Visible-light-promoted organic dye-catalyzed sulfidation and phosphorylation of arylhydrazines toward aromatic sulfides and diarylphosphoryl hydrazides

Article abstract of DOI:10.1039/c9nj03692j

Visible-light-promoted sulfidation and phosphorylation of arylhydrazines for the synthesis of aromatic sulfides and diarylphosphoryl hydrazides were developed using the organic dyes rose bengal and Na₂-eosin Y as photocatalysts, respectively. This strategy offers an efficient and mild transition-metal-free synthetic protocol for the formation of C-S and N-P bonds from arylhydrazines.

Full text of DOI:10.1039/c9nj03692j

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DOI: 10.1039/C9NJ03692J
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Visible-light-promoted organic dyes-catalyzed sulfidation and
phosphorylation of arylhydrazines toward aromatic sulfides and
diarylphosphoryl hydrazides
43Received 00th January 20xx,
Accepted 00th January 20xx
Rui Li,a,# Tao Shi,a,# Xiao-Lan Chen,a* Qi-Yan Lv,a,b* Yin-Li Zhang,a Yu-Yu Peng,c Ling-Bo Qu,a and
Bing Yua,b
*
DOI: 10.1039/x0xx00000x
The visible-light-promoted sulfidation and phosphorylation of
On the other hand, phosphorus compounds are of interest in
arylhydrazines for the synthesis of aromatic sulfides and coordination chemistry9 and homogenous catalysis.10 Moreover,
diarylphosphoryl hydrazides were developed using the organic ligands containing N-P bond can be utilized in asymmetric
dyes rose bengal and Na2-eosin Y as photocatalyst, respectively. catalysis.11 However, only limited cases for the synthesis of
This strategy offers an efficient and mild transition-metal-free phosphorylated hydrazides have been reported. For example,
synthetic protocol for the formation of C-S and N-P bonds from Gholivand et al synthesized phosphorylated hydrazides by the
o
arylhydrazines.
coupling of phosphoryl chlorides with arylhydrazines at 0 C
(Scheme 1b).12 However, phosphoryl chloride compounds are
usually unstable and sensitive to water, which will hamper their
applications. In this context, the employment of easily handled
diarylphosphine oxides to replace phosphoryl chlorides will
Organosulfur molecules, particularly sulfides, are ubiquitous
in organic chemicals,1 pharmaceuticals,2 medicines,3 and
materials.4 As a result, the development of efficient methods
toward aryl sulfides is a significant subject of research in
synthetic chemistry. The traditional methods for aryl sulfides
synthesis generally involved transition-metal-catalyzed cross
coupling of electrophilic partners with thiols or sulfides (Scheme
1a).5 For example, Zhao et al reported the synthesis of aryl
sulfides through a Pd-catalyzed cross-coupling of arylhydrazines
and arenethiols.6 Alternatively, transition-metal-free strategies
for the synthesis of aryl sulfides were also developed.7 For
instance, Taniguchi and co-workers reported a transition-metal-
free and oxidant-free protocol for the synthesis of
unsymmetrical aryl sulfides via the coupling of arylhydrazines
with disulfides, but the stoichiometric amount of base was
needed.7b Very recently, Hajra’s group developed an approach
to access aryl sulfides starting from arylhydrazines and thiols
and under visible-light irradiation.8 Despite these significant
advances, the development of transition-metal-free and base-
free procedure for the construction of aryl sulfides under mild
conditions are still highly desirable.
provide
a straightforward method for the synthesis of
phosphorylated hydrazides via the oxidative coupling of P-H
bond.
Visible-light photoredox catalysis has gained much attention for
their wide application in organic chemistry.13 They can act as
powerful and inexpensive tools to initiate organic reactions.14 The
classic photocatalysts like ruthenium and iridium polypyridyl
complexes have proved to be efficient in various reactions, but the
high price, multi-step synthesis and transition-metal contamination
issue might limit their applications.15 Consequently, the application
of organophotocatalysts is a significant metal-free alternative, since
they are usually less toxic, less expensive and easier to handle.16
In the recent years, arylhydrazines have attracted
considerable attention as alternative electrophilic partners in
cross-coupling reactions.17 Various chemical bonds including C-
Conventional synthesis
Pd, Cu, Fe etc
Ar1
X
+ (Ar2S)2 or Ar2SH
Ar1 SAr2
a)
ligand, ~12 h
X = I, Br, N2BF4, NH2, NHNH2, etc
O
O
H
Et3N
MeCN, 0 o
H
b)
Ar
NHNH2
+ Ph
P
Ar2
Cl
Ar
N
N
P
Ph
C
Ph
a. College of Chemistry, Zhengzhou University, Zhengzhou 450001, China. Email:
chenxl@zzu.edu.cn, qiyanlv@zzu.edu.cn, bingyu@zzu.edu.cn
b. Henan Nonferrous Metals Geological Exploration Institute, Zhengzhou 450052,
Henan Province, China.
