Photoelectrochemical cell for P-H/C-H cross-coupling with hydrogen evolution

Article abstract of DOI:10.1039/c9cc05375a

Photoelectrochemistry enables the formation of a variety of active intermediates for organic synthesis in an environmentally friendly manner. Herein, a photoelectrochemical cell is fabricated to realize activation of P-H/C-H bonds for cross-coupling hydro

Full text of DOI:10.1039/c9cc05375a

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DOI: 10.1039/C9CC05375A
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Photoelectrochemical cell for P-H/C-H cross-coupling with
hydrogen evolution
Received 00th January 20xx,
Accepted 00th January 20xx
Jing-Hao Wang,a,b Xu-Bing Li,a,b Jian Li,a,b Tao Lei a,b Hao-Lin Wu,a,b Xiao-Lei Nan,a,b Chen-Ho Tung,a,b
and Li-Zhu Wu*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Photoelectrochemistry enables formation of a variety of active widely existing in agrochemical, material chemistry, and
intermediates for organic synthesis in an environmental friendly biochemistry.13 As the analogues of natural α-amino acid,
manner. Herein, a photoelectrochemical cell is fabricated to there has been numerous advances in constructing the α-
realize activation of P-H/C-H bonds for cross-coupling hydrogen amino phosphonates. Traditional synthetic methods (e.g.,
evolution. As compared with electrochemical cell, nearly 90% transition metal catalysis,14 chemical oxidation15 and
external bias input is saved to drive the C-P bond construction photocatalysis16-20
)
usually require directing groups,
with good to excellent yields.
stoichiometric oxidants or metal catalysts. Our results show
that BiVO4 photoanode is able to construct C-P bond in good
to excellent yields with no aid of any external oxidants or
metal catalysts. For comparison, we also constructed a EC cell
composed of a glassy carbon anode, Pt plate counter electrode
and Ag/AgCl reference electrode for the same reaction. The
results demonstrate that the applied bias to produce a
(photo)-current of 5.0 mA is 0.1 V and 1.5 V for BiVO4 PEC
system and glassy carbon EC system, respectively. These
potentials afford the target products in very similar yields (i.e.,
90% in PEC Cell and 88% in EC Cell) after 12 h of
(photo)electrolysis, indicating the great potential of more
energy-saving PEC for organic synthesis.
The BiVO4 electrode was prepared by electrodeposition in a
three-electrode cell using a constant potential of -0.1 V vs
Ag/AgCl for 10 min at room temperature (FTO as working
electrode, Pt plate as the counter electrode and Ag/AgCl as the
reference electrode). Then, N-phenyl tetrahydroisoquinoline
1a and diphenyl-phosphine oxide 2a were used as model
substrates to perform the organic transformation. Solvents
and electrolytes were firstly screened in an undivided cell via
electrocatalysis. By utilizing nBu4NBF4 as electrolyte and
In view of the increasingly serious energy crisis and
environmental problems, the use of photoelectrochemical
(PEC) cells to realize water splitting1,2 and carbon dioxide (CO2)
reduction3 has received considerable attention across multiple
discipline. Upon irradiation the photoexcited electrons from
the light-sensitive electrode can be used to drive reduction
reaction,4 and the holes left can be employed for oxidation
reactions (Scheme 1).5,6 In this regard, electrochemical study
has made a rapid progress in organic synthesis.7 A large
number of dehydrogenation cross-coupling reactions via
electrochemistry have been developed to construct C–C, C–N,
C–O, C–S and C–P bonds.8-11 Through precise control of the
voltage used,12 the active intermediates are able to form at
electrode surface via single electron transfer. It is anticipated
that PEC can conduct the organic conversion in a more energy-
saving way because of contribution of light energy. By
modulating the composition, band position and morphology of
photoelectrode, it is subsequently simple and easy to control
the reactivity and selectivity.
