Avisible-light-promoted metal-free strategy towards arylphosphonates: Organic-dye-catalyzed phosphorylation of arylhydrazines with trialkylphosphites

Article abstract of DOI:10.1002/adsc.201801122

A visible-light-induced metal-free catalytic system was developed for the synthesis of arylphosphonates starting from arylhydrazines and trialkylphosphites. By using the inexpensive eosin B as catalyst, sub-stoichiometric amounts of DABCO, and ambient air as oxidant, diverse arylphosphonates were obtained under visible-light irradiation. Notably, this catalytic system is suitable for gram-scale reaction by utilizing sunlight as an illumination source.

Full text of DOI:10.1002/adsc.201801122

Title: A visible-light-promoted metal-free strategy towards
arylphosphonates: organic-dye-catalyzed phosphorylation of
arylhydrazines with trialkylphosphites
Authors: Rui Li, Xiaolan Chen, Shengkai Wei, Kai Sun, Lu-Lu Fan, Yan
Liu, Lingbo Qu, Yufen Zhao, and Bing Yu
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201801122
Link to VoR: http://dx.doi.org/10.1002/adsc.201801122

10.1002/adsc.201801122
Advanced Synthesis & Catalysis
FULL PAPERS
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
A Visible-light-promoted Metal-free Strategy towards
Arylphosphonates: Organic-dye-catalyzed Phosphorylation of
Arylhydrazines with Trialkylphosphites
Rui Li,a Xiaolan Chen,a,b,* Shengkai Wei,a Kai Sun,a Lulu Fan,a Yan Liu,a,c Lingbo Qu,a
Yufen Zhaoa,b and Bing Yua,*
a
College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001, China. E-mail:
chenxl@zzu.edu.cn; bingyu@zzu.edu.cn.
b
c
The Key Laboratory for Chemical Biology of Fujian Province, Xiamen University, Xiamen 361005, China.
College of biological and pharmaceutical engineering, Xinyang Agriculture & Forestry University, Xinyang, 464000,
China
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract. A visible-light-induced metal-free catalytic
system was developed for the synthesis of
arylphosphonates starting from arylhydrazines and
trialkylphosphites. By using the inexpensive eosin B as
catalyst, sub-stoichiometric amounts of DABCO, and
ambient air as oxidant, diverse arylphosphonates were
obtained under visible-light irradiation. Notably, this
catalytic system is suitable for gram-scale reaction by
utilizing sunlight as an illumination source.
Keywords: arylphosphonate; arylhydrazine; visible-light
irradiation; metal-free
Introduction
Phosphonates are significant structural motifs
existing in a large variety of pharmaceutically active
molecules,[1]
organic
materials[2]
and
agrochemicals.[3] Phosphonates have also been widely
used as ligands[4] and synthetic intermediates.[5] In the
past half century, many efforts have been devoted to
the preparation of structurally diverse phosphonates.
Michaelis-Arbuzov reaction is a well known method
Sunlight
irradiation
used
for
the
preparation
of
dialkyl
alkylphosphonates.[6] In the past few decades, many
synthetic methodologies have also been developed
for the synthesis of various arylphosphonates. The
main conventional methods published from 1981 to
2015 for the synthesis of arylphosphonates were the
transition-metal-catalyzed cross-coupling of aryl
halides (or pseudo halides) with trialkylphosphites or
H-phosphonate,[7] pioneered by the work of Hirao et
al published in 1981, known as the Hirao cross-
coupling (Scheme 1a).[8] Despite significant
achievements, from an environmentally friendly point
of view, those procedures still suffer from some
drawbacks, such as the use of metals even highly
toxic noble metals as catalysts, inconveniently
Scheme 1. Synthesis of arylphosphonates.
long reaction time (usually about 24 h) as well as
high reaction temperature.
