Room Temperature C-P Bond Formation Enabled by Merging Nickel Catalysis and Visible-Light-Induced Photoredox Catalysis

Article abstract of DOI:10.1002/chem.201500227

A novel and efficient C-P bond formation reaction of diarylphosphine oxides with aryl iodides was achieved by combining nickel catalysis and visible-light-induced photoredox catalysis. This dual-catalytic reaction showed a broad substrate scope, excellent functional group tolerance, and afforded the corresponding products in good to excellent yields. Compared with the previously reported use of photoredox/nickel dual catalysis in the construction of C-C bonds, the methodology described herein was observed to be the first to allow for C-heteroatom bond formation.

Full text of DOI:10.1002/chem.201500227

DOI: 10.1002/chem.201500227
Communication
&
Synthetic Methods
Room Temperature CÀP Bond Formation Enabled by Merging
Nickel Catalysis and Visible-Light-Induced Photoredox Catalysis
Jun Xuan,[a] Ting-Ting Zeng,[a] Jia-Rong Chen,[a] Liang-Qiu Lu,*[a] and Wen-Jing Xiao*[a, b]
Abstract: A novel and efficient CÀP bond formation reac-
tion of diarylphosphine oxides with aryl iodides was ach-
ieved by combining nickel catalysis and visible-light-in-
duced photoredox catalysis. This dual-catalytic reaction
showed a broad substrate scope, excellent functional
group tolerance, and afforded the corresponding products
in good to excellent yields. Compared with the previously
reported use of photoredox/nickel dual catalysis in the
construction of CÀC bonds, the methodology described
herein was observed to be the first to allow for C-hetero-
atom bond formation.
Over the past several years, transition-metal-catalyzed cross-
Scheme 1. Photoredox/nickel dual catalysis. Boc=tert-butyloxy carbonyl,
coupling reactions have been established as one of the most
useful and efficient methods for creating new CÀC and CÀhet-
eroatom bonds.[1] More intriguingly, dual catalysis realized by
merging transition-metal catalysis with visible-light-induced
photoredox catalysis has recently attracted considerable atten-
tion.[2] Exploration of this dual-catalytic strategy has allowed
for the development of various useful chemical transforma-
tions, which are unfeasible or not easily accessible by a single
catalytic system. In 2011, Sanford and co-workers published
a seminal contribution on the arylation of unactivated arenes
by combining palladium catalysis and visible-light photoredox
catalysis.[3a] Since that study, many other transition metals,
such as copper,[4] gold,[5] and rhodium,[6] have been subse-
quently introduced to this emerging research area. However,
very recently, a milestone was reached in the field of photore-
dox/nickel dual catalysis when two elegant examples of this
catalytic process appeared simultaneously. One example was
{dF(CF3)ppy}=2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine,
dtbbpy=4,4’-di-tert-butyl-2,2’-bipyridine, bpy=2,2’-bipyridine, CFL=com-
pact fluorescent light.
the coupling of a-carboxyl sp3-carbons with aryl halides
(Scheme 1a),[7] and the other was the coupling of benzylic tri-
fluoroborates with aryl bromides (Scheme 1b).[8] In each study,
the photogenerated carbon-centered radical was intercepted
by a NiII intermediate II to yield NiIII complex III, followed by
a reductive elimination to give the final product of CÀC bond
formation. Despite these impressive advances, further explora-
tion of the photoredox/nickel dual-catalytic system to develop
other useful chemical transformations, especially the formation
of new CÀheteroatom bonds, remains a highly desirable but
challenging goal.