With this in mind, we initiated to build PEC for chemical
reaction. Herein, P-H/C-H dehydrogenation cross-coupling to
construct C-P bond is chosen as a model reaction because
organophosphorus compounds are important structural motifs
e-
e-
e-
e-
e-
a. Key Laboratory of Photochemical Conversion and Optoelectronic Materials,
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing
100190, P. R. China
[Sub]
[Sub]
[Sub]
[Sub]
h
h
O2
b. School of Future Technology, University of Chinese Academy of Sciences, Beijing
100049, P. R. China
H2O
E-mail: lzwu@mail.ipc.ac.cn
Electronic Supplementary Information (ESI) available. (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
h+
h+
PEC
EC
PEC
Scheme 1. Photoelectrochemical and electrochemistry for organic conversion.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1. Optimization of the reaction conditionsa
Table 2. PEC phosphorylation of C−H bonda
View Article Online
DOI: 10.1039/C9CC05375A
O
R1
N
O
Undivided cell
BiVO4
Pt
N
Ph
H2
Ph
P
H
R1
R2
P
R2
H
Ar
H2
N
N
Ph
Ph
P
O
Ph
Blue LED, MeCN, RT
E = 0.1 V vs Ag/AgCl
Ar
R2
P
R2
O
Ph
3aa
1a
2a
1
2
3
Entry Electrolysis conditions
Yield(%)
90
RVC(+)/Pt(-), 10 mA / 2 h, nBu4NBF4,
MeCN, rt, Ar
N
N
N
1
Ph
P
O
Ph
P
O
Ph
P
O
OMe
CH3
Ph
Ph
Ph
2
3
4
5
6
7
8
nBu4NPF6 as electrolyte
nBu4NClO4 as electrolyte
MeOH as solvent
DMF as solvent
THF as solvent
79
83
53
48
n.d.
32
3aa, 90%
3ba, 88%
3ca, 90%
OMe
N
N
N
O
OMe
Ph
P
O
Ph
P
O
Ph
P
CF3
Ph
3da, 85%
Ph
Ph
3fa, 86%
3ea, 91%
Under air
No electric current
N
N
N
n.d.
Ph
Ph
Ph
BiVO4 as photoanode,
E= 0.5 V vs Ag/AgCl
H3C
P
O
MeO
P
O
F
P
O
9
39
BiVO4 as photoanode, NHPI as
mediator, E= 0.1 V vs Ag/AgCl
No irradiation under PEC cell
10
11
93
CH3
3ab, 85%
OMe
F
3ac, 80%
3ad, 72%
n.d.
a Reaction conditions: RVC anode (500 PPI, 1.0 cm × 1.0 cm × 0.5 cm), Pt plate
cathode (0.5 cm × 1.0 cm), 1a (0.2 mmol), 2a (0.2 mmol), nBu4NBF4 (0.1 M),
MeCN (5.0 mL), argon. Yield determined by 1H NMR analysis using
diphenylacetonitrile as the internal standard.
N
N
H3C
Ph
Ph
N
Ph
P
O
P
O
PhO
P
O
H3C
OPh
acetonitrile as solvent, the desired product 3aa was obtained
in 90% yield with reticulated vitreous carbon (RVC) anode and
Pt plate cathode (Table 1, entry 1). Slightly decreased reaction
yields were obtained with nBu4NPF6 or nBu4NClO4 as
electrolytes (Table 1, entries 2-3). By using nBu4NBF4 as
electrolyte, we replaced acetonitrile with other solvents such
as methanol (MeOH), N,N-dimethylformamide (DMF) and
tetrahydrofuran (THF). However, all of them resulted in lower
reaction yields (Table 1, entries 4-6). Remarkably, a significant
drop in yield was observed under air atmosphere (Table 1,
entry 7). Moreover, control experiment showed that electric
current was essential to this reaction (Table 1, entry 8). With
the validated electrochemical results, we explored the
possibility of PEC catalytic P-H/C-H cross-coupling under much
reduced external bias input. The initial PEC experiments were
carried out in an undivided cell equipped with BiVO4 as the
working electrode, Pt plate as the counter electrode and
Ag/AgCl as the reference electrode. With a constant potential
of +0.5 V vs Ag/AgCl, however, the coupling product was
obtained in 39% yield after 12 h of photoelectrolysis (Table 1,
entry 9). Introduction of 0.2 equivalent N-hydroxyphthalimide
(NHPI) mediator dramatically enhanced the photocurrent
density, thus leading to an excellent yield of desired product
(Table 1, entry 10).
