A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH

Article abstract of DOI:10.1039/c9cc01378d

A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.

Full text of DOI:10.1039/c9cc01378d

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
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DOI: 10.1039/C9CC01378D
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Scalable, Electrochemical Dehydrogenative Cross-Coupling of
P(O)H Compounds with RSH/ROH
Yujun Li, Qi Yang, Liquan Yang, Ning Lei and Ke Zheng*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
a) Traditional routes for the construction of P-S and P-O bonds
A practical, scalable electrochemical dehydrogenative cross-
coupling of P(O)H compounds with thiols, phenols and alcohols in
both undivided cell and continuous-flow setup is disclosed. The
broad substrate scope (>50 examples), good functional-group
tolerance and scalability (>10 g) show the potential for the practical
OTf
I
H-SR
R
,
H-OR
R
chemical oxidants
transition-metal (Pd, Ru, Cu) R1
O
O
O
transition-metal (Cu, Fe)
P
R1
P
R1
P
SR
X
OR
R2
high temperatures (>80 oC)
X = H, OH
R2
photoredox
strong alkoxide base
X = H
R2
synthesis.
A
preliminary mechanistic study suggests the
Using phosphorus radicals
b)
phosphorus radicals are involved in the catalytic cycle.
Ag2O (3 equiv), 100 oC, DMF
1.
O
O
Mn(OAc)2 (2 equiv), 40 o
C
2.
3.
R1
P
R1
P
organophosphorus
compounds
H
Organophosphorus compounds serve as important
intermediates in organic synthesis, medicinal chemistry,
materials and agrochemistry.1-2 Traditional routes for the
construction of P-S and P-O bonds generally (such as the
Atherton-Todd-type reactions) proceed by nucleophilic
substitution of the toxic and moisture sensitive halides RP(O)Cl
with RSX/ROH in presence of strong bases and toxic solvents, in
which with limited functional-group tolerance and multistep
reaction progress.3-4 Additionally, a variety of oxidative
methods including metal-catalyzed,5 photoredox-catalyzed6
and chemical oxidants catalyzed7 cross-coupling of P(O)-H
compounds with RSH or ROH has been developed in recent
years (Scheme 1a). In the meantime, organic radical reactions
have emerged as a powerful strategy for the synthesis of
versatile compounds.8 Given the accessible bond dissociation
energies (BDE ≈ 90 kcal mol−1) of the P−H bond of secondary
phosphine oxides and related structures,9 several radical
strategies10 by using stoichiometric amounts of metal oxides
Ag(I)10a-c and Mn(III) reagents10d; photocatalyst10e-g or other
reagents10h to generate phosphorus radicals, have been
R2
hv (Ir, Ru, eosin Y), base , rt
R2
c) This work
O
R1
P
A
SR
O
H
H
SR
OR
R2
R1
P
H2
+
+
H
oxidant-free
O
R2
R1
P
OR
R2
Mild reaction conditions
Broad substrate scopes
gram-scale synthesis
.
.
.
Scheme 1 Methods for construction of P-S and P-O bonds
Electrochemistry offers a green and efficient alternative to
conventional chemical approaches for redox transformations,
electrons as “reagents” are tunable in the activation of organic
molecules to generate reactive intermediates, which provides new
opportunities for the construction of important organic molecule in
an environmentally friendly way.11 Recently, efficient
electrochemical protocols have been achieved by groups of Baran,
Waldvogel, Lei, Xu, Ackermann, Stahl and others.12-13 Herein, we
report a new strategy for the generation of phosphorus radicals
reported for the synthesis of organophosphorus compounds through electrochemical and its application in the construction of P-
(Scheme 1b). Despite significant advances that have been made
in this field, the development of efficient, environmentally
friendly, scalable and facile approach is still highly desired,
especially in a oxidant-free fashion.
S and P-O bonds (Scheme 1c). Our strategy provides an efficient and
facile approach for the synthesis of organophosphates and sulphur-
containing organophosphorus compounds under the oxidant-free
conditions. In addition, the reaction can be easily scaled up to 10 g
scale by using a continuous-flow system under mild conditions.
