Mn(III)-mediated phosphinoylation of aldehyde hydrazones: Direct “one-pot” synthesis of α-iminophosphine oxides from aldehydes

Article abstract of DOI:10.1016/j.tet.2021.132053

A “one-pot” strategy for the straightforward Mn(III)-mediated phosphinoylation of aldehyde hydrazones with diphenylphosphine oxide to furnish α-iminophosphine oxides is described. This mild and practical method allows the direct use of aldehydes as substrates in one pot to generate the hydrazones, which are then engaged “in situ” by the phosphorus reagent in the presence of Mn(OAc)₃ oxidant. Thus, the requisite isolation of the hydrazones is not needed in this operation. Conducted mechanistic experiments implicate a pathway involving phosphorus-centered radicals.

Full text of DOI:10.1016/j.tet.2021.132053

Tetrahedron 85 (2021) 132053
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Mn(III)-mediated phosphinoylation of aldehyde hydrazones: Direct
“one-pot” synthesis of a-iminophosphine oxides from aldehydes
Xue-Wei Bian, Ling Zhang, Adedamola Shoberu, Jian-Ping Zou*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical Engineering, Soochow University, 199 Renai Street, Suzhou,
Jiangsu, 215123, China
a r t i c l e i n f o
a b s t r a c t
Article history:
A “one-pot” strategy for the straightforward Mn(III)-mediated phosphinoylation of aldehyde hydrazones
with diphenylphosphine oxide to furnish a-iminophosphine oxides is described. This mild and practical
method allows the direct use of aldehydes as substrates in one pot to generate the hydrazones, which are
then engaged “in situ” by the phosphorus reagent in the presence of Mn(OAc)3 oxidant. Thus, the
requisite isolation of the hydrazones is not needed in this operation. Conducted mechanistic experiments
implicate a pathway involving phosphorus-centered radicals.
Received 7 December 2020
Received in revised form
17 February 2021
Accepted 20 February 2021
Available online 5 March 2021
© 2021 Elsevier Ltd. All rights reserved.
Keywords:
CeH functionalization
Phosphinoylation
One-pot reaction
Aldehyde hydrazone
Manganese triacetate.
1. Introduction
(Scheme 1, a) [4aej]. For instance, the copper-catalyzed tri-
fluoromethylation of N,N-dialkylhydrazones using Togni reagent
Aldehyde hydrazones are a unique class of compounds with
important synthetic applications in organic chemistry. Although,
these versatile and readily available reagents are mainly used as
synthetic equivalents of carbonyl compounds, they can also
participate in a plethora of organic transformations including polar,
free radical, pericyclic, and organometallic catalytic reactions [1]. In
addition to the features of carbonyl compounds, the most signifi-
cant property of hydrazones is the umpolung imine reactivity due
to the presence of the electron-donating amino function which
activates the azomethine carbon towards electrophilic substitution
[2]. Thus, the direct functionalization of hydrazones is commonly
realized via electrophilic substitution with highly reactive electro-
philes such as Vilsmeier and Mannich reagents, perfluoroacetic
anhydride, halogens, phosphorus tribromide etc. [3aec] However,
the toxicity of these strong electrophilic reagents as well as poor
functional-group tolerance has limited its widespread application.
In recent times, efficient protocols for the direct C(sp [2])eH
functionalization of aldehyde hydrazones have been developed
including transition-metal catalyzed and radical based methods
was reported by Baudoin’s group [4c]. Zhu’s group also disclosed a
visible-light photoredox catalyzed C(sp [2])eH amination of alde-
hyde hydrazones with N-methyl-N-((phenylsulfonyl) oxy)
benzene-sulfonamide [4d].
Organophosphorus compounds have not only been extensively
used as ligands in catalysis but have also been widely applied for
the synthesis of medicines [5aed], agrochemicals [6a,b], and ma-
terials [7aec]. In particular, compounds (such as aminophosphonic
and aminophosphinic acids) which contain the PeCeN linkage
have been shown to exhibit important biological activities [8aec].
As a result of their importance, tremendous efforts have been
devoted to their synthesis and application [9aeg]. The
a-imino-
phosphine oxide is an important class of compounds which can be
used as ligands, intermediates, and transformed to other important
compounds. Within the context of hydrazone C(sp [2])eH func-
tionalization, Zhu’s group had previously disclosed an efficient
K2S2O8/Cu(OAc)2-mediated oxidative CeH/PeH cross coupling re-
action for the direct preparation of functionalized
a-iminophos-
phine oxides [10a], however the success of the reaction was heavily
reliant on the presence of the dialkyl group activating unit. More
recently, the electrochemical variant was also realized by Ruan and
co-authors [10b]. In spite of these advances, we reckon that the
development of a rapid, direct and step-economical, one-pot
* Corresponding author.
E-mail address: jpzou@suda.edu.cn (J.-P. Zou).
https://doi.org/10.1016/j.tet.2021.132053
0040-4020/© 2021 Elsevier Ltd. All rights reserved.

X.-W. Bian, L. Zhang, A. Shoberu et al.
Tetrahedron 85 (2021) 132053
3a was obtained in 25% yield (Table 1, entry 1). Unsurprisingly, the
reaction efficiency was almost non-existent under conditions pre-
viously described by Zhu’s group [10a] due to the absence of the
dialkyl group activating unit (Table 1, entry 2). Moreover, only trace
amounts of the desired product 3a were observed with other
commonly employed oxidation systems for generating
phosphorus-centered radicals (Table 1, entries 3e4). Notably, the
reaction proceeded more efficiently at ambient temperature for
short time (0.5 h) giving higher yields of 3a (Table 1, entries 5e6).
