General Oxidative Aryl C-P Bond Formation through Palladium-Catalyzed Decarbonylative Coupling of Aroylhydrazides with P(O)H Compounds

Article abstract of DOI:10.1021/acs.orglett.9b00922

Oxidative C-C/P-H cross-coupling is achieved via Pd-catalyzed decarbonylative cross-coupling of aroylhydrazides with P(O)H compounds. The unique cooperative reaction system, especially the Br?nsted acid and bidentate phosphine ligand, allows the selective activation of the inert C-C bond and the suppression of the undesired oxidation and coordination of >P(O)-H compounds, leading to a general oxidative synthesis of aryl phosphorus compounds from easily available substrates.

Full text of DOI:10.1021/acs.orglett.9b00922

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
General Oxidative Aryl C−P Bond Formation through Palladium-
Catalyzed Decarbonylative Coupling of Aroylhydrazides with P(O)H
Compounds
Jianyu Dong,†,‡ Long Liu,† Xuyu Ji,† Qian Shang,† Lixin Liu,† Lebin Su,† Bing Chen,∥ Ruifeng Kan,∥
Yongbo Zhou,*,† Shuang-Feng Yin,† and Li-Biao Han§
†State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan
University, Changsha 410082, China
‡Department of Educational Science, Hunan First Normal University, Changsha 410205, China
§National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan
∥Key Lab of Environmental Optics & Technology, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences,
Hefei 230031, China
S
* Supporting Information
ABSTRACT: Oxidative C−C/P−H cross-coupling is
achieved via Pd-catalyzed decarbonylative cross-coupling of
aroylhydrazides with P(O)H compounds. The unique
cooperative reaction system, especially the Brønsted acid
and bidentate phosphine ligand, allows the selective activation
of the inert C−C bond and the suppression of the undesired
oxidation and coordination of >P(O)−H compounds, leading
to a general oxidative synthesis of aryl phosphorus compounds
from easily available substrates.
rganophosphorus compounds, particularly arylated com-
pounds, are invaluable chemicals in the fields of organic
catalyzed coupling of ArX (X = Br, I) with P(O)−H
compounds under mild conditions.4 This reaction is now
known as one of the very few reliable approaches for
generating aryl phosphorus compounds via the precise
construction of C−P bonds due to its high efficiency and
good functional tolerance.5,6 As notable advances, many
electrophiles (pseudohalides) such as diazonium salts,7
sulfonates,8 boronic acids,9 aryl esters,10 silanes,11 sulfides,12
etc.13 have been used as coupling partners to replace
organohalides (Scheme 1).
O
synthesis, catalysis, medicinal chemistry, agricultural chemistry,
and materials chemistry.1 Despite the extreme importance of
these compounds and their extensive applications, general,
convenient, and step-economic methods for the synthesis of
these compounds from easily accessible starting materials are
highly limited. Classical methods for preparing organo-
phosphorus compounds rely on the transformation of
organohalides and pseudohalides (Scheme 1).2−13 Among
The exploration of convenient and general syntheses direct
from abundant, easily handled, and cost-saving materials, such
as hydrocarbons and carboxylic acid derivatives, is an eternal
pursuit for chemists.14 In this regard, oxidative synthesis of
organophosphorus compounds from these easily available and
inexpensive chemicals with P(O)−H compounds is undoubt-
edly ideal (Scheme 1). Compared to the known methods,
oxidative synthesis not only avoids the requirement of toxic,
sensitive, and/or prefunctionalized substrates but also provides
convenient operations. To date, a few advances of oxidative
phosphonation of sp2C−H bonds have been made by
employing the substrates bearing N-heterocycles, which act
as the directing groups.15 However, oxidative sp2C−C/P−H
cross-coupling is rarely reported (Scheme 2)16 due to different
Scheme 1. Methods for the Synthesis of Organophosphorus
Compounds
these transformations, nucleophilic substitution of toxic
phosphorus halides with Grignard reagents or organolithiums