This work
O
O
c)
HPPh2
Ar1HNN PPh2
H
rose bengal, Cs2CO3
c. Hunan Provincial Key Laboratory of Materials Protection for Electric Power and
Transportation, Changsha University of Science & Technology, Changsha 410114,
China
Ar1NHNH2
Ar2SSAr2
Na2-eosin Y, H2O2
Ar1 SAr2
# Rui Li and Tao Shi contributed equally
†Electronic Supplementary Information (ESI) available:
+ Visible-light-promoted + Room temperature
+ Cheap photocatalyst
+ One-pot reaction
+ Transition-metal-free + Tunable reactivity
See DOI: 10.1039/x0xx00000x
Scheme 1 Transformation of arylhydrazines for C-S and N-P bond formation
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C-Se,21 and C-P22 bonds could be optimal oxidant for further investigation due to its
1
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C,18 C-N,19 C-S,7b,
8, 20
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constructed from arylhydrazines. Particularly, arylhydrazines environmentally friendliness. SubsequeDnOtlIy: ,10.o10th39e/rC9sNoJl0v3e6n9t2sJ,
can function as arylating agents by releasing nitrogen gas. For such as DMF, THF, MeOH or PhCH3, were applied as the reaction
instance, in our recent work, the synthesis of arylphosphonates media, notable decrease of yields were observed (entries 11-
from arylhydrazines and trialkylphosphites was realized under 14). Then, we optimized the amount of substrate 2a and
visible-light irradiation with eosin B as photocatalyst.23 In our catalyst Na2-eosin Y (entries 15-19). To our delight, yields of 3a
continuing research on green chemistry and photocatalytic were increased significantly with increasing the loading of
organic synthesis,24 we envisioned that the reactivity of diphenyl disulfide and lowering the amount of photocatalyst.
arylhydrazines could be tuned by rational designed substrates Therefore, the optimized conditions were established using 5
and judicious selection of catalysts. Herein we report a mol% of Na2-eosin Y and 1 equiv of H2O2 under blue LEDs
controllable sulfidation and phosphorylation of arylhydrazines irradiation for 8 h (entry 19).
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with organic dyes as catalyst by visible-light irradiation under
mild conditions with/without the releasing of N2 (Scheme 1c).
With the optimal conditions in hand, we explored the scope
of visible-light promoted sulfidation of hydrazines (Table 2). As
Our studies were initiated by examining the model reaction it can be seen, diphenyl sulfide 3a was obtained in 68% isolated
of phenyl hydrazine 1a with diphenyl disulfide 2a under visible- yield. The arylhydrazines bearing electron-donating group (-
light irradiation in the presence of various photocatalysts, OMe) at the para-position showed good compatibility affording
oxidants and solvents (Table 1). Firstly, various organic dyes the desired product 3b in 64% yield. Gratifyingly, arylhydrazines
including rose bengal, Na2-eosin Y, eosin Y, Na2-eosin B, with strong electron-withdrawing group (-NO2) at the ortho-
rhodamine B, and eosin B were surveyed as photocatalysts (10 and para-positions also delivered the corresponding products
mol%) in the presence of H2O2 as oxidant in DMSO (entries 1-6). (3c and 3d) albeit with low yields. The heterocycle containing
Among them, Na2-eosin Y was found to be the most active hydrazine, i.e. 2-hydrazinylpyridine, reacting with 2a also gave
catalyst giving the desired product 3a in 30% yield (entry 2). the desired product 3e in good yield (71%). Moreover, various
Then several oxidants were screened employing Na2-eosin Y as diaryl disulfides were subjected into this transformation using
photocatalyst (entries 7-10). Although the yield of 3a obtained phenyl hydrazine 1a as the reaction partner. For example, the
with TBPB as oxidant was promising, H2O2 was chosen as the
diaryl disulfides containing electron-donating groups, such as -
OMe and -NH2, were converted into the desired products 3f and
3g in good yields, respectively. In contrast, diaryl disulfides
bearing a strong electron-withdrawing group -NO2 at ortho- and
para-positions showed relatively poor reactivities (3h and 3i).