Organophosphine compounds are an important class of
chemicals that have been widely used in organic synthesis,
medicinal chemistry, polymers, photoelectric materials, and co-
ordination chemistry.[9] Consequently, great effort has been de-
voted to the development of new and efficient catalytic meth-
ods for their synthesis.[10] Generally, the visible-light-mediated
CÀP bond formation reaction can be divided into two catego-
ries. One is the utilization of a phosphite ester as the nucleo-
phile to capture the photogenerated reactive species, such as
iminium ion[11] and arylgold(III) intermediates,[12] to create new
CÀP bonds. The other strategy has been reported by the Ko-
bayashi group and involves the visible-light-induced hydro-
phosphinylation of unactivated alkenes.[13] In the study by Ko-
bayashi and co-workers, a P-centred radical, generated by re-
ductive quenching of the excited state of the photoredox cata-
lyst with diarylphosphine oxide, was considered the key inter-
mediate. Inspired by these elegant studies, we hypothesized
[a] J. Xuan, T.-T. Zeng, Prof. Dr. J.-R. Chen, Dr. L.-Q. Lu, Prof. Dr. W.-J. Xiao
CCNU-u Ottawa Joint Research Centre
Key Laboratory of Pesticide & Chemical Biology
Ministry of Education, College of Chemistry
Central China Normal University (CCNU)
152 Luoyu Road, Wuhan, Hubei 430079 (China)
E-mail: luliangqiu@mail.ccnu.edu.cn
wxiao@mail.ccnu.edu.cn
Homepage: http://chem-xiao.ccnu.edu.cn/
[b] Prof. Dr. W.-J. Xiao
Collaborative Innovation Center of Chemical Science
and Engineering, Tianjin (China)
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
345 Lingling Road, Shanghai 200032 (China)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201500227.
Chem. Eur. J. 2015, 21, 1 – 5
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that the photogenerated P-centred radical can also be added
to the metal center of the NiII intermediate II in the photore-
dox/nickel dual-catalytic system, thus providing an efficient al-
ternative method for forging CÀP bonds in a controllable
manner. As part of our ongoing research interest in the devel-
opment of new photocatalytic chemical transformations,[14] we
herein describe an efficient redoxneutral CÀP bond formation
reaction by merging nickel catalysis with visible-light photore-
dox catalysis (Scheme 1c). To the best of our knowledge, this
is the first example of a CÀheteroatom bond formation reac-
tion by using the combination of visible-light photoredox cat-
alysis and nickel catalysis.
revealed that the GC yield of 3a could be slightly increased
when [Ru(bpy)3Cl6].6H2O was used as the photoredox catalyst
(entry 7, 72% yield). Next, we examined the influence of the
base on this CÀP bond formation reaction. Compared with the
reaction involving Cs2CO3, the reaction proceeded less effi-
ciently with other bases, such as K2CO3, KOH, and 1,8-diazabi-
cyclo[5.4.0]undec-7-ene (DBU; entries 8–10). Other reaction pa-
rameters, including the ratio of 1a to 2a and the catalyst load-
ing, were also carefully screened (entries 11–13). A similar GC
yield was obtained when 2.0 equivalents of 1a were employed
(entry 11). To our delight, the yield of 3a could be increased to
83% when a 1:2 ratio of 1a to 2a was used. Finally, 91% GC
yield (90% isolated yield) was achieved when the reaction was
performed in the presence of 5 mol% [Ru(bpy)3Cl6]·6H2O and
2 mol% [Ni(cod)2]/dtbbpy with 2.0 equivalents of Cs2CO3
(entry 13). The critical role of the nickel catalyst, the photore-
dox catalyst, light irradiation and the base, as well as the de-
gassing procedure were demonstrated through control experi-
ments in which no or only a trace amount of the desired prod-
uct was detected upon omission of any of these components
(Table 1, entries 14–18).
Our proposed dual-catalytic CÀP formation reaction was ini-
tially evaluated by using 4-iodoanisole (1a) and diphenylphos-
phine oxide 2a along with 10 mol% [Ni(cod)2], 10 mol%
dtbbpy as the ligand, 2 mol% [Ir{dF(CF3)ppy}2(dtbbpy)]PF6 pho-
toredox catalyst, Cs2CO3, and a 3W blue LED at room tempera-
ture (Table 1).[15] To our delight, we observed the desired CÀP
bond formation product 3a when using DMSO as the reaction
media, albeit in a modest 16% yield (entry 1). It was observed
that the solvent selection had a significant effect on the yield
of the coupling reaction (entries 2–4), with MeOH being the
best choice (entry 3, 65% yield). Moreover, the use of
a number of commonly used nickel catalysts did not improve
the reaction efficiency (entries 5 and 6). Further investigations
With the optimal reaction conditions in hand, we next
probed the scope of this dual catalytic CÀP formation process.