Meanwhile, a careful investigation of the reaction in other media
showed that MeOH was the best solvent (Table 1, entries 7e11).
Finally, in an attempt to render the reaction catalytic, we examined
the reaction using catalytic amounts of Cu(OAc)2 and K2S2O8 as
oxidant, however only 43% of product 3a was obtained (Table 1,
entry 12). Thus, the optimal conditions were determined to be the
initial reaction of benzaldehyde (1a) (0.053 g, 0.5 mmol) and p-
toluenesulfonylhydrazide (2a) (0.112 g, 0.6 mmol); followed by
diphenylphosphine oxide (0.30 g, 1.5 mmol) and then systematic
addition of Mn(OAc)3 (0.54 g, 2 mmol) resulting in 73% yield of 3a
(Table 1, entry 9).
With the optimal conditions in hand, the scope of the phos-
phinoylation reaction was examined with respect to aromatic and
aliphatic aldehydes (Table 2). With aromatic substrates, electron-
donating groups (methyl and methoxy) and the electron-
withdrawing halo groups were tolerated regardless of substitu-
tion patterns (3a-3f, 3h-3l). However, no desired reaction occurred
with the p-nitrobenzaldehyde substrate (3g). Furthermore, the re-
action was sensitive to steric hindrance as observed by the poor
reactivity of 2,6-dichlorobenzaldehyde substrate (3m). Meanwhile,
secondary alkyl aldehydes were also amenable to this reaction (3n
and 3o), on the contrary, primary and tertiary.
Scheme 1. C(sp [2])eH Functionalization of aldehyde hydrazones (FG ¼ functional
group) synthesis/isolation of hydrazone starting materials prior to phosphinoylation
was not necessary in this process.
strategy for forging hydrazonic C(sp [2])eP bond is highly desirable.
Such a strategy if successful, will allow the direct use of aldehydes
as substrates, to furnish hydrazones which can be then be engaged
“in situ” by the phosphorus reagent. In our previous studies,
Mn(OAc)3 was found a good oxidant for C(sp [2]) eP bond forma-
tion of alkenes [11aed], herein, we disclose a rapid, one-pot strat-
egy to access a-iminophosphine oxides directly from the parent
aldehydes via “in situ” generated varied hydrazones, using
Mn(OAc)3 as oxidant (Scheme 1, b). Notably, the requisite synthesis/
isolation of hydrazone starting materials prior to phosphinoylation
was not necessary in this process.
2. Results and discussion
We began preliminary investigations by employing benzalde-
hyde (1a), p-toluenesulfonylhydrazide (2a), and diphenylphos-
phine oxide as model substrates. At the initial stage, the
phosphinoylation reaction of preformed tosylhydrazone (1a’)
(prepared from the reaction of 1a and 2a) with diphenylphosphine
oxide under oxidative conditions was carried out. Fortunately, the
desired product 3a was isolated in 20% yield by utilizing Mn(OAc)3
as oxidant in CH3CN solvent at 80 ꢀC. Thus,
Alkyl aldehydes were not suitable substrates (3p and 3q). With
the exception of isoxazole-containing aldehyde (3r) (itself reacting
poorly), heteroaryl such as furyl, thienyl and pyridyl substrates
were not compatible under the oxidative conditions (3s-3u).
Next, we turned our attention to investigate the effect of N-
substitution with various hydrazones, obtained from benzaldehyde
(1a) and hydrazine derivatives (Table 3). Similar to aldehyde de-
rivatives studied above, phenylsulfonyl hydrazide and phenyl-
hydrazine derivatives containing electron-donating and electron-
We examined the “one-pot” phosphinoylation reaction of 1a’
(generated “in situ” from 1a and 2a) with diphenylphosphine oxide
under same conditions (Table 1). To our delight, the desired product
Table 1
Optimization of the reaction conditions.a
entry
oxidant (equiv)
solvent
temp (oC)
time (h)
yield (%)b
1c
2c
3c
4c
5
6
7
8
9
Mn(OAc)3 (4)
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
CH3CN
DMF
DMSO
CH3OH
AcOH
80
80
80
80
45
rt
rt
rt
rt
rt
20
20
20
12
0.5
0.5
0.5
0.5
0.5
0.5
0.5
20
25
Cu(OAc)2 (0.25) þ K2S2O8 (3)
AgNO3 (0.05) þ K2S2O8 (3)
AgNO3 (0.1) þ Mg(NO3)2ꢁ6H2O (2) þ 4 Å MS
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Mn(OAc)3 (4)
Trace
Trace
Trace
35
57
57
60
73
45
40
10
11
12c
DCE
CH3OH
rt
rt
Cu(OAc)2 (0.25) þ K2S2O8 (3)
43
a
Conditions: Benzaldehyde (1a) (0.5 mmol), p-toluenesulfonyl hydrazide (2a) (0.6 mmol), MeOH (3 mL) at 60 ꢀC for 0.5 h; then diphenylphosphine oxide (1.5 mmol),
oxidant in air.
b
c
Isolated yield.
Under argon atmosphere.
2

X.-W. Bian, L. Zhang, A. Shoberu et al.
Tetrahedron 85 (2021) 132053
Table 2
Scope of aldehydes.
Scheme 2. Control Experiments.
Reaction conditions: Aldehyde (1) (0.5 mmol), p-toluenesulfonyl hydrazide (2a)
(0.6 mmol), CH3OH (3 mL) at 60 ꢀC for 0.5 h; then diphenylphosphine oxide
(1.5 mmol), Mn(OAc)3 (2 mmol) at rt for 0.5 h in air. N.D. means not detected.