One of the major research endeavors in modern
synthetic chemistry is to find green methods that can
work under environmentally friendly conditions.[9]
The use of visible-light is an inexpensive and
nonpolluting
means
to
initiate
organic
transformations.[10] Over the last four decades,
photoredox catalysts have widely been used in the
1
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10.1002/adsc.201801122
Advanced Synthesis & Catalysis
fields of carbon dioxide reduction,[11] water
splitting,[12] and the development of solar cell
materials.[13] Only over the past ten years, a blooming
development of visible-light photoredox catalysis for
organic synthesis has been witnessed.[14] The recently
developed visible-light photoredox catalysts include
ruthenium and iridium polypyridyl complexes and
organic dyes, which efficiently facilitated the
conversion of visible-light into chemical energy
under extremely mild conditions.[15] In spite of the
excellent photocatalytic properties of ruthenium and
iridium polypyridyl complexes in organic synthesis,
the metal complexes are usually expensive and
potentially toxic. In contrast, organic dyes are an
attractive alternative to the transition metal
complexes as photoredox catalysis in that they are
usually less expensive, less toxic, and easier to
handle.[16] For example, the organic dyes such as
methylene blue,[17] eosins,[18] rhodamines,[19] etc. have
been proved to be excellent visible-light
photocatalysts in a number of synthetic reactions,
represented by visible-light induced aerobic oxidative
radical addition of aryl hydrazines to alkenes,[17a]
cross-dehydrogenative coupling reaction[20] and
visible-light photo-Arbuzov reaction[21] etc.
by a dye-catalyzed photocatalytic process under
irradiation of visible-light and metal-free reaction
conditions.
Results and Discussion
We initiated the meaningful study, starting with
establishing optimal experimental conditions using
the model reaction of phenylhydrazine 1a with
triethylphosphite 2a under visible-light irradiation in
the presence of various organic dyes and bases in
o
CH3CN at 45 C for 6 h as shown in Table 1. The
solvents and reaction time screening were
Table 1. Optimization of the reaction conditions. a)
b)
Yield
Entry
PC (Photocatalyst)
Base
(%)
15
15
14
16
16
27
21
11
9
1
2
3
4
5
6
7
8
Rose Bengal
Fluorescein
Rhodamine B
Eosin Y
Na2Eosin Y
Eosin B
Methylene blue
Eosin B
Eosin B
DABCO
DABCO
DABCO
DABCO
DABCO
DABCO
DABCO
NaHCO3
K2CO3
To date, photoredox catalysis has already been
extensively used to form C-C and C-X (X = O, N and
S) bonds. In contrast, photoredox catalysis is
relatively underdeveloped in organophosphorus
chemistry to form C-P bonds. Only limited examples
concerning using photoredox catalysis to synthesize
organophosphorus compounds have been reported
over the past five years.[22] Xia et al developed a
photocatalytic method for the C(sp2)-P bond
9
10
11
12
13
14
15
16
17c)
18cd)
19ce)
20cf)
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Eosin B
Cs2CO3
K3PO4
2,6-lutidine
TBD
DBU
TMG
22
8
7
formation via
a
denitrogenative coupling of
18
21
19
18
70
57
22
56
60
benzotriazoles with phosphites catalyzed by a iridium
polypyridyl complex.[22b] Two novel synthetic
methodologies, by using ruthenium polypyridyl
complexes as visible-light photoredox catalysis for
the synthesis of arylphosphonates, were reported
successively by Toste et al (Scheme 1b)[7l] and König
et al (Scheme 1c)[23]. Nevertheless, the high cost and
multi-step synthesis of the noble metal-based
Et3N
DABCO
DABCO
DABCO
DABCO
DABCO
21cg)
photocatalysts,
and
the
transition-metal
a)
Reaction conditions unless otherwise specified: To a
reaction tube, 1a (0.5 mmol), 2a (1.0 mmol), photocatalyst
(5 mol%), CH3CN (1.5 mL), base (50 mol%) were added,
then the tube was capped and stirred under the irradiation
of white LEDs at 45 oC for 6 h. DABCO = 1,4-
contamination issue might limit their applications.
Very recently, Breugst and Lakhdar group developed
an approach to access aryl phosphonates starting from
diaryiodonium salts and phosphites under blue-light
irradiation.[22c] However, diaryiodonium salts have
very limited commercial availability. Therefore, it is
highly desirable to exploit inexpensive, metal-free,
efficient and environmentally friendly photochemical
approaches for the synthesis of arylphosphonates.