As shown in Table 2, a series of diversely substituted aryl io-
dides reacted readily with diphenylphosphine oxide 2a under
the optimal conditions. Incorporation of electron-donating
(-Me, -OMe) or electron-withdrawing groups (-F, -Cl, -Br) at the
para-position of iodobenzene were tolerated well, affording
the corresponding coupling products 3a–f in generally high
yields (entries 1–6, 71–91% yields). In addition, this dual cata-
lytic reaction allowed for a broad range of functional groups
on the aryl ring (e.g., phenols, amines, amides, and ethers) to
be accommodated (entries 7–11, 81–86% yield). More signifi-
cantly, the sterically encumbered 1-iodonaphthalene 1l proved
to be a viable partner, affording the CÀP formation product 3l
in 90% yield (entry 12). To our delight, the methyl-modified
secondary phosphine oxide 2b also proved to be a competent
reactant to provide triarylphosphine oxide 3m in 69% yield
(entry 13). It is well documented that electron-rich secondary
phosphine oxides exist nearly exclusively in their pentavalent
tautomeric form, which prevents them from participating in
the photo-oxidation step to give the key P-centered radical in-
termediates.13,16 As expected, no desired CÀP bond formation
products were detected when dicyclohexylphosphine oxide 2c
and ethyl phenylphosphinate 2d were utilized under the best
reaction conditions (entries 14 and 15).
Table 1. Optimization of the reaction conditions.[a]
Entry
[Ni]
PC
Solvent
Base
Yield [%][b]
1
2
3
4
5
6
7
8
9
10
11[c]
12[d]
13[e]
14
15
16
17[g]
18[h]
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
NiCl2(PPh3)2
[Ir]
[Ir]
[Ir]
[Ir]
[Ir]
[Ir]
[Ru]
[Ru]
[Ru]
[Ru]
[Ru]
[Ru]
[Ru]
[Ru]
–
DMSO
CH3CN
MeOH
DCM
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
K2CO3
KOH
16
6
65
4
45
42
72
63
39
71
70
83
91 (90)[f]
6
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
.
NiCl2 glyme
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
–
Ni(cod)2
Ni(cod)2
Ni(cod)2
Ni(cod)2
DBU
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
Cs2CO3
–
0
[Ru]
[Ru]
[Ru]
trace
0
Notably, this photoredox/nickel dual-catalytic process could
be extended further to the coupling of diarylphosphine oxide
with heteroaryl iodides. For example, 5-iodo-1H-indole (1m)
and 2-iodopyridine (1n) can facilely react with diphenylphos-
phine oxide 2a, giving the corresponding CÀP bond formation
products 3p and 3q in 84 and 75% yield, respectively [Eq. (1)
and (2)]. It is worth noting that the photoredox catalyst
[Ir(ppy)2(bpy)]PF6 was observed to be superior in the latter case.
A plausible reaction mechanism was proposed in Scheme 2
to explain this dual catalytic CÀP bond formation process. The
photocatalytic cycle starts with the reductive quenching of ex-
Cs2CO3
Cs2CO3
0
[a] Reaction conditions: 1a (0.36 mmol), 2a (0.3 mmol), Ni catalyst
(10 mol%), dtbbpy (10 mol%), PC (2 mol%), base (0.6 mmol), and solvent
(3 mL) at RT for 24 h under the irradiation of a 3W blue LED. [b] GC yield
by using tetradecane as the internal standard. [c] 1a (0.6 mmol), 2a
(0.3 mmol). [d] 1a (0.3 mmol), 2a (0.6 mmol). [e] [Ni(cod)2] (2 mol%),
dtbbpy (2 mol%), photocatalyst (5 mol%). [f] Isolated yield in parentheses.
[g] Without visible-light irradiation. [h] Without the degassing procedure.
[Ir]: [Ir{dF(CF3)ppy}2(dtbbpy)]PF6, [Ru]: [Ru(bpy)3Cl2]·6H2O, cod=1,5-cyclo-
octadiene, glyme=1,2-dimethoxyethane, DMSO=dimethyl sulfoxide,
DBU=1,8-diazabicyclo[5.4.0]undec-7-ene. PC=photocatalyst.
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Table 2. Substrate scope.