Scheme 3. Proposed reaction mechanism.
the hydrazine derivative bearing a p-methoxy group did not
materialize presumably due to the ease of oxidation of the starting
substrate. Furthermore, the N-ester-based aldehyde hydrazones
Table 3
Scope of hydrazine derivatives.
also underwent smooth conversion to the corresponding
a-imi-
nophosphine oxides in high yields (4l-4m). While N-acetyl alde-
hyde hydrazone afforded the desired phosphinoylation product
(4n), the N-benzoyl derivative surprisingly did not gave the desired
product 4o. In addition, the stability imparted by N-substitution
was underscored by the reaction of hydrazine derivatives, where
the reaction efficiency was lost upon moving from N-tert-butyl (4p,
52%) to N-methyl (4q, trace) and unsubstituted derivative (4r).
Finally, cinnamaldehyde was conducted for the reaction, the
desired product 4s was obtained in 70% yield. However, using
diethyl-phosphite and phenylethoxy phosphine oxide instead of
diphenyl phosphine oxide for the reaction, no corresponding
imino-phosphine oxide products were detected.
a-
In order to gain a better understanding of the reaction, some
control experiments were conducted as shown in Scheme 2. First,
we established that the reaction could not take place without the
Mn(III) oxidant, thus ruling out a electrophilic substitution pathway
(Scheme 2, a). Moreover, the addition of the radical trapping re-
agent, 1,1-diphenylethylene led to significant suppression of the
formation of expected product 3a, as well as isolation of radical
adduct 5 (Scheme 2, b). This result implicates the involvement of
phosphorus-centered radicals in this reaction.
On the basis of the results from control experiments and liter-
ature reports [4], we proposed a mechanism for the formation of 3a
(Scheme 3). Aldehyde hydrazone 1aʹ is initially generated “in situ”
from the reaction of benzaldehyde (1a) and p-toluenesulfonyl hy-
drazide (2a). Then, phosphorus-centered radicals (formed via
Mn(III)-mediated single electron oxidation of diphenylphosphine
oxide) add to the carbonenitrogen double bond of 1aʹ to form the
radical intermediate I, which could then undergo oxidation to the
cationic intermediate II. Subsequent deprotonation step will
furnish the expected product 3a.
Reaction conditions: Benzaldehyde (1a) (0.5 mmol), hydrazine derivative (2)
(0.6 mmol), CH3OH (3 mL) at 60 ꢀC for 0.5 h; then diphenylphosphine oxide
(1.5 mmol), Mn(OAc)3 (2 mmol) at rt 0.5 h in air. N.D. means not detected.
withdrawing para-substituents afforded the corresponding prod-
ucts in moderate to good yields (4a-4d, 4f-4g, 4i-4j). As observed
above, the presence of strongly electron-withdrawing substituent
such as nitro and cyano groups tends to inhibit the phosphinoyla-
tion reaction (4e and 4k). Notably, the product 4h expected from
3

X.-W. Bian, L. Zhang, A. Shoberu et al.
Tetrahedron 85 (2021) 132053
3. Conclusion
4.3.2. Nʹ-((diphenylphosphoryl) (p-tolyl)methylene)-4-
methylbenzenesulfonohydrazide (3b)
In summary, we have developed a mild and practical method for
the phosphinoylation of “in situ” generated aldehyde hydrazones
with diphenylphosphine oxide utilizing Mn(OAc)3 as oxidant.
Notably, the mild setup allowed the direct use of aldehydes as
substrates in a “one-pot” process, thus circumventing any need for
the separate synthesis/isolation of the hydrazones prior to the
phosphinoylation reaction. Mechanistic studies implicate a radical
pathway involving phosphorus-centered radicals.
White solid; m. p. 198e199 ꢀC (173.6 mg, 71% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 5H), 7.38e7.31 (m, 4H), 7.30e7.22 (m, 4H), 2.44 (s, 3H), 2.32 (s,
3H); 13C NMR (101 MHz, DMSO‑d6):
d 11.39 (s, 1H), 7.68e7.58 (m, 5H), 7.57e7.50
d
152.4 (d, J ¼ 124.0 Hz), 143.7,
139.6, 135.2, 132.0 (d, J ¼ 2.5 Hz), 131.9, 131.4, 131.3, 130.8, 129.3,
129.1, 128.5, 128.41, 128.36, 127.7, 127.5, 127.3, 21.1, 20.9; 31P NMR
(162 MHz, DMSO‑d6):
d
23.57. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd
for C27H26N2O3PS 489.1402, found 489.1403.
4.3.3. Nʹ-((diphenylphosphoryl) (4-methoxyphenyl)methylene)-4-
methylbenzenesulfonohydrazide (3c)
4. Experimental section
White solid; m. p. 173e174 ꢀC (141.1 mg, 56% yield); 1H NMR
4.1. General
(400 MHz, DMSO‑d6): d 11.32 (s, 1H), 7.65e7.45 (m, 10H), 7.40e7,25
(m, 6H), 6.98 (d, J ¼ 8.1 Hz, 2H), 3.76 (s, 3H), 2.41 (s, 3H); 13C NMR
Unless stated otherwise, all reactions were performed under
(101 MHz, DMSO‑d6):
d
160.8, 152.6 (d, J ¼ 124.7 Hz), 144.1, 135.6,
aerobic conditions. 1H NMR (400 MHz), 13C NMR (101 MHz) and 31
P
132.4 (d, J ¼ 2.8 Hz), 131.9, 131.8, 131.4, 130.7 (d, J ¼ 3.1 Hz), 129.8,
NMR (162 MHz) spectra were determined on a Varian-Inova
300 MHz or 400 MHz spectrometer using CDCl3 or DMSO‑d6 as
solvent and tetramethylsilane (TMS) as internal standard or 85%
H3PO4 as external standard for 31P NMR (162 MHz). Chemical shifts
128.9, 128.8, 128.1, 126.0.123.0, 122.8, 114.5, 55.7, 21.5; 31P NMR
(162 MHz, DMSO‑d6):
d
23.70. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd
for C27H26N2O4PS 505.1351, found 505.1343.
