Exogenous-oxidant-free electrochemical oxidative C-H phosphonylation with hydrogen evolution

Article abstract of DOI:10.1039/c9cc00975b

We herein report a versatile and environmentally friendly electrochemical oxidative C-H phosphonylation protocol. This protocol features a broad substrate scope; not only C(sp²)-H phosphonylation, but also C(sp³)-H phosphonylation is tolerated well under exogenous-oxidant-free and metal catalyst-free electrochemical oxidation conditions.

Full text of DOI:10.1039/c9cc00975b

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DOI: 10.1039/C9CC00975B
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Exogenous-oxidant-free electrochemical oxidative C-H
phosphonylation with hydrogen evolution
Received 00th January 20xx,
Accepted 00th January 20xx
Yong Yuan,†ab Jin Qiao,†a Yangmin Cao,a Jingmei Tang,a Mengqin Wang,a Guojuan Ke,a Yichen Lu,a
Xue Liu,a and Aiwen Lei*ab
DOI: 10.1039/x0xx00000x
www.rsc.org/
We herein reported a versatile and environmental friendly thiolation,9
alkylation,10
etc.11
Nevertheless,
the
electrochemical oxidative C-H phosphonylation protocol. This electrochemical oxidative C-H phosphonylation is still
ptotocol features broad substrates scope, not only C(sp2)-H underexplored.12 As part of our recent research interests in the
phosphonylation, but also C(sp3)-H phosphonylation is tolerated area of electrochemical oxidative C-H functionalization, we
well under the exogenous-oxidants-free and metal catalysts-free herein reported an elegant and versatile electrochemical
electrochemical oxidation conditions.
oxidative C-H phosphonylation protocol. Overall, notable
features of this reaction include: (1) neither metal catalyst nor
Phosphorus containing compounds are of much importance
because they are widely found in a vast number of natural
products, biological compounds, and agricultural chemicals,1
as well as represent the outstanding synthetic intermediates
for the preparation of complex organic molecules.2 As such,
methods for the preparation of these valuable molecules are
very important synthetic technologies. Over the past decades,
considerable works have been conducted on the synthesis of
significant phosphorus containing compounds.3 Compared
with the conventional synthetic methods that employed the
pre-functionalized aryl halides or arylboronic acids as the
starting materials,4 direct C-H phosphonylation represents a
much more attractive strategy for C-P bond formation.5
Although this strategy avoided the use of pre-functionalized
starting materials and has achieved considerable
development, most of the reported reactions still suffer from
some drawbacks, such as the need of metal catalysts or
stoichiometric oxidants. Therefore, developing a much more
elegant method for producing phosphorus containing
compounds under a metal catalyst-free and exogenous-
oxidant-free reaction conditions is urgently needed.
exogenous-oxidant/additive
is
required;
(2)
broad
substrate scope, not only C(sp2)-H phosphonylation, but also
C(sp3)-H phosphonylation is tolerated well under the
electrochemical conditions.
Table 1: Optimization of the reaction conditions.a
N
N
+
P(OEt)3
N
N
OEt
P
OEt
O
1a
2a
3a
Entry
Electrolysis conditions
Yield (%)b
1
2
3
4
5
6
carbon rod anode, platinum plate cathode, nBu4NBF4
entry 1 but nBu4NClO4 as electrolyte
entry 1 but nBu4NPF6 as electrolyte
entry 3 but nickel plate cathode
70
54
77 70c
,
61
49
0
entry 3 but carbon cloth anode
entry 3 but no electric current
a
Reaction conditions: carbon rod anode, platinum plate cathode, undivided
n
cell, 1a (0.3 mmol), 2a (0.6 mmol), Bu4NBF4 (0.1 mmol), MeCN (10 mL), 50
oC, 4 mA, 6 h (3 F/mol). b Yields were determined by 31P NMR using PPh3 as
the internal standard. c Isolated yield.