To start our investigation, diphenylphosphine oxide 1 and 4-
methylbenzenethiol 2 were selected as the model substrates for
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of
Chemistry, Sichuan University, Chengdu 610064, P. R. China
n
optimization studies. Initial screening revealed that using Bu4NBF4
as the electrolyte and acetonitrile as the solvent, combined with the
use of platinum anode and cathode with a constant current density
of 3.3 mA cm-2 after 4 hours in the ambient atmosphere, resulted in
E-mail: kzheng@scu.edu.cn
† Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Table 1 Optimization of reaction conditionsa
Table 2 Scope of P-S bond formation with various thiols and different
View Article Online
P(O)H compoundsa
DOI: 10.1039/C9CC01378D
O
P
O
P
SH
Pt
Pt
S
H2
+
H
+
nBu4NBF4 (0.18 M)
MeCN, rt, air, 4 h
j = 3.3 mA/cm2
undivided cell
Pt
Pt
Ar
SR
j = 3.3 mA/cm2
Ar
H
+
H2
RS
H
+
P
"standard conditions"
nBu4NBF4 (0.18 M)
rt, air
undivided cell
3
1
2
P
O
Ar
O
Ar
Entry Deviation from standard conditions
Yield (%)b
1
2
3
4
5
6
7
8
9
None
84
62
71
83
49
68
58
64
56
n.d.
O
O
Ph
P
S
LiClO4 as electrolyte
nBu4NPF6 as electrolyte
DMF as solvent
Ph
P
S
Ph
Ph
e
b
c
4
, 66%
3
, 84%, 81% ; (2.2 g, 85%)
3
X-ray of
CCDC: 1888995
MeOH as solvent
RVC as anode
O
O
O
P
O
Ph
Ph
P
S
Ph
Ph
P
S
F
Ph
Ph
S
Cl
Ph
P
S
Ph
Ph
GC as anode
Ph
Ph
Cl
j = 2.7 mA/cm2, 5 h
j = 4.7 mA/cm2, 3 h
Without current
d
5
, 73%
6
8
, 80%
7
, 66%
, 78%
O
P
O
O
O
S
P
S
Ph
P
S
Br
P
S
O
10
Ph
Ph
Ph
Ph
O
Br
d
d
d
12
11
, 75%
, 70%
10
, 66%
9
,86%
a Standard condition A: Pt plate anode (15 mm×10 mm×0.1 mm), Pt
plate cathode (15 mm×10 mm×0.1 mm), 1 (0.3 mmol), 2 (0.9 mmol),
nBu4NBF4 (0.18 M), MeCN (5.0 mL), rt, I= 5 mA ( j = 3.3 mA/cm2), 4 h.
b Isolated yield. RVC = Reticulated Vitreous Carbon; GC = graphite
rod; n.d. = not detected
O
O
P
O
O
P
Ph
Ph
P
S
Ph
S
Ph
Ph
P
S
Ph
Ph
S
Ph
Ph
Ph
Ph
15
b
16
, 67%
, 62%
13
14
, 75%
, 47%, 46%
O
O
P
O
O
the highest yield for the desired product 3 (84% yield; Table1, entry1).
S
P
S
Ph
P
S
P
S
O
n
n
Ph
when using LiClO4 or Bu4NPF6 instead of Bu4NBF4 as electrolyte,
lower yields were observed (Table 1, entries 2 and 3). The solvent
DMF showed no negative effect, and MeOH afforded the product 3
in only 49% yield (Table1, entries 4 and 5). Among the anode
electrode materials screened, platinum anode proved to be the most
effective at facilitating transformation. Either using RVC (Reticulated
Vitreous Carbon) or GC (graphite rod) to replace the platinum led to
a decreased yield, respectively (Table1, entries 6 and 7). The current
density had a great influence on the reaction, increase or decrease
of electric current gave lower yields (Table1, entries 8 and 9). Control
experiment indicated that the electricity was essential for this
reaction (Table1, entry 10).