were reported in ppm from internal TMS (
d
). The following ab-
4.3.4. Nʹ-((4-chlorophenyl) (diphenylphosphoryl)methylene)-4-
methylbenzenesulfonohydrazide (3d)
breviations were used to explain the multiplicities: s ¼ singlet,
d ¼ doublet, t ¼ triplet, q ¼ quartet, m ¼ multiplet, br ¼ broad. All
coupling constants (J values) were reported in Hertz (Hz). High
resolution mass spectra were recorded on a microTOF-Q III (ESI).
Column chromatography was performed with 300e400 mesh silica
gel using flash column techniques. All of the reagents and solvents
procured from commercial sources were used directly without
further purification. Manganese triacetate was prepared according
to a reported procedure.
White solid; m. p. 180e181 ꢀC (210.8 mg, 83% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 10H), 7.39e7.32 (m, 6H), 2.44 (s, 3H); 13C NMR (101 MHz,
DMSO‑d6):
d 11.53 (s, 1H), 7.70e7.63 (m, 2H), 7.63e7.49
d
151.1 (d, J ¼ 124.1 Hz), 143.8, 135.1, 134.6, 132.1 (d,
J ¼ 2.5 Hz), 131.5, 131.4, 131.3, 130.5, 130.4 (d, J ¼ 2.8 Hz), 129.4,
129.2, 129.0, 128.8, 128.6, 128.5, 127.5, 21.1; 31P NMR (162 MHz,
DMSO‑d6):
C
d
23.49. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for
26H23ClN2O3PS 509.0856, found 509.0843.
4.3.5. Nʹ-((diphenylphosphoryl) (4-fluorophenyl)methylene)-4-
methylbenzenesulfonohydrazide (3e)
4.2. Representative procedure for the preparation of compounds 3
and 4
White solid; m. p. 249e250 ꢀC (177.1 mg, 72% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 6H), 7.42e7.32 (m, 4H), 7.31e7.23 (m, 4H), 2.41 (s, 3H); 13C NMR
(101 MHz, DMSO‑d6): 162.7 (d, 247.6 Hz), 151.4 (d,
d 11.45 (s, 1H), 7.66e7.57 (m, 4H), 7.57e7.48
To a solution of aldehyde 1 (0.5 mmol) in methanol (3 mL) was
added p-tolylsulfonylhydrazide 2 (0.6 mmol) and the mixture
stirred at 60 ꢀC for 0.5 h. The reaction mixture was subsequently
cooled to room temperature, then diphenylphosphine oxide
(1.5 mmol) was added, and Mn(OAc)3 (2 mmol) was added for three
times. The resultant mixture was further stirred at room temper-
ature for 0.5 h in air. After completion of the reaction (as indicated
by TLC), the solvent was removed under vacuum. The resulting
residue was diluted with water (20 mL) and extracted by ethyl
acetate (10 mL ꢂ 3). The combined organic extracts were dried over
anhydrous MgSO4, and concentrated under vacuum to give the
crude product, which was purified by silica gel column chroma-
tography using petroleum ether/EtOAc (1:1) as eluent to give pure
product 3 or 4.
d
J
¼
J ¼ 124.4 Hz), 143.8, 132.1 (d, J ¼ 2.5 Hz), 131.6, 131.4, 131.3, 131.1 (d,
J ¼ 2.9 Hz), 131.0 (d, J ¼ 2.8 Hz), 130.6, 129.4, 128.5, 128.4, 127.6,
126.8 (d, J ¼ 3.3 Hz), 126.6 (d, J ¼ 3.1 Hz), 115.8 (d, J ¼ 21.9 Hz), 21.1;
31P NMR (162 MHz, DMSO‑d6):
d 23.55. HRMS (ESI-TOF) m/z:
(M þ H)þ Calcd for C26H23FN2O3PS 493.1151, found 493.1167.
4.3.6. Nʹ-((4-bromophenyl) (diphenylphosphoryl)methylene)-4-
methylbenzenesulfonohydrazide (3f)
White solid; m. p. 157e158 ꢀC (234.6 mg, 85% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 8H), 7.38e7.17 (m, 6H), 2.41 (s, 3H); 13C NMR (101 MHz,
DMSO‑d6):
151.2 (d, J ¼ 123.9 Hz), 143.8, 135.1, 132.1, 131.7, 131.5,
131.4, 131.3, 130.6 (d, J ¼ 2.8 Hz), 130.5, 129.54, 129.45, 129.4, 128.6,
d 11.51 (s, 1H), 7.77e7.60 (m, 4H), 7.59e7.47
d
128.5, 127.5, 123.5, 21.1; 31P NMR (162 MHz, DMSO‑d6):
d 23.43.
4.3. Characterization
HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for C26H23BrN2O3PS 553.0350,
found 553.0370.