Table 2. (Continued)
[a]
Entry
1
2
Product
Yield
[%][b]
15
2d
n.d.[e]
Entry
1
2
Product
Yield
[%][b]
[a] Reaction conditions: 1 (0.3 mmol), 2 (0.6 mmol), [Ni(cod)2] (2 mol%),
dtbbpy (2 mo%), [Ru(bpy)3Cl2].6H2O (5 mol%), Cs2CO3 (0.6 mmol), and
MeOH (3 mL) at RT for 24 h under the irradiation of a 3W blue LED.
[b] Yield of the isolated product. [c] 1c (0.6 mmol), 2a (0.3 mmol). [d] 1b
(0.6 mmol), 2b (0.3 mmol). [e] n.d.=not detected. Ts=p-toluenesulfonyl,
Ac=acetyl.
1
2a
2a
2a
2a
2a
90
91
71
83
88
2
3[c]
4
5
cited state RuII* with phosphinous acid V to yield the corre-
sponding radical-cation intermediate VI and the low-valence
RuI complex. Then, the base-promoted deprotonation of VI de-
livers the key P-centered radical VII.[13] Meanwhile, the oxida-
tive addition of the Ni0 species I to aryl halide 1 would give
the NiII intermediate II, which rapidly intercepts the P-centered
radical VII to afford the organometallic NiIII complex III.[7,8] Re-
ductive elimination of III gives the final CÀP bond formation
product 3, as well as the NiI species IV. Finally, single-electron
reduction of the NiI species IV by the low-valence photocata-
lyst RuI completes both of the catalytic cycles. Another reac-
tion pathway involving the addition of P-centered radical VII
to the Ni0 species might be possible and cannot be totally
ruled out at the current stage (see Section S4 in the Support-
ing Information for details).
6
7
2a
2a
81
84
8
9
2a
2a
2a
2a
85
86
81
83
10
11
In conclusion, we have developed an efficient dual-catalytic
CÀP formation reaction by combining nickel catalysis and visi-
ble-light-induced photoredox catalysis. The method takes ad-
vantage of the visible-light photoredox catalytic cycle to gen-
erate P-centered radicals from diarylphosphine oxides under
very mild reaction conditions (room temperature, visible-light
irradiation) and combines the reaction with the nickel-cata-
lyzed functionalization of aryl iodides. These reactions are com-
patible with a wide range of functional groups (e.g., phenols,
amines, amides, and ethers) and give the corresponding im-
portant triarylphosphine oxides in good to excellent yields.
12
2a
90
13[d]
2b
2c
69
14
n.d.[e]
Experimental Section
Representative procedure
To a 10 mL Schlenk flask equipped with a magnetic stir bar 1a
(0.3 mmol), 2a (0.6 mmol), [Ru(bpy)3Cl2]·6H2O (0.015 mmol),
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blue LED and stirred at room temperature for 24 h. Then, the sol-
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by flash chromatography on silica gel (silica: 200–300 mm; eluent:
petroleum ether/ethyl acetate 3:1 to 1:1) to provide the pure prod-
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Acknowledgements
We are grateful to the National Science Foundation of China
(NO. 21232003, 21202053, 21272087, and 21472057) and the
National Basic Research Program of China (2011CB808603) for
support of this research.
Keywords: CÀP bond formation · dual catalysis · nickel ·
photochemistry · radicals
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[15] For more details on condition optimization, please see the Supporting
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Received: January 19, 2015
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Published online on && &&, 0000
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Communication
COMMUNICATION
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Synthetic Methods
J. Xuan, T.-T. Zeng, J.-R. Chen, L.-Q. Lu,*
W.-J. Xiao*
&& – &&
Dual catalysis: A novel and efficient CÀ
P bond formation reaction of diary-
lphosphine oxides with aryl iodides was
achieved by combining nickel catalysis
and visible-light-induced photoredox
catalysis (see scheme). This dual-catalyt-
ic reaction showed a broad substrate
scope, excellent functional-group toler-
ance, and afforded the corresponding
products in good to excellent yields.
Compared with previously reported
photoredox/nickel dual catalytic sys-
tems, this methodology is the first to
allow for CÀheteroatom bond forma-
tion.
Room Temperature CÀP Bond
Formation Enabled by Merging Nickel
Catalysis and Visible-Light-Induced
Photoredox Catalysis
Chem. Eur. J. 2015, 21, 1 – 5
www.chemeurj.org
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ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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These are not the final page numbers! ÞÞ