con-
trol experiments revealed that Ni, CdS, base, and light were all
essential components for obtaining high efficiency (Table S3).
After the optimized conditions were established, the gener-
Scheme 1
Substrate scope of aryl bromides.
Reaction conditions: 1 (0.5 mmol), 2a (1.0 mmol, 2.0 equiv.), base (1.0
mmol, 2.0 equiv) NiCl2•6H2O (0.025 mmol, 5 mol%), dtbbpy (0.025
mmol, 5 mol%), CdS (0.1 mmol, 20 mol%), and DMA (2.0 mL) under
irradiation by 2- × 3-W blue LEDs; isolated yields.
Fig. 1. Visible-light photocatalytic C–P bond formation.

Ernest Koranteng et al. / Chinese Journal of Catalysis 40 (2019) 1841–1846
1843
Scheme 2
Representative results of aryl chlorides and triflates.
Scheme 3
Substrate scope of phosphine oxides.
O
O
O
P
O
Ph
Ph
Ph
Ph
P
P
P
Ph
Ph
Ph
Ph
EtOOC
EtOOC
Ac
NC
3aa (Cl): 69% yield 3aa (OTf): 65% yield
3ba (Cl): 65% yield
3ba (Cl): 46% yield
O
O
O
P
O
P
Ph
Ph
Ph
Ph
N
P
P
N
Ph
Ph
Ph
Ph
Reaction conditions: 1a (0.5 mmol), 2 (1.0 mmol, 2.0 equiv.), NEt3 (1.0
mmol, 2.0 equiv), NiCl2.6H2O (0.025 mmol, 5 mol%), dtbbpy (0.025
mmol, 5 mol%), CdS (0.1 mmol, 20 mol%), and DMA (2.0 mL) under
irradiation by 2- × 3-W blue LEDs; yield after isolation by column
chromatography.
F3C
3ra (Cl): 81% yield
Me
MeO
3ea (OTf): 54% yield 3fa (OTf): 49% yield
3qa (Cl): 75% yield
Reaction conditions: 4 or 5 (0.5 mmol), 2a (1.0 mmol, 2.0 equiv), NEt3
(1.0 mmol, 2.0 equiv.), Ni(II) salt (0.025 mmol, 5 mol%), dtbbpy (0.025
mmol, 5 mol%), CdS (0.1 mmol, 20 mol%), and DMA or DMF (2.0 mL)
under irradiation by 2- × 3-W blue LEDs; isolated yields.
and diaryl-substituted vinyl bromides were successfully con-
verted into alkenyl phosphine oxides in good yields under the
standard dual catalysis conditions (Scheme 4, Eq. (2): 7aa-7ca,
67%-93% yields). In addition, it was found that the CdS photo-
catalyst can be easily recovered through a simple filtration and
washing with DMA after each run. Subsequently, substrates 1a
and 2a, together with a Ni salt, a ligand, Et3N, and DMA, were
added for a new run. As shown in Fig. 2, the catalyst could be
recycled at least five times without any significant loss of effi-
ciency (note: a control experiment revealed that no desired
product is observed in the absence of a Ni catalyst and the lig-
and after each run).
partners (3aa-3da, 3ka, and 3la: 70%‒95% yields). With the
existence of a competing chlorine group, the reaction exhibits
good chemoselectivity, giving the C–P coupled product a good
yield (3ja: 82% yield). Furthermore, aryl bromides bearing
electron-donating groups, such as methyl, methoxyl, tert-butyl,
protected amine, and phenyl, as well as 3,5-dimethylphenyl and
fused rings, can readily participate in this coupling reaction
(3ea-3ia, 3ma, and 3na: 53%‒86% yields). Moreover, het-
eroaryl bromides were also compatible in this coupling system
and converted to the corresponding products in good yields
(3oa: 73% yield; 3pa: 65% yield).
Furthermore, an attempt was made to gain insight into the
reaction mechanism. When 2.0 equiv. of the radical scavenger
2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was added to
the reaction under standard conditions, the formation of 3aa
was completely inhibited, and the phosphine-TEMPO adduct
was detected by HRMS, which indicated the involvement of
radicals in this reaction. Based on this result and previous re-
ports [30,32–44,51], a plausible reaction mechanism was pro-
posed for the formation of the desired C–P bond (Fig. 3). Upon
exposure to visible light, isomer A from substrate 2a was oxi-
Next, a representative set of aryl chlorides and triflates was
examined as possible partners for the C–P coupling. As exem-
plified in Scheme 2, because of the lower reactivity of aryl chlo-
rides compared with aryl bromides, long reaction times were
required for aryl chlorides, and, generally, decreased yields
were observed for aryl chlorides and triflates (from chlorides
4: 46%‒69% yields; from triflates 5: 49%‒65% yields). How-
ever, the C–P coupling reactions of 2-chloropyridines 4q and 4r
can produce the corresponding products in high yields (3qa:
75% yield; 3ra: 81% yield).
Then, the scope of the phosphine oxide substrate was eval-
uated. As shown in Scheme 3, a series of P–H compounds, in-
cluding H-phosphinates, H-phosphonates, and secondary
phosphine oxides, with varied electronic and steric properties,
can be well applied as efficient substrates, affording the corre-
sponding organophosphorus products with excellent levels of
efficiency (3ab-3ae: 90%‒98% yields). However, aliphatic
secondary phosphine oxides failed to participate in this trans-
formation at the current stage for unknown reasons.
Scheme 4
Gram-scale reaction and scope of vinyl bromides.
To demonstrate the practicality of this protocol, the cou-
pling reaction of 1a and 2a was performed on a gram scale (10
mmol) under the standard reaction conditions, finally affording
product 3aa (3.01 g) in an excellent yield (Scheme 4, Eq. (1)).
Moreover, considering the importance of vinylphosphine mo-
tifs in polymer science and in the synthesis of heterocycles
[52–56], whether vinyl bromides could be used as suitable
coupling partners for this coupling was considered. Alkyl, aryl,
a Reaction conditions: NiCl2•6H2O (0.5 mmol, 0.12 g), dtbbpy (0.5 mmol,
0.13 g), CdS (2.0 mmol, 0.29 g), 1a (10 mmol, 1.6 mL), 2a (20 mmol, 4.0
g), NEt3 (20.0 mmol, 2.0 equiv.), and DMA (40.0 mL); isolated yield.
b Reaction conditions: 6 (0.5 mmol), 2a (1.0 mmol, 2.0 equiv.), NEt3 (1.0
mmol, 2.0 equiv.), NiCl2•6H2O (0.025 mmol, 5 mol%), dtbbpy (0.025
mmol, 5 mol%), CdS (0.1 mmol, 20 mol%), and DMA (2.0 mL) under
irradiation by 2 × 3 W blue LEDs; isolated yield.