As an ideal alternative to chemical oxidants, electrochemical
anodic oxidation provides an efficient and environmentally
benign synthetic method for C-H functionalization.6 In this
context, considerable progress has been made, such as the
electrochemical oxidative C-H amination,7 oxygenation,8
We initiated our studies by investigating the reaction of 2-
phenylimidazo[1,2-a]pyridine (1a) with triethyl phosphite (2a)
because the imidazopyridine unit is widely existing
substructures in many commercially available drugs and the
resultant C-H phosphonylation products may also have a
potential utility in pharmaceutical chemistry (Table 1).13 To our
delight, when the reaction was performed in an undivided cell
employing carbon rod as anode and platinum plate as cathode
a National Research Center for Carbohydrate Synthesis, Jiangxi Normal University,
Nanchang 330022, P. R. China. E-mail: aiwenlei@whu.edu.cn.
b College of Chemistry and Molecular Sciences, Institute for Advanced Studies (IAS),
Wuhan University, Wuhan 430072, P. R. China.
n
as well as using Bu4NBF4 as electrolyte, the reaction worked
† Yong Yuan and Jin Qiao contributed equally to this work.
‡
Electronic Supplementary Information (ESI) available: See DOI:
smoothly in acetonitrile under a 4 mA constant current,
10.1039/x0xx00000x.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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providing the desired C-H phosphonylation product 3a in 70% a]pyridine could be transformed into the C-H phosphonylation
View Article Online
DOI: 10.1039/C9CC00975B
NMR yield (Table 1, entry 1). At the same time, H2 was also products in 70% and 61% yields, respectively (Table 2, 3a and
detected by GC-TCD. Further explorations showed that 3b). 2-Phenylimidazo-[1,2-a]pyridines bearing both electron-
nBu4NPF6 was a better choice for electrolyte, yielding 3a in 77% donating groups and weak electron-withdrawing groups at the
NMR yield and 70% isolated yield (Table 1, entries 2 and 3). In 2-phenyl moiety afforded the products in moderate to good
comparison, conducting the reaction with a nickel plate yields (Table 2, 3c-3g). In comparison, 2-phenylimidazo-[1,2-
cathode or carbon cloth anode, showed decreased reaction a]pyridine with strong electron-withdrawing group at the 2-
efficiency (Table 1, entries 4 and 5). In addition, control phenyl moiety delivered the C(sp2)-H phosphonylation product
experiment showed that the constant current was crucial for in moderate yield (Table 2, 3h). When 8-methyl, 7-methyl, or
the reaction (Table 1, entry 6) (For more details about 6-methyl substituted imidazopyridines were treated with
optimization of reaction conditions, see ESI). Note that for triethyl phosphite (2a), the corresponding products could still
some conditions with low yields, 1a and its homo-coupling be obtained with moderate to good yields (Table 2, 3i-3k).
product were often observed.
However, when using imidazo[1,2-a]pyridine as the substrate,
only trace amount of C(sp2)-H phosphonylation product (Table
2, 3l) was obtained, the reason for this may because
imidazo[1,2-a]pyridine has a relative high oxidation potential
and is not easily oxidized. It is worth noting that other
heteroarenes, such as important benzo[d]-imidazo[2,1-
Table 2: Substrate scope for the electrochemical oxidative C(sp2)–H
phosphonylation.a
O
C
Pt
P(OR)3
+
Het
Het
H
P
OR
OR
b]thiazole
derivatives,
3-phenylbenzofuran,
2-
1
2
3
phenylbenzofuran, N-methylindole, and p-xylene were also
suitable for this reaction, affording the respective products in
33% to 85% yields (Table 2, 3m-3s). Other phosphonylation
reagents for this electrochemical oxidative C(sp2)-H
phosphonylation protocol were investigated as well.
Delightfully, despite the bulky steric hindrance or a long alkyl
chain, P(OiPr)3 and P(OnBu)3 were well suitable for the reaction
and obtained the C(sp2)-H phosphonylation products in 75%
and 74% yields, respectively (Table 2, 3t and 3u). Note that for
some examples with a longer duration of electrolysis (Table 2,
3c, 3e, 3j, 3k, 3m, 3o, and 3r), the reason for prolonging the
duration of electrolysis is mainly to increase the conversion
rates, thereby further improving the yields.