To our delight, the heterocyclic and aliphatic hydrazines e.g.,
di(2-pyridinyl) disulfide and dimethyl disulfide can also afford
the desired product 3j and 3k in in yields of 75% and 71%,
respectively. The above-mentioned results suggested that the
transformation of substrates with strong electron-withdrawing
groups into the corresponding sulfides (3c, 3d, 3h, 3i) were not
efficient in this procedure, probably due to the lower reactivity
of the corresponding radical intermediates.
Table 1 Optimization of reaction conditions[a]
Photocatalyst
Oxidant
PhSSPh
Ph NHNH2
+
Ph
S
3a
Ph
Solvent
Blue LEDs
1a
2a
Photocatalyst
Oxidant
Solvent
Yield[b] (%)
Entry
rose bengal
Na2-eosin Y
eosin Y
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
BPO
TBPB
TBHP
DDQ
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
H2O2
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMF
6
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15[c]
16[d]
17[e]
18[f]
19[g]
30
11
18
12
15
18
30
16
18
15
10
6
Na2-eosin B
rhodamine B
eosin B
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Na2-eosin Y
Table 2 The substrate scope of sulfidation of hydrazine
Na2-eosin Y (5 mol%)
H2O2 (1 equiv.)
Ar1 NHNH2
Ar2SSAr2
+
Ar2
S
3
Ar1
S
Blue LEDs, 8 h
1
2
THF
S
S
MeOH
PhCH3
DMSO
DMSO
DMSO
DMSO
DMSO
O2N
MeO
3c
, 20%
3a
, 68%
S
3b
, 64%
0
S
S
10
46
58
62
70
N
OMe
NO2
, 17%
3f
, 74%
S
3e
, 71%
S
3d
S
H2N
3g
O2N
NO2
3h
3i
, 18%
[a] Reaction conditions unless otherwise specified: To a reaction tube, 1a (0.5
mmol), 2a (1.0 mmol), photocatalyst (10 mol%), DMSO (1.5 mL), oxidant (1
equiv.) were added, then the tube was capped and stirred under the irradiation
of blue LEDs at room temperature for 8 h. H2O2 (aq. 30 wt%), BPO = benzoyl
peroxide, TBPB = tert-butyl peroxybenzoate, TBHP = tert-butyl hydroperoxide
(aq. 70 wt%), DDQ = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. [b] GC yields
were given by using biphenyl as internal standard. [c] 2a (0.5 mmol). [d] 2a (2.0
, 70%
, 15%
S
S
Me
N
3k
, 71%
3j, 75%
Reaction conditions: 1 (0.5 mmol), 2 (3.5 mmol), Na2-eosin Y (5 mol%), H2O2 (1
equiv.), DMSO (1.5 mL), blue LEDs, room temperature, 8 h. Isolated yields were
given.
[e]
[g]
mmol). 2a (3.0 mmol). [f] 2a (3.5 mmol). 2a (3.5 mmol), photocatalyst (5
mol%).
2 | J. Name., 2012, 00, 1-3
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Based on the above-mentioned results, we hypothesized that standard conditions (70% yield, Table 1, entry 19).VTiehweAsreticrleeOsunllintes
if hydrazine could undergo a direct N-H functionalization suggested that the oxygen molecule in the air or in situ
without releasing N2, the direct formation of hydrazine generated from H2O2 might play an important role in this
derivatives might be expected. After extensive optimization, it transformation.
DOI: 10.1039/C9NJ03692J
is pleasing to find that the direct coupling of phenylhydrazine
Additionally, when the sulfidation reaction was treated with
and diphenylphosphine oxide toward phosphorylated 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or 2,6-di-tert-
hydrazide could be achieved by rose bengal catalysis in the butyl-4-methyl-phenol (BHT), only trace amount of 3a was
presence of Cs2CO3 under the irradiation of white light (for detected based on GC analysis (Scheme 2b-c). The adducts 4a
details, see supporting information). It’s worth mentioning that and 5a were detected using HRMS (Figure S2-3), demonstrating
in this protocol the desired products could be easily isolated by the radical intermediates Ph• and PhS• were involved in the
simply washing and filtration, which avoided the tedious reaction. Similarly, the phosphorylation reaction was supressed
column chromatography (see supporting information for by adding TEMPO, and the adduct of phosphorous-centred
details). Accordingly, the product 7a can be obtained in isolated radical and TEMPO was observed by HRMS (Figure S4),
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yield of 55%.