4.3.1. Nʹ-((diphenylphosphoryl) (phenyl)methylene)-4-
methylbenzenesulfonohydrazide (3a)
4.3.7. Nʹ-((diphenylphosphoryl) (m-tolyl)methylene)-4-
methylbenzenesulfonohydrazide (3h)
White solid; m. p. 227e228 ꢀC (173.0 mg, 73% yield).; 1H NMR
(400 MHz, DMSO‑d6):
(m, 5H), 7.49e7.41 (m, 3H), 7.41e7.32 (m, 6H), 2.45 (s, 3H); 13C NMR
(101 MHz, DMSO‑d6):
d
11.46 (s, 1H), 7.69e7.58 (m, 5H), 7.58e7.51
White solid; m. p. 193e194 ꢀC (195.2 mg, 80% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 5H), 7.25 (d, J ¼ 7.3 Hz, 1H), 7.16 (s, 1H), 7.11 (d, J ¼ 7.3 Hz, 1H),
2.44 (s, 3H), 2.30 (s, 3H); 13C NMR (101 MHz, DMSO‑d6):
152.6 (d,
d 11.42 (s, 1H), 7.68e7.51 (m, 10H), 7.41e7.29
d
152.4 (d, J ¼ 123.4 Hz), 143.7, 135.2, 132.0 (d,
J ¼ 2.5 Hz), 131.8, 131.4, 131.3, 130.8, 130.4, 130.2, 129.8, 129.4, 128.6,
d
128.5, 128.4 (d, J ¼ 3.0 Hz), 128.4, 127.7, 21.1; 31P NMR (162 MHz,
J ¼ 123.6 Hz), 143.7, 137.7, 135.2, 132.0 (d, J ¼ 2.4 Hz), 131.9, 131.4,
131.3, 130.9, 130.5, 130.3, 130.1, 129.4, 128.8 (d, J ¼ 2.8 Hz), 128.5,
128.4, 127.8, 125.53, 125.50, 21.1, 21.0; 31P NMR (162 MHz,
DMSO‑d6):
C
d
23.45. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for
26H24N2O3PS 475.1245, found 475.1263.
4

X.-W. Bian, L. Zhang, A. Shoberu et al.
Tetrahedron 85 (2021) 132053
DMSO‑d6):
d
23.33. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for
(m, 8H), 7.32 (dd, J ¼ 20.1, 7.8 Hz, 4H), 2.40 (s, 3H), 1.96e1.81 (m,
1H), 1.11 (d, J ¼ 3.0 Hz, 2H), 0.82 (d, J ¼ 6.3 Hz, 2H); 13C NMR
C
27H26N2O3PS 489.1402, found 489.1410.
(101 MHz, DMSO‑d6):
d
155.5 (d, J ¼ 125.6 Hz), 143.6, 135.5, 132.4,
4.3.8. Nʹ-((diphenylphosphoryl) (o-tolyl)methylene)-4-
methylbenzenesulfonohydrazide (3i)
131.89, 131.86, 131.4, 131.1, 131.0, 129.4, 128.4, 128.3, 127.4, 21.0, 12.0,
11.8, 6.6; 31P NMR (162 MHz, DMSO‑d6):
d 24.23. HRMS (ESI-TOF) m/
White solid; m. p. 179e180 ꢀC (195.2 mg, 80% yield); 1H NMR
z: (M þ H)þ Calcd for C23H24N2O3PS 439.1245, found 439.1239.
(400 MHz, DMSO‑d6):
d 11.37 (s, 1H), 7.59 (m, 12H), 7.44e7.11 (m,
5H), 6.77 (d, J ¼ 4.4 Hz, 1H), 2.46 (s, 3H), 2.00 (s, 3H); 13C NMR
4.3.14. Nʹ-((3,5-dimethylisoxazol-4-yl) (diphenylphosphoryl)
methylene)-4-methylbenzenesulfonohydrazide (3r)
(101 MHz, DMSO‑d6):
d
153.9 (d, J ¼ 123.2 Hz), 143.7, 136.60, 136.57,
135.6, 132.1 (d, J ¼ 2.2 Hz), 132.0 (d, J ¼ 2.7 Hz), 131.4, 131.3, 131.2,
White solid; m. p. 182e183 ꢀC (88.7 mg, 36% yield); 1H NMR
130.3, 129.5, 128.6, 128.5, 128.4, 128.3, 128.0, 127.4, 125.7, 21.1, 19.3;
(400 MHz, DMSO‑d6):
d
11.80 (s, 1H), 7.65 (dd, J ¼ 12.7, 5.9 Hz, 2H),
31P NMR (162 MHz, DMSO‑d6):
d
20.86. HRMS (ESI-TOF) m/z:
7.63e7.50 (m, 8H), 7.48 (d, J ¼ 8.1 Hz, 2H), 7.38 (d, J ¼ 8.0 Hz, 2H),
(M þ H)þ Calcd for C27H26N2O3PS 489.1402, found 489.1413.
2.44 (s, 3H), 2.01 (s, 3H), 1.88 (s, 3H); 13C NMR (101 MHz, DMSO‑d6):
d
168.7 (d, J ¼ 3.7 Hz), 158.2 (d, J ¼ 1.5 Hz), 144.8, 144.0, 143.6, 135.3,
4.3.9. Nʹ-((diphenylphosphoryl) (2-methoxyphenyl)methylene)-4-
methylbenzenesulfonohydrazide (3j)
132.3, 131.4 (d, J ¼ 2.3 Hz), 131.3 (d, J ¼ 2.4 Hz), 130.3 (d, J ¼ 3.8 Hz),
129.7, 128.7 (d, J ¼ 2.0 Hz),128.5 (d, J ¼ 2.1 Hz), 127.4, 125.5, 107.0 (d,
White solid; m. p. 177e178 ꢀC (189.0 mg, 75% yield); 1H NMR
J ¼ 18.4 Hz), 21.1, 11.8, 10.4; 31P NMR (162 MHz, DMSO‑d6):
d 21.30.