is extensively used to produce these compounds.2 The reaction
of an excess amount of a halide with a phosphite (Michaelis−
Arbuzov reaction) is also one of the most frequently used
methods.3 In the 1980s, Hirao et al. proposed palladium-
Received: March 14, 2019
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.9b00922
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
reported oxidative arylation reactions using aroyl hydrazides as
aryl sources, respectively.21 Enlightened by these works, we
treated benzoyl hydrazide (1a) with diphenylphosphine oxide
(2a) in the presence of Pd(OAc)2, bis(diphenylphosphino)
methane (dppm), K2S2O8, and PhSO2OH in mixed DMSO
and DCE at 100 °C. The C(aryl)−C(O)/P−H cross-coupling
product (3a) was produced in 35% GC yield (Table 1, entry
Scheme 2. Decarboxylative C−C/P−H Cross-Coupling
a
Table 1. Optimization of Conditions
b
entry
catalyst
ligand
oxidant
additive
yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
Pd(OAc)2
dppm
dppm
dppm
dppm
dppm
dppp
dcype
phen
dpppy
Ph3P
-
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
K2S2O8
Na2S2O8
Na2S2O8
PhSO2OH
-
Et3N
K2CO3
Cs2CO3
PhSO2OH
PhSO2OH
PhSO2OH
PhSO2OH
PhSO2OH
PhSO2OH
PhSO2OH
PhSO2OH
35
17
trace
trace
trace
25
15
trace
8
9
7
reactivities of the substrates. First, because unstrained C−C
bonds are thermodynamically stable, their activation proves to
be difficult and generally requires a transition metal catalyst
and relatively high temperature.14e−h Meanwhile, the similar
nature of C−C bonds and the harsh reaction conditions result
in a lack of selectivity. More seriously, >P(O)−H compounds,
especially H-phosphine oxides, can coordinate with metal17
and are easily oxidized to their corresponding acids, which not
only poisons the metal catalyst but also disfavors the desired
C−P bond formation. Undoubtedly, the suppression of the
undesired oxidation of >P(O)−H compounds, the avoidance of the
passification of the metal catalyst, and the selective oxidative
activation of inert C−C bonds, which require different reaction
conditions, represent a great challenge. Indeed, the decarbox-
ylative C(aryl)−P formation reactions are achieved under
exotic oxidant-free conditions at high temperature (150−170
°C, Scheme 2a and 2b)18 and by the use of the strong electron-
withdrawing group (o-NO2) substituted substrates with the
assistance of microwave irradiation (Scheme 2c),16 respec-
tively.
c
dppm
dppm
61
71
c d
,
a
Reaction conditions: benzoyl hydrazide (1a, 0.6 mmol), Ph2P(O)H
(2a, 0.2 mmol), catalyst (0.02 mmol, 10 mol %), ligand (0.02 mmol,
10 mol %), oxidant (0.4 mmol), additive (0.4 mmol) in DMSO/DCE
b
(v/v = 3/5, 1.6 mL) at 100 °C under N2 for 20 h. GC yield using
c
tridecane as an internal standard. DMSO/DMAc (3/5) as a solvent.
d
Pd(OAc)2 (30 mol %).
1). It was proved that Pd(OAc)2, dppm, Na2S2O8, PhSO2OH,
and mixed DMSO/DMAc (v/v = 3/5) were the best reaction
parameters as the catalyst, ligand, oxidant, additive, and
solvent, respectively, and 3a was obtained in 61% yield
(Table 1, entry 12). With the increased loading of the catalyst,
the yield of 3a increased to up to 71% (Table 1, entry 13).
Both the Brønsted acid and bidentate phosphine ligand were
critical to the reaction. The addition of bases that are generally
required in the known C−P bond formations5−13 resulted in
traces of the desired product (Table 1, entries 3−5). Bidentate
ligand dppm that has P−C−P structure is the best for the
reaction, probably due to its relatively stable and difficult
dissociation with metal. Indeed, the alkylated bidentate
phosphine ligand (Table 1, entry 7) that is liable to be
oxidized, the bidentate nitrogen ligand that is easily protonated
(Table 1, entry 8), and monodentate ligands (Table 1, entries
9 and 10) that can be dissociated and exchanged with >P(O)−
H compounds were all ineffective. Other reaction parameters
such as the metal catalyst, oxidant, solvent, and reaction
temperature also played important roles in the reaction (for
details see the Supporting Information (SI), Tables S1−S7).