Based on our continuing study of organophosphorus
chemistry and green chemistry,[24] we herein reported
a novel visible-light-driven organic-dye-catalyzed
diazabicyclo[2.2.2]octane,
TBD
DBU
TMG
=
1,5,7-
1,8-
Triazabicyclo[4.4.0]dec-5-ene,
Diazabicyclo[5.4.0]undec-7-ene,
=
=
1,1,3,3-
tetramethylguanidine. b) Yields were given by 31P NMR.
c)
d)
e)
f)
g)
Open air. Blue LEDs. Red LEDs. Green LEDs
Reaction under sunlight irradiation.
photoredox
reaction,
by
which
various
arylphosphonates were efficiently synthesized from
arylhydrazines and trialkylphosphites under mild and
metal-free conditions (Scheme 1d). To the best of our
knowledge, this is the first example for the
construction of arylphosphonates from arylhydrazines
initially carried out and the yields were determined
by 31P NMR with area normalization (for details see
Table S1). Then, various organic dyes, such as Rose
Bengal, fluorescein, Rhodamine B, eosin Y,
Na2Eosin Y, eosin B and methylene blue, as the
2
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10.1002/adsc.201801122
Advanced Synthesis & Catalysis
photocatalysts were surveyed in the presence of
DABCO (50 mol%) in CH3CN for 6 h in closed tubes,
respectively (entries 1-7). Among them, eosin B was
the most promising photocatalyst, delivering the
desired product 3a in 27% yield.
By using eosin B as photocatalyst, bases, including
NaHCO3, K2CO3, Cs2CO3, K3PO4, 2, 6-lutidine, TBD
DBU, TMG, and Et3N were screened, respectively
(entries 8-16). The results indicated that DABCO was
superior to the others (entry 6 vs entries 8-16).
Surprisingly, the yield of 3a was significantly
improved to 70% when the reaction was conducted in
open air by using eosin B (5 mol%) and sub-
stoichiometric amounts of DABCO (50 mol%) (entry
17). Then the model reaction was evaluated under
blue, red and green light in open air, affording the
product 3a in 57%, 22% and 56% yield, respectively.
Further investigations on the amounts of DABCO and
eosin B were finally carried out (For details, see
Table S1). After intensive experimentation, the
optimal conditions were established as follows: 1a
Scheme 2 A: Gram-scale synthesis of 3a with sunlight
irradiation: phenylhydrazine 1a (13.8 mmol, 1.5 g),
triethylphosphites 2a (27.6 mmol, 4.59 g), eosin B (5
o
mol%), CH3CN (25 mL), DABCO (50 mol%), 6 h, 45 C;
B: A specially designed apparatus for gram-scale synthesis
of 3a.
Table 2. Substrate scope of the visible-light-promoted
arylphosphonates formation a)
(0.5 mmol), 2a (1.0 mmol), eosin B (5 mol%),
DABCO (50 mol%), CH3CN (1.5 mL) in open air at
45 oC for 6 h with the irradiation of white LEDs.
With the optimized conditions in hand, we further
explored the scope of this novel visible-light-induced
dye-catalyzed reaction via the reaction of a variety of
commercially available arylhydrazines 1 with various
phosphites 2 as shown in Table 2. As it can be seen,
diethyl phenylphosphonate 3a was obtained in 60%
isolated yield under the standard conditions. The
arylhydrazines bearing electron-rich groups such as
t
MeO-, Bu-, Me- groups at different positions of
benzene ring showed good reactivities in the catalytic
system, giving the corresponding arylphosphonates
3b-e in moderate to good yields. The mono- or di-
substituted arylhydrazines with electron-withdrawing
groups at different positions of benzene ring,
including F-, Cl-, Br-, CF3-, and CN-, reacted
smoothly with triethylphosphite 2a, affording the
desired arylphosphonates 3f-m in moderate to good
yields. No obvious electronic effects were observed
in cases of 3b-m. However, in contrast, arylhydrazine
substrates containing a strong electron-withdrawing
nitro group at para- or ortho-position showed
a) Reaction conditions: 1 (0.5 mmol), 2 (1.0 mmol), eosin B
(5 mol%), CH3CN (1.5 mL), DABCO (50 mol%), white
LEDs, 6 h, 45 oC, open air. Isolated yields were given.
relatively
poor
reactivities,
delivering
the
corresponding arylphosphonates 3n-o in 14% and
22% yields, respectively. The reason of low yields
was the formation of two by-products confirmed by
GC-MS (for details, see the Supporting Information).