N
N
S
N
N
N
N
OEt
OEt
OEt
OEt
OEt
P
P
P
OEt
O
O
O
b
3a
3b
, 70%
, 61%
3c
, 66%
N
N
N
OMe
Cl
N
N
N
OEt
OEt
OEt
OEt
OEt
OMe
P
P
P
OEt
O
O
O
b
3d
3f
, 55%
, 63%
3e
, 65%
N
N
N
Br
CN
N
N
N
OEt
OEt
OEt
OEt
OEt
P
P
P
OEt
O
O
O
3g
3h
3i
, 67%
, 46%
, 67%
N
N
N
H
N
N
N
Table 3: Substrate scope for the electrochemical oxidative C(sp3)-H
OEt
OEt
OEt
OEt
OEt
OEt
phosphonylation.a
P
P
P
O
O
O
b
b
3l
, trace
3j
3k
, 58%
, 62%
O
MeO
S
S
S
C
Pt
R1
H
R1
P
OR
P(OR)3
+
N
N
N
N
N
N
OR
5
EtO
EtO
EtO
EtO
4
2
EtO
P
P
P
EtO
3o
, 79%
O
O
O
OMe
O
OEt
OEt
b
b
O
OEt
O
OEt
OEt
3n
, 58%
O
3m
, 85%
O
P
P
O
P
P
OEt
OEt
OEt
O
P
EtO OEt
P
N
N
Ph
OEt
N
O
OEt
N
EtO
EtO
O
N
Ph
P
O
Me
, 74%
b
c
b
b
3p
3q
5a
, 87%
, 51%
, 33%
N
3r
5b
5c
5d
, 30%
, 37%
N
, 46%
O
OMe
O
OnBu
OnBu
O
OC2H4Cl
OC2H4Cl
O
Ph
Ph
P
P
P
P
N
N
OMe
OiPr
OiPr
OnBu
OnBu
P
EtO
EtO
P
P
O
O
O
O
, 62%
O
, 88%
O
, 68%
O
, 68%
3s
3t
3u
, 74%
, 38%
, 75%
d
5f
5g
5e
5h
a Reaction conditions: carbon rod anode, platinum plate cathode, undivided
cell, 1 (0.3 mmol), 2 (0.6 mmol), nBu4NPF6 (0.1 mmol), MeCN (10 mL), 50 oC,
4 mA, 6 h (3 F/mol), isolated yield. b 8 h (4 F/mol).
a Reaction conditions: carbon rod anode, platinum plate cathode, undivided
cell, 4 (0.3 mmol), 2 (0.6 mmol), nBu4NPF6 (0.1 mmol), MeCN (10 mL), 70 oC,
4 mA, 6 h (3 F/mol), isolated yield. b 50 oC. c Yields were determined by 31P
NMR using PPh3 as the internal standard. d 4 (0.6 mmol), 2 (0.3 mmol).
With the optimized reaction conditions in hand, the scope of
the exogenous-oxidant-free electrochemical oxidative C(sp2)-H
phosphonylation was subsequently explored. Initially, different
heteroarenes were investigated. As shown in Table 2, 2-
phenylimidazo-[1,2-a]pyridine and 2-thiophenylimidazo-[1,2-
Subsequently, we turned our attention to the more
challenging C(sp3)-H phosphonylation because no examples
have been reported in which C(sp2)-H phosphonylation and
2 | J. Name., 2012, 00, 1-3
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C(sp3)-H phosphonylation were accomplished concurrently electrochemical oxidative C-H phosphonylation really begins
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under the same or similar reaction conditions. Gratefully, with the oxidation of 1a or 4a instead of D2Oa.I: 10.1039/C9CC00975B
under the electrochemical conditions, the C(sp3)-H Based on the studies above and the previous reports,3b,5b
a
phosphonylation was also accomplished. As shown in table 3, plausible mechanism for this electrochemical oxidative C-H
when xanthene and N-methyl-9,10-dihydroacridine were phosphonylation was proposed in Scheme 2. For C(sp2)-H
employed as substrates, the reaction worked smoothly and phosphonylation, 1a first is oxidized at the anode to form the
afforded the corresponding C(sp3)-H phosphonylation products radical cation intermediate A, which then is captured by P(OR)3
in 87% and 74% yields, respectively (Table 3, 5a and 5b). (2) and delivers the adduct B. B undergoes further anodic
Besides, N,N-dimethylaniline derivative and N-phenyl oxidation and dehydrogenation result in the formation of
tetrahydroisoquinoline were also compatible with the reaction phosphorus cation intermediate D. Finally, the ensuing
conditions (Table 3, 5c-5d). Notably, other phosphonylation dealkylation of D forms the C(sp2)-H phosphonylation product
reagents, such as P(OMe)3, P(OnBu)3, P(OC2H4Cl)3, and even 3. At the same time, protons were reduced at cathode and
diphenylphosphine oxide all were suitable substrates and form H2. With respect to C(sp3)-H phosphonylation, the
obtained the C(sp3)-H phosphonylation products in good to generated intermediate E does not directly react with P(OR)3
high yields (Table 3, 5e-5h). Unfortunately, only trace amounts (2), but sequentially loses one proton and one electron to
of product was detected when P(OiPr)3 was applied as afford intermediate G, G then is captured by P(OR)3 (2) and
substrate, possibly because of the bulky steric hindrance.