indicating the phosphoryl radical was involved in this
The substrate scope of the phosphorylation of arylhydrazines photocatalyzed phosphorylation reaction.
was further studied and the results were showed in Table 3. A
standard conditions
range of arylhydrazines reacted well with diphenylphosphine
oxide, leading to the corresponding products in good yields. The
arylhydrazines bearing electron-donating group gave the
corresponding products 7b-7d in moderate to good yields (67-
76%). Additionally, the catalytic system also displayed good
tolerance to various electron-withdrawing groups, including -F,
-Cl, -Br and -CN, affording the corresponding products 7e-7i in
good yields (63-87%). Overall, no significant electron effect was
observed in this procedure. Notably, 2-hydrazinylpyridine also
worked well in this reaction to give desired product 7j smoothly.
(a)
Ph NHNH2
+
Ph
Ph
S
3a
PhSSPh
1a
2a
trace
30%
24%
36%
66%
Without light
Without rose bengal
Without H2O2
Without air (under N2)
Under O2 (without H2O2)
(b)
Ph NHNH2
standard conditions
TEMPO (2 equiv.)
1a
PhSSPh
2a
+
Ph
+
Ph
S
3a
N
O
SPh
trace
4a
Detected by HRMS
OH
Table 3 The scope of phosphorylation of hydrazine [a]
(c)
(d)
Ph NHNH2
standard conditions
BHT (2 equiv.)
+
1a
Ph S Ph
3a
rose bengal (10 mol%)
Cs2CO3 (1 equiv.)
+
O
O
H
H
N
5a
PhSSPh
Ar1 NHNH2
Ar1
N
Ph
P
H
+
P
Ph
trace
2a
White LEDs, 9 h
Ph
Ph
Ph
1
7
6
Detected by HRMS
O
O
O
H
H
H
N
H
N
H
N
H
N
N
P
Ph
MeO
P
Ph
Me
Cl
N
P
Ph
O
Ph NHNH2
Ph
Ph
Ph
H
H
standard conditions
1a
N
+
O
b
N
P
N
Ph
+
Ph
7a
7b
7c
, 67%
, 62% , 55%
, 76%
O
TEMPO (2 equiv.)
O
Ph
trace
P
Ph
P
H
O
O
O
Ph
H
H
H
N
H
N
H
H
8a
Ph
6a
7a
Ph
N
N
P
Ph
F
P
Ph
Ph
N
N
P
Ph
Ph
Detected by HRMS
Ph
Ph
Ph
7e
, 74%
7d
, 68%
7f
, 69%
Me
Scheme 2 Control experiments
O
O
O
P
H
H
H
H
H
H
N
N
P
Ph
Br
N
N
P
NC
N
N
Furthermore, luminescence quenching studies were carried
out to gain a deeper insight into the reaction mechanism. The
studies were conducted by mixing Na2-eosin Y (Na2-EY) with 1a,
Ph
Ph
Ph
Cl
N
7g
7h
7i
, 63%
, 78%
, 87%
O
H
H
N
N
P
Ph
2a and H2O2, respectively. As
a result, the significant
Ph
7j
, 50%
luminescence quenching effect was detected when Na2-eosin Y
was mixed with 2a (Figure 1a). While the quenching effect of 1a
and H2O2 was not obvious (Figure S5). As shown in Figure 1b, a
linear relationship between the concentration of 2a and I0/I (I0
and I are the fluorescence intensity before and after adding 2a)
was observed. The results indicated that 2a was an effective
[a] Reaction conditions: 1 (0.55 mmol), 6 (0.5 mmol), rose bengal (10 mol%),
Cs2CO3 (1 equiv.), CH3CN (1.5 mL), white LEDs, room temperature, 9 h.
Isolated yields were given. [b] 31P NMR yield.
To further understand the mechanism of these
transformations, we carried out preliminary mechanistic
investigation. As illustrated in Scheme 2a, when the sulfidation
reaction was performed in the absence of visible-light,
photocatalyst, or oxidant, only trace or lower yield of products
3a were obtained. The results indicated that visible-light, Na2-
eosin Y, H2O2 and air were all necessary for the reaction. Then
the reaction without H2O2 under the atmosphere of O2 gave the
product 3a in 66% yield, which is similar with that of the
quencher of Na2-eosin
information).
Y (for details, see supporting
Based on the above experimental observations and related
reports,25 a plausible mechanism was proposed in Scheme 3.