Furthermore, various phosphites were employed as
substrates for this protocol to further examine the
reaction scope. As it can be seen, both
tributylphosphite and triisopropylphosphite displayed
good compatibilities with various arylhydrazines,
affording the corresponding arylphosphonates 3p-u in
good yields under the standard reaction conditions.
To our delight, triphenylphosphite, a sterically
3
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10.1002/adsc.201801122
Advanced Synthesis & Catalysis
hindered phosphite, was also suitable for the
synthesis of arylphosphonates 3v-w although with
diminished yields.
conditions at every 30 min interval for a total of 150
min. The yield of 3a was determined by 31P NMR
every 30 min. As it can be seen, rapid increases in
yields were always observed in those situations as the
reaction being carried out under irradiation conditions.
However, in contrast, slow increases in yields were
always observed in those situations as the reaction
being done in the absence of irradiation conditions,
demonstrating an essential role of the visible-light
irradiation in the reaction transformation.
Given the fact that this photocatalysis system
works well for the synthesis of arylphosphonates
under irradiation of white LEDs, we conducted the
reaction to access 3a with solar irradiation (Table 1,
entry 17). As it can be seen, 60% 31P NMR yield of
3a was obtained when the reaction was irradiated by
sunlight for 6 h in the open air. Following that, a
gram-scale experiment was carried out under solar
irradiation for 6 h in the open air in our specially
designed reactor as illustrated in Scheme 2. We were
delighted to find that the arylphosphonate 3a was
60
On
Off
On
Off
On
31
obtained in 55% P NMR yield. The results indicate
sunlight, as a renewable and clean energy source, is
suitable for being employed as our energy source for
synthesizing arylphosphonates as well (For details,
see the Supporting Information).
40
20
0
To gain a deeper insight into the mechanism of this
photocatalysis reaction, we carried out a series of
control experiments. As shown in Scheme 3a, when
the reaction was conducted in the absence of visible-
light, or air, or photocatalyst, or base, none or trace
amounts of product 3a were observed. When the
reaction was treated with 2,2,6,6-tetramethyl-1-
piperidinyloxy (TEMPO), a radical scavenger, only a
trace of 3a was detected based on 31P NMR analysis
(Scheme 3b). Additionally, when the reaction was
treated with 2,6-di-tert-butyl-4-methyl-phenol (BHT),
another radical scavenger, the reaction was seriously
inhibited with only 30% product of 3a being detected.
Meanwhile, a radical coupling adduct 4a was
detected in the reaction solution using HRMS (see
Fig S1), reminding that phenyl radical was produced
and trapped by BHT (Scheme 3c).
0
30
60
Time/min
90
120 150
Figure 1. “On/off” LED irradiation experiment for the
synthesis of phenylphosphonate 3a.
We subsequently conducted
a
series of
luminescence quenching studies to gain further
insight into the related photocatalytic mechanism. We
carried out the luminescence quenching studies
(Stern-Volmer quenching experiments) by mixing
eosin B (EB) with 1a, 2a, and DABCO, respectively.
The significant luminescence quenching effect of
DABCO was observed. However, in contrast, the
luminescence quenching effects from the other
reactants like 1a and 2a were not obvious (Figure 2a).
As delineated in Figure 2b-c, a linear relationship
between I0/I (I0 and I are the fluorescence intensities
before and after the increasing the concentration of
DABCO, respectively) and the concentration of
DABCO was observed, indicating the DABCO was
an effective quencher of EB.
Based on the above-mentioned results and
literature reports,[17a,
a plausible mechanism for
21]
this visible-light-mediated reaction was proposed
(Scheme 4). First, EB is excited to form EB* in the
Scheme 3. Control experiments.
One more experiment was carried out for further
demonstrating the important role of visible-light
irradiation in the synthesis as depicted in Figure 1.