1844
Ernest Koranteng et al. / Chinese Journal of Catalysis 40 (2019) 1841–1846
Acknowledgment
We are grateful to the National Science Foundation of China
(21822103, 21820102003, 21772052, 21772053, 21572074,
21472057), the Program of Introducing Talents of Discipline to
Universities of China (111 Program, B17019), the Natural Sci-
ence Foundation of Hubei Province (2017AHB047), and the
International Joint Research Center for Intelligent Biosensing
Technology and Health for support of this research.
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Graphical Abstract
Chin. J. Catal., 2019, 40: 1841–1846 doi: S1872-2067(19)63379-6
Practical C–P bond formation via heterogeneous photoredox and nickel synergetic catalysis
Ernest Koranteng, Yi-Yin Liu, Si-Yue Liu, Qiang-Xian Wu, Liang-Qiu Lu *, Wen-Jing Xiao
Central China Normal University; Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences
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协同的非均相光氧化还原催化和镍催化构建碳磷键
Koranteng Ernest a,†, 刘以银a,†, 刘思跃a, 伍强贤a, 陆良秋a,b,*, 肖文精a
a华中师范大学化学学院, 农药与化学生物学重点实验室, 华师-渥太华大学国际联合研究中心, 湖北武汉430079
b中国科学院兰州化学物理研究所, 羰基合成与选择氧化国家重点实验室, 甘肃兰州730000
摘要: 作为一类重要的功能有机分子, 有机膦化合物广泛用于医药、农药、材料以及生命科学等众多领域中. 因此, 实现
C–P键的高效、高选择性构建一直是合成化学家们的一项重要研究内容. 过渡金属催化的碳磷成键反应为有机磷化物的合
成提供了一个行之有效的方法, 芳基卤代物、硼酸、三氟磺酸酯等前体均可用于该偶联反应. 但是, 这些反应往往需要用
到价格昂贵、空气敏感的金属催化剂或配体以及当量的氧化试剂, 且反应条件苛刻. 为此, 人们迫切需要发展经济、高效、
条件温和且具有普适性的绿色合成方法来解决有机膦化合物合成领域的这一难点问题.
近年来, 可见光促进的光氧化还原催化因其绿色、环保的优点而受到越来越多合成化学家们的关注. 目前, 所使用的
光催化剂大多是基于贵金属钌、铱的金属有机络合物或一些有机染料分子. 相比于均相催化的有机光化学反应, 非均相催

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化过程在催化剂的稳定性与回收利用以及产物分离等方面具有明显的优势.
本文使用商业可得的半导体材料硫化镉作为非均相光催化剂, 金属镍复合物作为过渡金属催化剂, 实现了过渡金属与
光敏剂协同催化的碳磷成键反应. 该反应具有非常广的底物适用范围, 芳基氯代物、溴代物、三氟磺酸酯以及烯基溴代物
均能较好地参与该反应, 温和条件下高效地合成得到一系列有机磷化物. 将反应规模扩大至克级时, 我们发现反应效率几
乎不受影响, 且反应结束后过滤得到的光催化剂在循环5次后反应效果仍相近. 由此可见硫化镉/镍非均相催化体系在有机
膦化合物的光化学合成中的有效性和实用性. 此外, 我们还通过控制实验和自由基捕获实验以及相关文献, 提出了该反应
的可能机理.
关键词: 光氧化还原催化; 镍催化; 碳磷键构建; 非均相催化
收稿日期: 2019-04-19. 接受日期: 2019-05-11. 出版日期: 2019-12-05.
*通讯联系人. 电话/传真: (027)67862041; 电子信箱: luliangqiu@mail.ccnu.edu.cn
†共同第一作者.
基金来源: 国家自然科学基金(21822103, 21820102003, 21772052, 21772053, 21572074, 21472057); 高等学校学科创新引智计划
(B17019); 湖北省自然科学基金(2017AHB047).
本文的电子版全文由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18722067).