First, the photocatalyst Na2-eosin Y was irradiated to the excited
state PC*, which then was converted into PC•- through a single
electron transfer (SET). Then the oxidation of PC•- by dioxygen
(from H2O2 and air) afforded the ground state photocatalyst and
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O2•-. Meanwhile, phenyl hydrazine 1a was oxidized to afford photocatalytic strategies might pave the way foVrietwhAerticrleelOantleinde
radical cation 9. The deprotonation of radical cation 9 by O2•- or transformation of arylhydrazines.
DOI: 10.1039/C9NJ03692J
base afforded radical 10. Then via a SET process followed by
deprotonation rendered radical 10 converted into radical 11,
which then was converted into radical 12. Subsequently, the
Conflicts of interest
elimination of nitrogen from 12 formed the phenyl radical 13.
On the other hand, the phenyl sulfide radical 14 was generated
through homolytic cleavage of 2a under the irradiation of
visible-light. Finally, the radical coupling of 13 and 14 delivered
the target product diphenyl sulfide 3a. Similarly, the mechanism
of the phosphorylation reaction was also proposed (See
supporting information, Scheme S2).
There are no conflicts to declare.
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11
12
13
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Acknowledgements
We acknowledge the Centre of Advanced Analysis
&
Computational Science (Zhengzhou University) for the
characterization and financial support from NSFC (21501010),
China Postdoctoral Science Foundation (2019M652561), Key
Research Projects of Universities in Henan Province
(19A350011, 20A150006), Henan Province Young Talents
Elevation Program (2019HYTP023) and Hunan Provincial Key
Laboratory of Materials Protection for Electric Power and
Transportation (2019CL03).
8000
6000
4000
2000
0
2.5
2.3
2.1
1.9
1.7
1.5
Na2-EY (0.05 mM)
Na2-EY + 2a (1 mM)
Na2-EY + 2a (3 mM)
Na2-EY + 2a (5 mM)
Na2-EY + 2a (7 mM)
Na2-EY + 2a (9 mM)
(a)
(b)
500
550
600
650
700
0
2
4
6
8
10
Wavelength/nm
2a/mM
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-H+
N
11
-e
-H+
PC
+e
PC
Ph
NH
PC*
PC = Na2Eosin Y
6.
7.
-N2
Ph
13
Ph
N
12
N
Ph S Ph
hv
3a
PhSSPh
PhS
14
2a
8.
9.
G. Kibriya, S. Mondal and A. Hajra, Org. Lett., 2018, 20, 7740.
J. G. Patrick, M. Mary, M. L. Patrick, P. S. Cormac, K. Sarah and
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Scheme 3 Proposed mechanism of sulfidation reaction
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Conclusion
In summary, we have developed a novel visible-light
promoted method to realize controllable sulfidation and
phosphorylation of arylhydrazines under metal-free conditions.
In these protocols, a series of diaryl sulfides and phosphorylated
hydrazides were obtained in moderated to good yields via C-S
bond and N-P bond construction from the easily available
arylhydrazines under mild conditions. Particularly, for the
11. (a) A. Lightfoot, P. Schnider and A. Pfaltz, Angew. Chem. Int.
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synthesis
of
phosphorylated
hydrazides
column
chromatography is avoided. Such a simple and controllable
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9NJ03692J
Table of Contents
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Visible-light-promoted organic dyes-catalyzed sulfidation and phosphorylation
of arylhydrazines toward aromatic sulfides and diarylphosphoryl hydrazides
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Rui Li,a,# Tao Shi,a,# Xiao-Lan Chen,a* Qi-Yan Lv,a,b* Yin-Li Zhang,a Yu-Yu Peng,c Ling-Bo Qu,a and Bing
Yua,b
*
O
O
HPPh2
Ar1HNN PPh2
H
rose bengal, Cs2CO3
Ar1NHNH2
Ar2SSAr2
Na2-eosin Y, H2O2
Ar1 SAr2
+ Visible-light-promoted + Room temperature
+ Cheap photocatalyst
+ One-pot reaction
+ Transition-metal-free + Tunable reactivity
The visible-light-promoted sulfidation and phosphorylation of arylhydrazines for the synthesis
of aromatic sulfides and diarylphosphoryl hydrazides were developed using the organic dyes
rose bengal and Na2-eosin Y as photocatalyst, respectively. This strategy offers an efficient
and mild transition-metal-free synthetic protocol for the formation of C-S and N-P bonds from
arylhydrazines.