The model reaction of 1a with 2a was designed to be
conducted under successive on/off LED irradiation
4
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10.1002/adsc.201801122
Advanced Synthesis & Catalysis
hydrazine 1a is oxidized by DABCO•+, affording
hydrazine radical ion 5 together with DABCO. Then
(a)
EB
200
EB + 1a
EB + 2a
EB + DABCO
•-
the deprotonation of radical ion 5 by O2 or DABCO
results the formation of radical 6 and hydroperoxyl
radical (HOO•) or [HDABCO]+. Afterwards, a single-
electron oxidation of radical 6 by DABCO•+,
followed with deprotonation, leads to the formation
of phenyldiazene 7. Then another single-electron
oxidation followed by deprotonation realizes the
transformation of 7 to radical 8. The subsequent
release of a molecule of nitrogen from 8 generates the
phenyl radical 9. Finally, an addition of phenyl
radical 9 to trialkylphosphites is followed, generating
an unstable phosphoranyl radical 10, which is then
quickly transformed into the target phosphonate (3a)
and ethane (EtH) with participation of a proton and
an electron generated in the process of the
photocatalytic reaction.
100
0
500
600
700
800
Wavelength/nm
(b)
EB + DABCO (2 mM)
60
EB + DABCO (3 mM)
EB + DABCO (4 mM)
EB + DABCO (5 mM)
EB + DABCO (6 mM)
EB + DABCO (8 mM)
30
0
500
600
700
800
900
Wavelength/nm
1.6
(c)
A
measurement on quantum yield of the
1.4
1.2
1
photoreaction was further conducted. The result of
the quantum yield of the photoreaction showed that 4
equivalents of product were formed for every photon
absorbed (for details, see the Supporting Information),
which was a result that could be consistent with the
chain mechanism shown in Scheme 4.[25]
0.8
0.0
2.0
4.0
6.0
8.0
10.0
DABCO/mM
Figure 2. Luminescence quenching study: (a) the emission
spectra of a 5 × 10-5 M solution of eosin B with reactants in
degassed anhydrous CH3CN excited at 508 nm; (b) the
emission spectra of a 5 × 10-5 M solution of eosin B with
various concentrations of DABCO in degassed anhydrous
CH3CN excited at 508 nm; (c) The linear relationship
between I0/I and the increasing concentration of DABCO.
Conclusions
In summary, we have developed a metal-free
photocatalysis system for the construction of
arylphosphonates
from
easily
available
arylhydrazines and trialkylphosphites under visible-
light irradiation. By using the organic dye eosin B as
catalyst, sub-stoichiometric amounts of DABCO, and
ambient air as oxidant, a variety of arylphosphonates
were successfully synthesized. Notably, this catalytic
system is also possible for gram-scale reaction by
utilizing sunlight as an illumination source. The
eminent merits of the synthetic method include an
inexpensive and non-toxic photocatalyst (eosin B), a
simple one-pot operation, metal-free and mild
reaction conditions as well as eco-friendly energy
source (solar light) and oxidant (oxygen in air). This
strategy demonstrates that visible-light-mediated
organic dye-catalyzed photocatalysis as an eco-
friendly method has high potential for the synthesis
of various arylphosphonates.
Experimental Section
Scheme 4. The proposed mechanism.
To a 25 mL reaction tube, arylhydrazines (0.5 mmol),
trialkylphosphite (1.0 mmol), eosin B (5 mol%), DABCO
(50 mol%) were dissolved in CH3CN (1.5 mL), and then
the tube was stirred under the irradiation of white LEDs in
presence of white LEDs light. Then via a single
electron transfer (SET) process from DABCO to EB*,
the excited state of EB (EB*) is reductively quenched
by DABCO with generation of the radical cation
DABCO•+ and anion EB•-. The oxidation of EB•- by
dioxygen (air) in the following step affords the
o
open air at 45 C for 6 h. After reaction, the mixture was
diluted with water and extracted with ethyl acetate (25 mL
× 3). The combined organic layers were collected and
dried by anhydrous Na2SO4. The residue was purified by
column chromatography on silica gel to afford the desired
products.
•-
ground state EB and O2 . In those process, DABCO
is also partially consumed by protonation. Meanwhile,
Acknowledgements
5
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10.1002/adsc.201801122
Advanced Synthesis & Catalysis
We acknowledge financial support from National Natural Science
Foundation of China (No. 21501010), the 2017 Science and
Technology Innovation Team in Henan Province (No. 22120001),
Major scientific and technological projects in Henan Province
(No. 181100310500).
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