(400 MHz, DMSO‑d6):
(m, 3H), 3.54 (s, 3H), 2.49 (s, 3H); 13C NMR (101 MHz, DMSO‑d6):
156.8 (d, J ¼ 2.8 Hz), 150.3 (d, J ¼ 127.2 Hz), 143.7, 135.9, 132.7,
d
11.24 (s, 1H), 7.64e7.38 (m, 15H), 7.11e6.92
HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for C23H24N2O3PS 494.1303,
found 494.1292.
d
131.71, 131.65 (d, J ¼ 2.4 Hz), 131.4, 131.3, 131.2, 129.5, 129.2 (d,
4.3.15. Nʹ-((diphenylphosphoryl) (phenyl)methylene)
benzenesulfono-hydrazide (4a)
J ¼ 1.9 Hz), 128.2, 128.1, 127.5, 120.2, 119.1, 118.9, 111.9, 55.2, 21.1; 31
P
NMR (162 MHz, DMSO‑d6):
d
21.42. HRMS (ESI-TOF) m/z: (M þ H)þ
White solid; m. p. 162e163 ꢀC (195.5 mg, 85% yield); 1H NMR
Calcd for C27H26N2O4PS 505.1351, found 505.1354.
(400 MHz, DMSO‑d6):
d
11.54 (s, 1H), 7.74e7.70 (m, 1H), 7.67e7.47
152.7
(m, 14H), 7.36e7.32 (m, 5H); 13C NMR (101 MHz, DMSO‑d6):
d
4.3.10. Nʹ-((3-chlorophenyl) (diphenylphosphoryl)methylene)-4-
methylbenzenesulfonohydrazide (3k)
(d, J ¼ 112.3 Hz), 138.0, 133.3, 132.8, 132.0, 131.7, 131.4, 131.3, 130.7,
130.4, 130.2, 129.9, 128.9, 128.6, 128.5, 128.4, 127.6; 31P NMR
White solid; m. p. 180e181 ꢀC (189.0 mg, 75% yield); 1H NMR
(162 MHz, DMSO‑d6):
for C25H22N2O3PS 461.1089, found 461.1100.
d
23.44. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd
(400 MHz, DMSO‑d6):
d
11.58 (s, 1H), 7.67 (dd, J ¼ 11.0, 4.2 Hz, 2H),
7.63e7.52 (m, 8H), 7.48 (dd, J ¼ 14.5, 7.0 Hz, 2H), 7.39e7.31 (m, 5H),
7.27 (d, J ¼ 7.4 Hz, 1H), 2.45 (s, 3H); 13C NMR (101 MHz, DMSO‑d6):
4.3.16. Nʹ-((diphenylphosphoryl) (phenyl)methylene)-4-
methoxybenzenesulfonohydrazide (4b)
d
150.6 (d, J ¼ 122.7 Hz), 143.9, 135.1, 133.2, 132.3, 132.2 (d,
J ¼ 2.5 Hz), 132.1, 131.5, 131.4, 130.6, 130.4, 129.8, 129.5, 128.6, 128.5,
White solid; m. p. 157e158 ꢀC (195.5 mg, 46% yield); 1H NMR
128.2 (d, J ¼ 2.6 Hz), 127.5, 127.14, 127.12, 21.1; 31P NMR (162 MHz,
(400 MHz, DMSO‑d6):
(m, 5H), 7.32 (d, J ¼ 2.8 Hz, 2H), 7.01 (d, J ¼ 8.8 Hz, 2H), 3.86 (s, 3H);
13C NMR (101 MHz, DMSO‑d6):
d 11.34 (s, 1H), 7.64e7.48 (m, 10H), 7.43e7.38
DMSO‑d6):
C
d
23.67. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for
26H23ClN2O3PS 509.0856, found 509.0844.
d
162.8, 152.3 (d, J ¼ 123.4 Hz), 132.0
(d, J ¼ 2.0 Hz), 131.9, 131.44, 131.35, 130.8, 130.4, 130.2, 129.9, 129.8,
4.3.11. Nʹ-((2-chlorophenyl) (diphenylphosphoryl)methylene)-4-
methylbenzenesulfonohydrazide (3l)
129.6, 128.6, 128.5, 128.4 (d, J ¼ 2.8 Hz), 128.4, 114.1, 55.8; 31P NMR
(162 MHz, DMSO‑d6):
d
23.39. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd
White solid; m. p. 183e184 ꢀC (221.0 mg, 87% yield); 1H NMR
for C26H24N2O4PS 491.1194, found 491.1206.