Ph
Ph
Ph
O
e
e
17
, 90%
20
19
, 82%
,
84%
18
,
80%
O
P
O
O
P
F
S
P
S
S
F
d
d
80%d
23
,
21
22
, 53%
, 84%
a Standard condition A: the same to table 1. Isolated yield. b Using continuous-
flow setup as reaction instrument, 25 mins. Gram-scale synthesis. Using
c
d
DMF as solvent. e Reaction time = 6 h
using DABCO as the additive, the cross-coupling process proceeded
efficiently to generate the desired organophosphinates in high yields
(up to 93% yield, 24-57). The results indicated this method exhibited
excellent functional group tolerance, and a wide variety of phenols
bearing different substituents including OMe (24), Me (26-27), t-Bu
(28), F (30-31), Cl (32), Br (33-34), I (35) on the benzene ring had been
successfully applied to the reaction to produce the corresponding
products in moderate to high yields. A substrate bearing a highly
coordinative SMe group was successfully subjected to the reaction,
giving the organophosphinate 29 in 65% yield. Other functional
groups such as SO2Me, Ac and CO2Me, as well as strongly electron-
withdrawing NO2, easily hydrolyzed OCF3, easily oxidized CHO groups
were also well-tolerable, affording the corresponding products in
high yield (36-42). The reaction of Bpin substituted phenol (43) gave
a slightly decreased yield. Naphthols and disubstituted phenols were
also proved to be suitable substrates in the reaction (44-51). To our
delight, this method can be applied to the coupling of alcohols, and
various alcohols such as methanol, ethanol and isopropanol were
proven tolerable by using RVC as anode (52-54). Diphenylphosphine
oxide were also investigated, finishing the desired products 55-57 in
30-69% yields. The reaction under flow condition was performed
using Pt as anode, the products 52-54 were obtained with superior
outcomes. To further demonstrate the synthetic utility of this
method, the reaction was conducted on gram scale under the
optimal conditions. 8 mmol 1 reacted with 2 to furnish the desired
With the optimal conditions in hand, the scope of the reaction
was investigated. As shown in Table 2, methyl-substituted
benzenethiols showed good reactivities in this transformation (3-6).
Using flow electrochemical reactor, the product 3 was obtained in
81ꢀ% yield with a shorter reaction time (25 mins vs 4 h). Thiophenols
bearing halide (Cl, Br, F) substituents were successfully coupled with
1, affording the products 6-10 in 66-86% yields. In addition, the
electron-rich or electron-neutral substituents at different positions
of benzene ring of thiophenols gave the desired products 10-13 in
good yields. Naphthalenethiol afforded the desired product 14 in 47%
yield (46% yield in 25 mins with the flow system). Moreover, aliphatic
thiols were also suitable substrates for this P-S bond formation
reaction. Phenylmethanethiol and 1-phenylethane-1-thiol were
tolerable, giving the products 15-16 in moderate yields.
cyclohexanethiol, butane-2-thiol, pentane-1-thiol and methyl 2-
mercaptoacetate furnished the desired products in high yields (up to
90% yield; 17-20). The scope of diphenylphosphine oxide was next
investigated, substrates bearing methyl, fluoro and di-methyl groups
at phenyl ring were able to afford desired products 21-23 in 53-84%
yields.
Next, we further applied this electrochemical system to the cross-
coupling of various phenols and alcohols under similar conditions (for
more details, see SI, Table S2). As shown in Table 3, with minor
alterations of anode electrode material (GC-Pt) and electrolyte (KI),
2 | J. Name., 2012, 00, 1-3
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Table 3 Scope of P-O bond formation with various Phenols/alcohols condition without an electric current. These results indicated that
View Article Online
DOI: 10.1039/C9CC01378D
and different P(O)H compoundsa
the
GC
Pt
Ar
OR
O
SH
Ar
j = 3.3 mA/cm2
O
H
standard conditions A
2.0 equiv TEMPO
H2
+
a)
+
RO
H
P
S
N
Ph PH
Ph
O
+
Ph
P
S
P
+
DABCO (50 mol%)
KI (0.12 M)
O
Ar
O
Ph
Ar
MeCN, rt, air
undivided cell
1
2
3
, 72%
59
, 24%
OH
b
c
34
, R = 2-Br, 71%
, R = 4-I, 75%
24
25
26
27
28
29
30
31
32
33
, R = 4-OMe, 78%, 71% ; (1.7 g, 68%)
, R = H, 54%
O
R
35
36
37
38
39
40
41
42
43
Ph
P
O
MeO
, R = 4-SO2Me, 64%
, R = 4-CO2Me, 77%
, R = 4-OCF3, 70%
, R = 4-CHO, 46%
, R = 4-Ac, 79%
, R = 4-Me, 64%
Ph
58
O
O
O
, R = 3-Me, 69%
standard conditions A
2.0 equiv TEMPO
standard conditions B
b)
t
Ph
P
O N
Ph
P
O
O
, R = 4- Bu, 63%
Ph PH
Ph
1.0 equiv TEMPO
d
Ph
Ph
, R = 4-SMe, 65%; (72%, 25 min)
, R = 4-F, 77%
, R = 3-F, 81%
, R = 4-Cl, 76%
, R = 4-Br, 73%
1
24,
22%
60
, 26%
No electric current : n.d.