H3C
CH3
3ae, 84%
3af, 79%
3ag, 75%
N
N
N
Ph
Ph
Ph
MeO
P
O
EtO
P
O
BuO
P
O
OMe
OEt
OBu
3ak, 64%
3ai, 81%
3aj, 70%
a Reaction conditions: BiVO4 photoanode as the working electrode (1.0 cm × 2.0
cm), Pt plate as the counter electrode (0.5 cm × 1.0 cm), Ag/AgCl as the
reference electrode, 1 (0.2 mmol), 2 (0.2 mmol), NHPI (0.2 equiv.), 2,6-Lutidine
(1.5 equiv.), nBu4NBF4 (0.1 M), MeCN (5.0 mL), E= 0.1 V vs Ag/AgCl, 12h, argon,
Blue LEDs (λ = 450 nm). Isolated yields are shown.
could proceed smoothly with good yields (3ea-3fa).
Subsequently, the scope of P(O)H compounds was also studied.
A variety of P(O)H substrates with electron-rich or electron-
deficient groups were all tolerated in this reaction (3ab-3ad).
Moreover, the reaction took place efficiently when the meta-
position of the phenyl ring was substituted with two methyl
group (3ae). Other substrates, such as di(naphthalen-1-yl)
phosphine oxide and phosphite esters, also generated the
desired products in moderate yields (3af-3ak).
In the absence of light irradiation, we found
electrochemistry catalytic P-H/C-H cross-coupling with
a
significant increase in external bias input (Table 3). The tertiary
amines derivatives with either electron-donating or electron-
withdrawing groups were well tolerated and afforded products
in moderate to excellent yields (3aa-3la). Moreover, various
substituents of P(O)H compounds were also tolerated in the EC
cell (3ab-3ag). However, an electron-deficient chloro group at
the para-position of the aromatic ring led to a lower reaction
yield (3ah). Importantly, phosphite esters were found suitable
for EC system, but the yield gradually decreased with the
increase of chain length (3ai-3ak). From the above results, we
inferred that both PEC and EC systems can work well for C−P
bond construction.
To examine the generality of the PEC strategy, the scope of
the substrates was investigated using BiVO4 photoelectrode
under the standard conditions (Table 2). Firstly, we studied the
reactivity of diverse tertiary amines. The derivatives bearing
methoxyl and methyl at the para-position of the aromatic ring
showed good reactivity in this transformation (3ba-3ca). The
strong electron-withdrawing group trifluoromethyl was well
tolerated to afford products in good yields (3da). In the case of
ortho- or meta-substituents on the phenyl ring, the reaction
2 | J. Name., 2012, 00, 1-3
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Table 3. EC phosphorylation of C−H bonda
View Article Online
DOI: 10.1039/C9CC05375A
R1
O
RVC
Pt
N
R1
R2
P
H
Ar
H2
N
Ar
R2
P
O
MeCN, RT
10 mA / 2 h
R2
R2
1
2
3
3aa, R=H, 85%
OMe
3ba, R=OMe, 80%
3ca, R=Me, 87%
3da, R=CF3, 95%
3ga, R=Et, 84%
3ha, R=F, 84%
3ia, R=Cl, 58%
3jg, R=Br, 76%
N
N
O
Ph
P
O
Ph
P
R
Ph
Ph
3ea, 84%
N
OMe
N
CH3
N
CH3
Ph
P
O
Ph
P
O
Ph
P
O
CH3
Ph
Ph
Ph
3la, 90%
3fa, 99%
3ka, 99%
N
N
Ph
H3
C
C
Ph
N
R
P
R
O
P
O
Ph
RO
P
O
H3
OR
Fig. 1 (a) LSVs of a BiVO4 photoanode obtained under Blue LEDs (λ = 450 nm)
illumination (red) and containing NHPI (green); under dark (black) and containing
NHPI (blue). (b) CVs obtained in MeCN with 0.1 M nBu4NBF4 containing 5 mM 1a
(black), 5 mM 2a (red), 5 mM NHPI (blue); 5 mM NHPI solution containing 10
mM 2,6-Lutidine (green); 5 mM NHPI solution containing 10 mM 2,6-Lutidine
H3
C
CH3
3ae, 92%
3ag, R=Ph, 78%
3ai, R=Me, 89%
3aj, R=Et, 62%
3ak, R=Bu, 43%
3ab, R=Me, 76%
3ac, R=OMe, 84%
3ad, R=F, 78%
3ah, R=Cl, 48%
and 5 mM 1a (pink). Scan rate: 100 mV s−1
.