(400 MHz, DMSO‑d6):
d 11.75 (s, 1H), 7.77e7.28 (m, 17H), 6.99 (d,
J ¼ 6.6 Hz, 1H), 2.47 (s, 3H); 13C NMR (101 MHz, DMSO‑d6):
d
149.2
4.3.17. 4-Chloro-Nʹ-((diphenylphosphoryl) (phenyl)methylene)
benzene-sulfonohydrazide (4c)
(d, J ¼ 126.8 Hz), 143.8, 135.74, 132.2 (d, J ¼ 3.2 Hz), 132.1 (d,
J ¼ 3.2 Hz), 132.0 (d, J ¼ 2.4 Hz), 131.4, 131.34, 131.32, 131.3, 131.1,
130.1, 129.8, 129.7, 129.61, 129.55, 128.5 (d, J ¼ 11.9 Hz), 128.3 (d,
J ¼ 12.0 Hz), 127.4, 127.2, 21.1; 31P NMR (162 MHz, DMSO‑d6):
White solid; m. p. 172e173 ꢀC (187.7 mg, 76% yield); 1H NMR
(400 MHz, DMSO‑d6):
(m, 7H); 13C NMR (101 MHz, DMSO‑d6):
138.3, 136.7, 132.1, 131.7, 131.4, 131.3, 130.3, 130.1, 130.0, 129.5, 129.1,
d
11.56 (s, 1H), 7.68e7.47 (m, 12H), 7.46e7.15
d
153.4 (d, J ¼ 130.7 Hz),
d
20.96. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for C26H23ClN2O3PS
509.0856, found 509.0865.
128.6, 128.5, 128.4; 31P NMR (162 MHz, DMSO‑d6):
d 23.69. HRMS
(ESI-TOF) m/z: (M þ H)þ Calcd for C25H21ClN2O3PS 495.0699, found
4.3.12. Nʹ-(1-(diphenylphosphoryl)-2-methylpropylidene)-4-
methylbenzenesulfonohydrazide (3n)
495.0715.
White solid; m. p. 172e173 ꢀC (176.0 mg, 80% yield); 1H NMR
4.3.18. 4-Bromo-Nʹ-((diphenylphosphoryl) (phenyl)methylene)
benzene-sulfonohydrazide (4d)
(400 MHz, DMSO‑d6):
d
11.39 (s, 1H), 7.56 (dd, J ¼ 14.6, 7.1 Hz, 2H),
7.47e7.39 (m, 10H), 7.32 (d, J ¼ 8.0 Hz, 2H), 3.44e3.03 (m, 1H), 2.41
White solid; m. p. 162e163 ꢀC (223.3 mg, 83% yield); 1H NMR
(s, 3H), 1.07 (d, J ¼ 6.8 Hz, 6H); 13C NMR (101 MHz, DMSO‑d6):
(400 MHz, DMSO‑d6):
d
11.56 (s, 1H), 7.73 (d, J ¼ 8.3 Hz, 2H),
d
160.1 (d, J ¼ 117.8 Hz), 143.7, 135.5, 133.3, 132.3, 131.7 (d,
7.66e7.60 (m, 2H), 7.58e7.48 (m, 8H), 7.41 (d, J ¼ 1.8 Hz, 3H), 7.36
J ¼ 2.5 Hz), 131.4, 131.04, 130.95, 129.5, 128.3, 128.2, 127.5, 29.8 (d,
(d, J ¼ 8.3 Hz, 4H); 13C NMR (101 MHz, DMSO‑d6):
d 153.4 (d,
J ¼ 16.2 Hz), 21.1, 18.4; 31P NMR (162 MHz, DMSO‑d6):
d
23.40.
J ¼ 122.6 Hz), 137.2, 132.11, 132.06, 131.7, 131.4, 131.3, 130.6, 130.3,
HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for C23H26N2O3PS 441.1402,
130.1, 130.0, 129.5, 128.63, 128.55, 128.4, 127.4; 31P NMR (162 MHz,
found 441.1411.
DMSO‑d6):
d
23.71. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for
C
25H21BrN2O3PS 539.0194, found 539.0181.
4.3.13. Nʹ-(cyclopropyl(diphenylphosphoryl)methylene)-4-
methylbenzenesulfonohydrazide (3o)
4.3.19. Diphenyl(phenyl(2-phenylhydrazono)methyl)phosphine
oxide (4f)
White solid; m. p. 161e162 ꢀC (203.7 mg, 93% yield); 1H NMR
(400 MHz, DMSO‑d6):
d
11.44 (s, 1H), 7.65e7.57 (m, 2H), 7.52e7.39
White solid; m. p. 198e199 ꢀC (121.4 mg, 61% yield); 1H NMR
5

X.-W. Bian, L. Zhang, A. Shoberu et al.
Tetrahedron 85 (2021) 132053
(400 MHz, DMSO‑d6):
d
7.94 (dd, J ¼ 11.9, 7.1 Hz, 4H), 7.63e7.46 (m,
140.6 (d,
(400 MHz, CDCl3):
d
8.82 (s, 1H), 7.89e7.77 (m, 4H), 7.58e7.44 (m,
8H), 7.43e7.27 (m, 9H); 13C NMR (101 MHz, DMSO‑d6):
d
6H), 7.43e7.35 (m, 3H), 7.28 (d, J ¼ 6.6 Hz, 2H),1.98 (s, 3H); 13C NMR
J ¼ 11.6 Hz), 136.9 (d, J ¼ 6.4 Hz), 134.9, 132.9, 132.7, 132.6, 132.4 (d,
(101 MHz, CDCl3):
d
172.7, 149.0 (d, J ¼ 126.6 Hz), 131.7 (d,
J ¼ 2.6 Hz), 131.6, 130.9 (d, J ¼ 2.6 Hz), 130.4, 129.6, 129.2, 129.1,
J ¼ 2.8 Hz), 131.6, 131.5, 130.5, 129.9, 129.5, 129.2, 128.4, 128.3, 128.0,
128.9, 128.8, 126.8; 31P NMR (162 MHz, DMSO‑d6):
d
26.01. HRMS
127.9, 127.8 (d, J ¼ 2.8 Hz), 19.8; 31P NMR (162 MHz, CDCl3):
d 25.94.