, R = 3-NO2, 61%
, R = 4-Ph, 62%
28
X-ray of
CCDC:
60
, detected by HRMS
1888996
, R = 4-Bpin, 41%
Scheme 2 Control experiments.
O
5
3
O
O
O
Ph
P
O
Ph
P
O
4
Ph
P
O
Ph
P
O Ar
Ph
Ph
Ph
Ph
R
X
P-O bond formation
P-S bond formation
e
44
45
, Ar = 2-Naphthyl, 72%
, Ar = 1-Naphthyl, 47%
46
47
, X = CN, 68%
52
, 91%
48
, R = 3-F,4-Cl, 81%
, R = 3,5-F2, 72%
, R = 3-Me, 4-F, 57%
, R = 3,4-Me2, 41%
(93%, 25 min)d
, X = Br, 63%
49
50
51
N
N
GC
Pt
e-
Pt
R1S-H
H
3
O
R1OH
O
P
R
P
O
H+
R1
N
e-
O
O
O
O
4
O
N
O
R1O
Ph
P
O
Ph
P
O
R1S
I
S
R2
P
R3
OR1
5
V
S
R1
O
F
Ph
Ph
II
O
R2
P
H
R3
5
3
R
R2
VI
4
O
I
P
1/2H2
I
R2
P
H
R3
e
e
55
56
, R = 3,5-Me2, 54%
, R = 4-F, 69%
53
54
R3
, 79%
, 40%
57, 3
0%
R2
P
H
R3
O
P
R1S
e-
(75%, 25 min)d
(64%, 25 min)d
H+
I
R2
SR1
IV
I
IV
R1S-H
O
R3
I
e-
Flow electrosynthesis
O
R3
P
R2
Pt(+) Pt(-)
II
j = 3.8 mA/cm2
R3
P
R2
HI
III
1/2H2
O
O
III
Ph PH
Ph
+
MeOH
Ph
P
O
I
Ph
180 mL
1
Figure 1. Proposed mechanism.
52
KI (0.12 M)
MeCN, rt
flow rate = 0.2 mL/min
50 mmol
10.8 g, 93% yield
a Standard condition B: GC anode (ϕ 6 mm), Pt plate cathode (15 mm×10
mm×0.1 mm), 1 (0.3 mmol), Phenols (0.9 mmol), DABCO (50 mol%), KI (0.12
M), MeCN (5.0 mL), rt, j = 3.3 mA/cm2 3 h. Isolated yields. b Using ElectraSyn
phosphorus radicals might be generated under the standard
conditions (Scheme 2b). Furthermore, EPR experiments were also
performed. Compare to no signal was observed under the condition
without the electricity, the signal of phosphorus radicals further lent
support to the hypothesis that the formation of phosphorus radicals
in the reaction (SI, Figure S3). For the P-O bond formation reactions,
when 1.0 equiv TEMPO was added under the standard condition B,
the yield of the coupling product 24 decreased to 22% yield, and the
adduct 60 was also detected by ESI-HRMS (Scheme 2b). The EPR data
provided further support for the involvement of phosphorus radical
in the P-O bond formation reaction (SI, Figure S3). In addition, no
product was detected for the control experiment for the reaction
without KI indicated that the iodine ion was essential for this reaction.
Different from the previous report,14 only trace amount of 24 was
obtained, when using I2 instead of KI, suggesting that the I2 was not
involved in the catalytic cycle (SI, Figure S4).