delivers the phosphorus cation intermediate H. Subsequently,
To demonstrate the practicality of this electrochemical as with the C(sp2)-H phosphonylation, the ensuing dealkylation
oxidative C-H phosphonylation, reactions of P(OEt)3 with 1a of H leads the C(sp3)-H phosphonylation product 5.
and 4a on 6.0 mmol scale were performed. The reactions
Oxidative C(sp2)-H Phosphonylation
Oxidative C(sp3)-H Phosphonylation
worked smoothly and afforded the corresponding C-H
phosphonylation products in 55% and 50% yield (For more
details about gram scale synthesis, see ESI), respectively.
2 H+
H2
2 H+
H2
+ 2 e
+ 2 e
Pt Cathode
Pt Cathode
N
+
O
O
+
P(OR)3
P(OR)2
N
P(OR)2
Ph
P(OR)3
C
C
C
Pt
Pt
Pt
N
HPO(OEt)2
+
+
+
A
OEt
OEt
- R+
- R+
N
N
N
Ph
P
N
N
O
H
O
5
O
1a
3a
, n.d.
D
3
- H+
P(OR)3
+
N
+
+
H
H
P(OR)3
P(OR)3
N
N
N
N
PO(OEt)3
B
+
N
Ph
Ph
OEt
OEt
, n.d.
N
O
G
O
F
N
P
C
B
- e
- e
C anode
- e
O
O
1a
3a
- H+
C anode
P(OR)3
- e
O
+
+
O
N
N
+
N
Ph
Ph
HPO(OEt)2
C
D
N
O
4a
O
E
OEt
1a
A
P
OEt
4a
5a
, 12%
Scheme 2. Proposed mechanism.
O
O
C
Pt
In summary, we have disclosed a versatile and environmental
friendly electrochemical oxidative C-H phosphonylation
protocol. Under an exogenous-oxidants-free and metal
catalysts-free electrochemical oxidation conditions, a series of
complex and significant phosphorus containing compounds
were constructed with moderate to high yields accompanying
with the hydrogen evolution. Notably, during the reaction,
neither exogenous oxidant nor metal catalyst is required. With
respect to the substrate scope, not only C(sp2)-H
phosphonylation, but also C(sp3)-H phosphonylation is
tolerated well under the electrochemical conditions.
This work was supported by the National Natural Science
Foundation of China (21520102003, 21702081, 21702150), the
Hubei Province Natural Science Foundation of China
(2017CFA010), and the Jiangxi Provincial Education
Department Foundation (GJJ160325). The Program of
Introducing Talents of Discipline to Universities of China (111
Program) is also appreciated.
PO(OEt)3
+
OEt
OEt
P
O
4a
5a
, n.d.
Scheme 1. Control experiments.
To shed light on this exogenous-oxidant-free electrochemical
oxidative C-H phosphonylation mechanism, cyclic voltammetry
(CV) experiments on 1a, 2a, and 4a were performed,
respectively. The oxidation peak of 1a and 4a were observed
at 1.68 V and 2.28 V, respectively, while no obvious oxidation
peak of 2a was observed in 0-2.5 V (For more details about
cyclic voltammetry (CV) experiments, see ESI). This result
suggests that our electrochemical oxidative C-H
phosphonylation might begin with the oxidation of 1a or 4a at
anode. To further gain some insights into the mechanism, the
reactions of 1a and 4a with HPO(OEt)2 or PO(OEt)3 were
performed (Scheme 1), respectively. Besides the reaction of 4a
with HPO(OEt)2 afforded the desired product in 12% yield, no
desired products were detected in any other reactions. These
results indicated that neither HPO(OEt)2 nor PO(OEt)3 are the
reaction intermediates, and once again indicated that our
Conflicts of interest
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There are no conflicts to declare.
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DOI: 10.1039/C9CC00975B
TOC
Electrochemical Oxidative C(sp2)-H & C(sp3)-H Phosphonylation
C
Pt
R-PO(OR)2
P(OR)3
+
R-H
metal-free
26 examples
up to 88% yield
exogenous-oxidant-free
We herein report a versatile and environmental friendly electrochemical oxidative C-H
phosphonylation protocol.