Next, the scope and generality of the reaction were
investigated. As shown in Table 2, the Pd-catalyzed oxidative
C(aryl)−C(O)N/P(O)−H cross-coupling exhibits a wide
scope of substrates, producing various aryl phosphorus
compounds in satisfactory yields. For aroyl hydrazides,
electron-donating groups, such as Me, t-Bu, and OMe on the
phenyl rings, significantly facilitated the reaction, and the
As a topic of increasing interest,10a,19 we think that >P(O)−
H compounds, especially H-phosphine oxides, may be
protonated to form phosphonium salts by the addition of a
strong Brønsted acid because they can tautomerize to form P−
OH species.20 In addition, a transition metal catalyst can be
chelated to a bidentate ligand that is stronger than a
monodentate ligand, and it may coordinate to a bidentate
ligand rather than a >P(O)−H compound, which is a
monodentate ligand.17 Thus, by using a suitable Brønsted
acid and a bidentate ligand that is not protonated by the acid,
the undesired oxidation and coordination of >P(O)−H
compounds may be restrained. Based on these considerations,
we have attempted to address the long-standing challenge over
the past decade. After numerous attempts, we finally realized
the strategy. Herein, we report how we overcame the
challenges and describe a general oxidative synthesis of aryl
phosphorus compounds from aroylhydrazides without any
directing groups15,16 and >P(O)−H compounds (Scheme 2d).
Aroylhydrazides are readily acessible carboxylic acid
derivatives. Compared with many other types of carboxylic
acid derivatives, simple aroyl hydrazides are stable solids and
compatible with moisture. The groups of Wang and Tian have
B
DOI: 10.1021/acs.orglett.9b00922
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Organic Letters
Letter
a
CF3-substituted aromatic secondary phosphine oxides were
used as substrates, the corresponding products (3n−p) were
obtained in 75%, 64%, and 87% yields, respectively (Table 2,
entries 14−16). The good performance of these substrates was
probably due to their relatively low oxidability and the easy
tautomerization to their trivalent isomers (vide infra). In
comparison, the methyl-substituted substrate gave a 56% yield
of the desired product (3q, Table 2, entry 17). Even
dibutylphosphine oxide that is more oxidizable than
diphenylphosphine oxides also reacted with 1a to give the
desired product (3r) in 43% yield (Table 2, entry 18).
In addition to the secondary phosphine oxides, other
>P(O)−H compounds are also good substrates for the C−P
formation. H-Phosphinates such as dibenzo[c,e][1,2]-
oxaphosphinine 6-oxide and ethyl phenylphosphinate could
react well under this oxidative system, generating the aryl
phosphorus compounds 3t and 3s in 56% and 72% yields,
respectively (Table 2, entries 19 and 20). When H-
phosphonates, such as diethyl phosphite, diisopropyl phos-
phite, and diisobutyl phosphite, were subjected to the reaction
system, the desired products (3u−w) were obtained in good
yields (Table 2, entries 21−23).
Table 2. Substrate Scope
It was worth noting that the C(aryl)−C/P−H cross-
coupling proceeded stereospecifically. The reaction of optically
pure (RP)-(−)-menthyl phenylphosphinate (RP‑2) with p-
methoxyl benzoyl hydrazide (1f) afforded the corresponding
optically pure product (SP‑3x) in 51% yield (Scheme 3). The
Scheme 3. Reaction of Optically Pure H-Phosphinate
configuration at the phosphorus of the product was determined
to be SP by comparison with the authentic sample,22 suggesting
that the reaction proceeds with the retention of the
configuration at the phosphorus atom.
Control experiments were carried out to gain additional
insights into the reaction mechanism (Scheme 4). At first, the
reaction of benzoyl hydrazide (1a) with Ph2P(O)H (2a)
generated benzophenone (4) in 12% yield, with a concomitant
release of CO and CO2 in 74% and 6% yields, respectively
(Scheme 4, eq 1; for details, see the SI).23 In the absence of 2a,
4 was also observed in an 8% yield with generation of a 27%
yield of CO and a 6% yield of CO2 (Scheme 4, eq 2). CO
could not be converted to CO2 under Pd-catalyzed oxidative
conditions (Scheme 4, eq 3). These results suggested that Ar−
PdOAc and Ar−C(O)−PdOAc intermediates were involved.