(ESI-TOF) m/z: (M þ H)þ Calcd for C25H22N2OP 397.1470, found
HRMS (ESI-TOF) m/z: (M þ H)þ Calcd for C21H20N2O2P 363,1262,
397.1472.
found 363.1261.
4.3.20. Diphenyl(phenyl(2-(p-tolyl)hydrazono)methyl)phosphine
oxide (4g)
4.3.26. ((2-(tert-Butyl)hydrazono) (phenyl)methyl)
diphenylphosphine oxide (4p)
White solid; m. p. 169e170 ꢀC (112.8 mg, 55% yield); 1H NMR
White solid; m. p. 166e167 ꢀC (97.8 mg, 52% yield); 1H NMR
(400 MHz, CDCl3):
7.45e7.38 (m, 4H), 7.32e7.27 (m, 3H), 7.24e7.19 (m, 4H), 7.18 (s, 1H),
7.16e7.11 (m, 2H), 2.32 (s, 3H); 13C NMR (101 MHz, CDCl3):
140.0
d 7.99e7.90 (m, 4H), 7.50e7.46 (m, 2H),
(400 MHz, DMSO‑d6):
(m, 6H), 7.36e7.24 (m, 5H), 1.39 (s, 9H); 13C NMR (101 MHz,
DMSO‑d6):
159.8 (d, J ¼ 9.3 Hz), 134.7, 133.9, 133.4, 131.9, 131.8,
d 8.04 (s, 1H), 7.80e7.68 (m, 4H), 7.52e7.42
d
d
(d, J ¼ 11.8 Hz), 138.3, 134.5, 133.31, 133.25, 132.2, 132.11, 132.05,
131.39, 131.36, 130.2, 128.5, 128.4, 128.3, 126.9, 60.4, 29.4 (d,
J ¼ 2.7 Hz); 31P NMR (162 MHz, DMSO‑d6):
d 28.98. HRMS (ESI-TOF)
131.3 (d, J ¼ 2.7 Hz), 130.8, 130.2, 130.0 (d, J ¼ 2.4 Hz), 128.5, 128.0,
127.8, 127.6, 126.2, 20.8; 31P NMR (162 MHz, CDCl3):
d 28.37. HRMS
m/z: (M þ H)þ Calcd for C23H26N2OP 377.1783, found 377.1796.
(ESI-TOF) m/z: (M þ H)þ Calcd for C26H24N2OP 411.1626, found
411.1610.
Declaration of competing interest
4.3.21. ((2-(4-Chlorophenyl)hydrazono) (phenyl)methyl)
diphenylphosphine oxide (4i)
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
White solid; m. p. 207e208 ꢀC (154.8 mg, 72% yield); 1H NMR
(400 MHz, DMSO‑d6):
d
7.92 (dd, J ¼ 11.1, 7.9 Hz, 4H), 7.65e7.45 (m,
8H), 7.40e7.25 (m, 8H); 13C NMR (101 MHz, DMSO‑d6):
d
140.7 (d,
Acknowledgements
J ¼ 11.6 Hz), 135.53, 135.47, 134.4, 133.2, 132.2, 132.13, 132.11, 132.07,
132.05, 130.8, 130.0, 129.3, 128.6, 128.5, 128.4, 126.4; 31P NMR
J.-P. Zou appreciates the generous financial support by National
Natural Science Foundation of China (No. 21472133), the Priority
Academic Program Development of Jiangsu Higher Education In-
stitutions (PAPD) and Key Laboratory of Organic Synthesis of
Jiangsu Province (KJS1749).
(162 MHz, DMSO‑d6):
for C25H21ClN2OP 431.1080, found 431.1075.
d
26.34. HRMS (ESI-TOF) m/z: (M þ H)þ Calcd
4.3.22. ((2-(4-Bromophenyl)hydrazono) (phenyl)methyl)
diphenylphosphine oxide (4j)
White solid; m. p. 201e202 ꢀC (154.1 mg, 65% yield); 1H NMR
Supplementary data
(400 MHz, CDCl3):
d
7.93 (dd, J ¼ 11.8, 7.7 Hz, 4H), 7.57e7.48 (m, 4H),
7.44e7.40 (m, 4H), 7.33e7.21 (m, 6H), 7.14 (d, J ¼ 8.1 Hz, 2H); 13C
Experimental procedures, characterization data, and copies of
the 1H NMR and 13C NMR spectra for the products 3 and 4 are
available.
NMR (101 MHz, CDCl3):
d
140.0 (d, J ¼ 11.3 Hz), 134.8, 134.7, 133.6,
132.2, 131.5, 131.4, 131.2, 131.0, 129.8, 128.2, 127.5, 127.3, 127.2, 125.7,
121.8; 31P NMR (162 MHz, CDCl3):
d 28.85. HRMS (ESI-TOF) m/z:
(M þ H)þ Calcd for C25H21BrN2OP 475.0575, found 475.0583.
Appendix A. Supplementary data
4.3.23. Methyl 2-((diphenylphosphoryl) (phenyl)methylene)
hydrazine-1-carboxylate (4l)
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.tet.2021.132053.
White solid; m. p. 176e177 ꢀC (168.2 mg, 89% yield); 1H NMR
(400 MHz, DMSO‑d6):
7.66e7.50 (m, 6H), 7.48e7.39 (m, 3H), 7.35e7.25 (m, 2H), 3.68 (s,
3H); 13C NMR (101 MHz, DMSO‑d6):
d
10.44 (s, 1H), 7.86 (dd, J ¼ 10.6, 8.0 Hz, 4H),
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6

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