a Reaction conditions: RVC anode (500 PPI, 1.0 cm × 1.0 cm × 0.5 cm), Pt plate
cathode (0.5 cm × 1.0 cm), 1 (0.2 mmol), 2 (0.2 mmol), nBu4NBF4 (0.1 M), MeCN
(5.0 mL), argon, 10 mA/ 2 h. Isolated yields are shown.
Based on the aforementioned results,
a plausible
mechanism for photoelectrochemical P-H/C-H cross-coupling is
outlined (Scheme 2). Initially, BiVO4 photoelectrode is excited
by the incident photons to generate high energy electron–hole
pairs. Then, the holes reach the surface of BiVO4 to oxidize 1a
into radical cation intermediate (1a•+). At the same time, the
deprotonated NHPI by 2,6-lutidine goes through an anodic
oxidation to give the corresponding PINO radicals.
Subsequently, PINO radical extracts a hydrogen atom from
1a•+ to regenerate NHPI, and the 1a•+ is further oxidized to
afford an iminium ion intermediate (1a+), which reacts with
diphenyl-phosphine oxide via the nucleophilic attack to enable
the formation of final product with C-P bond. Simultaneously,
the released protons are reduced to evolve molecular
hydrogen at the surface of counter electrode.
In summary, we have realized P-H/C-H cross-coupling with
hydrogen evolution via PEC and EC systems. The approaches
show good functional-group tolerance, broad substrate scope
and good to excellent yield. In contrast to the EC system, PEC
system can considerably decrease the applied voltage (i.e.,
>90% external bias) for the C-P bond construction because of
combining visible light energy. From the perspective of energy
saving, PEC has significant advantages over EC that requires a
higher applied potential and electric energy input. Further
extension of PEC to diverse organic synthesis are actively
ongoing in our laboratory.
In the PEC cell, NHPI play a key role in this transformation.
When NHPI was added, the bias required to produce 5.0 mA
photocurrent negatively shifted from 0.5 to 0.1 V (Figure 1a),
the yield of final product increased from 39% to 93% after 12 h
photoelectrolysis. Furthermore, the cyclic voltammetry (CV)
was also performed to explore the reaction mechanism.
Initially, the oxidation peak of N-phenyl tetrahydroisoquinoline
(1a), diphenyl-phosphine oxide (2a) and NHPI was observed at
0.83 V, 1.05 V and 1.62 V (Figure 1b). After adding 2,6-lutidine
in the NHPI solution, a redox couple were appeared at 0.82 V
(half-wave potential). Then, upon the addition of 1a, the
anodic current was enhanced and a significant decrease in the
cathodic current, indicating the regeneration of NHPI via the
reaction between phthalimide-N-oxyl (PINO) radical and 1a.21
These results also indicated that NHPI was involved in the
reaction as a redox mediator.
Undivided cell
e-
e-
N
N
Ph
Ph
1a
e-
Ph
P
O
Ph
O
_
Ph
P
H
H
Ph
H2
N
Ph
O
N
h
Ph
O
N
O
We are grateful for financial support from the Ministry of
Science and Technology of China (2017YFA0206903,), the
National Natural Science Foundation of China (21861132004
and 21603248), the Strategic Priority Research Program of the
Chinese Academy of Science (XDB17000000), Key Research
Program of Frontier Sciences of the Chinese Academy of
Science (QYZDY-SSW-JSC029), the Youth Innovation Promotion
Association of Chinese Academy of Sciences (2018031), and
K.C. Wong Education Foundation.
2H
O
N
OH
O
O
h+
N
O
N
O
_
H
HN
BiVO4 photoanode
Pt cathode
Scheme 2. A plausible PEC oxidation mechanism.
This journal is © The Royal Society of Chemistry 20xx
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Conflicts of interest
There are no conflicts to declare.
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