The higher yield of CO than that of CO2 in eqs 1 and 2
demonstrated that the attack at Ar−PdOAc by 2a occurred,
which accelerated the main catalytic cycle. The lower yield of
CO2 (6%) indicated that the generation of CO2 was minor in
the C(aryl)−C/P(O)−H coupling reaction (vide infra). When
2a reacted with benzaldehyde (5a), benzoic acid (5b), or
benzoic amide (5c) under the optimized conditions, no
desired product was observed (Scheme 4, eq 4), which
demonstrated that the aroylhydrazides released N2 in the
presence of Pd(OAc)2 to generate Ar−C(O)−PdOAc species,
triggering the reaction. This finding was further confirmed by
replacing 1a with N-phenyl-substituted aroyl hydrazide 6
a
Reaction conditions: 1 (0.6 mmol), 2 (0.2 mmol), Pd(OAc)2 (0.02
mmol, 10 mol %), dppm (0.02 mmol, 10 mol %), Na2S2O8 (0.4
mmol), PhSO2OH (0.4 mmol), DMSO (0.6 mL), and DMAc (1.0
b
c
mL), at 100 °C for 20 h under N2. 30 mol % of Pd(OAc)2. 1 (3.0
mmol) and 2 (1.0 mmol).
desired products (3b−f, 3k, and 3l) were obtained in 61−88%
yields (Table 2, entries 2−6, 11, and 12). Aroylhydrazides
substituted with electron-withdrawing groups, such as CF3, F,
Cl, and Br, produced lower yields of the desired products (3g−
j, 40−50%; Table 2, entries 7−10), while significant improve-
ment was gained (59−69% yields) by using 30 mol % of
Pd(OAc)2. 2-Naphthohydrazide also worked well, producing
the corresponding product (3m) in good yield (70%, Table 2,
entry 13). A different substituent effect on the phenyl ring of
>P(O)H compounds was observed. When the F-, Cl-, and
1
(Scheme 4, eq 5). In the H NMR spectra, the signals of two
C
DOI: 10.1021/acs.orglett.9b00922
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Organic Letters
Letter
oxidation of Pd0 to PdII by Na2S2O8 closes the catalytic cycle.
In addition, intermediate C possibly also undergoes a Pd
insertion to form a Ar−C(O) bond followed by quenching
with water to release CO2, N2, and arylpalladium E, which is a
minor pathway.21b
Scheme 4. Control Experiments
In summary, we have developed a strategy of oxidative cross-
coupling of inert C−C bonds between easily oxidizable P−H
bonds for the facile and general synthesis of aryl phosphorus
compounds from readily available, easily handled, and cost-
saving materials. All three kinds of >P(O)H compounds are
suitable for the reaction, and various aryl phosphorus
compounds, as well as optically pure aryl phosphorus
compounds, are produced in satisfactory yields. The
association of the Brønsted acid and the bidentate phosphine
ligand along with the other reaction parameters allows the
suppression of the undesired oxidation of >P(O)−H
compounds and the selective oxidative activation of the
sp2C−C bonds, which not only provides a platform for the
ideal synthesis of aryl phosphorus compounds but also opens a
window for exploring oxidative synthesis between reactive
substrates and inert starting materials.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.9b00922.
■
hydrogen atoms of −NHNH2 disappeared in the presence of
1.0 equiv of Pd(OAc)2, which probably resulted in the
formation of intermediate B (Scheme 5). Two signals of OAc
S
Scheme 5. Possible Reaction Mechanism
Detailed experimental procedures, spectra data for all
1
compounds, H, 13C and 31P NMR spectra (PDF)
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: zhouyb@hnu.edu.cn.
ORCID
Jianyu Dong: 0000-0003-2161-1372
Yongbo Zhou: 0000-0002-3540-8618
Li-Biao Han: 0000-0001-5566-9017
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
Financial support from the NSF of China (Grant Nos.
21573065, 21878072, 21706058, and 21273066) and the
NSF of Hunan Province (Nos. 2016JJ1017 and 2018JJ3031) is
much appreciated.
with the ratio of 3:1 were observed when 2.0 equiv of
Pd(OAc)2 was added at room temperature, in which
intermediate C was probably formed and 3 equiv of HOAc
was released (for details, see the SI).
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