Based on the above experimental results, a plausible mechanism
for this electrochemical dehydrogenative cross-coupling reaction is
proposed in Figure 1. Single-electron-transfer (SET) oxidation of the
thiols by the anode leads to the formation of sulfur radicals,12c-d
followed by rapid dimerization of sulfur radicals to give disulfides II.
In the meantime, the phosphorus radicals III are generated from the
I by a hydrogen atom transfer (HAT) process. The phosphorus radical
intermediates III can undergo either direct coupling with the sulfur
radicals or disulfides to form the final products. Alternatively, the
product also can be produced by nucleophilic attack of the P(O)H
compound with the disulphide (SI, Figure S4). Meanwhile, H2 is
released by cathodic reduction at the cathode. Similarly, for the P-O
bond formation reactions, iodine radical intermediates IV can be
c
2.0 as reaction instrument. Gram-scale synthesis. d Using continuous-flow
e
setup as reaction instrument. DABCO = 1,4-Diaza[2.2.2]bicyclooctane. RVC
anode (100 PPI, 15 mm×10 mm×10 mm), MeCN : alcohol = 4 : 1 (5 mL),
without DABCO.
product 3 in 85% yield (2.2 g; Table 2). Similarly, a gram-scale
reaction between 8 mmol 1 and 58 afforded the desired product 24
in 68% yield (1.7 g; Table 3). Notably, simple continuous-flow
electrochemical reactor was assembled for the scale up to the 10 g
scale, which showed potential for the practical synthesis (52, 93ꢀ%
yield, 10.8 g/70 h; Table 3).
To shine light on the mechanism of this electrochemical
dehydrogenative cross-coupling reaction, several control
experiments were conducted (for more details, see SI). For the P-S
bond formation reactions, when 2.0 equiv TEMPO (2,2,6,6-
Tetramethylpiperidin-1-oxy) was added under the standard
condition A, coupling product 3 was obtained in 72% yield with 24%
radical trapping product 59 (Scheme 2a). In addition, 4-
methylbenzenethiol 2 reacted with styrene to afford the thioether in
78% yield when using styrene instead of substrate 1, and the
disulfide was obtained in 96% yield without substrate 1 under the
standard condition A (SI, Figure S4). These results suggested that
thiyl radical intermediates were involved in the catalytic cycle.
Notably, the radical trapping product 60 was isolated in 26% yield
when 2.0 equiv TEMPO was added without 4-methylbenzenethiol 2
under the standard condition A, which not been detected under the
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ChemistrySelect, 2017, 2, 6891; (f) B. Xiong, X. Feng, L. Zhu, T.
formed from iodide ions through anodic oxidation. Sequentially, the
radical coupling reaction occurs between phosphorus radicals III and
the iodine radicals IV to produce diphenylphosphinyl iodine
intermediates VI, which easily react with phenols or alcohols anions
V to form the P-O bonds. Moreover, several alternative mechanisms
were also proposed in the SI (for more details, see Figure S4).
In summary, we developed an efficient electrochemical
method to construct P-S and P-O bonds under oxidant-free
conditions. Various cheap thiols, phenols and alcohols were
suitable substrates for this transformation with excellent
functional-group tolerance. Importantly, the reaction can be
conducted on a gram scale with good reaction efficiency and a
flow electrochemical method has been developed for >10 g
scale up synthesis, which showed the potential for the practical
synthesis. Further studies on synthetic application are ongoing
in our laboratory.
We thank the National Natural Science Foundation of China
(No. 21602142), and the Fundamental Research Funds for the
Central Universities. We thank the Xiaoming Feng laboratory
(SCU) for access to equipment. We also thank the
comprehensive training platform of the Specialized Laboratory
in the College of Chemistry at Sichuan University for compounds
testing.
Chen, Y. Zhou, C.-T. Au and S.-F. Yin, ACS Catal.,V2ie0w1A4r,tic5le, O5n3li7ne.
DOI: 10.1039/C9CC01378D
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Conflicts of interest
There are no conflicts to declare
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DOI: 10.1039/C9CC01378D
A practical, scalable electrochemical dehydrogenative cross coupling of P(O)H compounds with
thiols, phenols and alcohols