Manganese-Promoted Regioselective Direct C3-Phosphinoylation of 2-Pyridones

Article abstract of DOI:10.1002/ejoc.202100336

A highly efficient and regioselective manganese-induced radical oxidative direct C?P bond formation between 2-pyridones and secondary phosphine oxides was developed. The C3-selective phosphinoylation was conveniently achieved through a combination of substoichiometric manganese and persulfate oxidant under mild conditions. Various 3-phosphinoylated pyridone products can be obtained in moderate to high yields. Preliminary mechanistic studies suggest that the reaction is likely to involve a radical pathway induced by catalytically active Mn³⁺ species.

Full text of DOI:10.1002/ejoc.202100336

European Journal of Organic Chemistry
Accepted Article
Accepted Article
Title: Manganese - Catalyzed Regioselective Direct C3 -
Phosphinoylation of 2 - Pyridones
Authors: Tanakorn Kittikool, Kunita Phakdeeyothin, Teera
Chantarojsiri, and Sirilata Yotphan
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.202100336
Link to VoR: https://doi.org/10.1002/ejoc.202100336
0
1/2020

European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
Manganese-Promoted Regioselective Direct C3-Phosphinoylation
of 2-Pyridones
[
a]
[a]
[a]
[a]
Tanakorn Kittikool, Kunita Phakdeeyothin, Teera Chantarojsiri and Sirilata Yotphan*
Dedication ((optional))
[
a]
T. Kittikool, K. Phakdeeyothin, Dr. T. Chantarojsiri and Dr. S. Yotphan
Department of Chemistry and Center of Excellence for Innovation in Chemistry,
Faculty of Science, Mahidol University
Rama VI Road, Bangkok 10400, Thailand.
E-mail: sirilata.yot@mahidol.ac.th
Supporting information for this article is given via a link at the end of the document. ((Please delete this text if not appropriate))
Abstract: A highly efficient and regioselective manganese-induced
radical oxidative direct C−P bond coupling of 2-pyridones and
secondary phosphine oxides was developed. The C3-selective
phosphinoylation was conveniently achieved through a combination
of a substoichiometric manganese and a persulfate oxidant under mild
conditions, giving various 3-phosphinoylated pyridone products in
moderate to high yields. Preliminary mechanistic studies suggest that
the reaction is likely to involve a radical pathway induced by
interest in developing numerous synthetic methodologies to
construct and access substituted 2-pyridone compounds.[11] With
a tremendous and rapid progress in the field of C‒H bond
functionalization, continuous efforts to incorporate various
functional groups directly and regioselectively to the 2-pyridone
core under catalytic C‒H bond functionalization strategies were
extensively explored in recent years. Based on the four
electronically different C‒H bonds on the 2-pyridone ring, the
published work on site-selective catalytic C‒H transformation
3+
catalytically active Mn species.
have been reported, including alkylation,[12] alkenylation,[13]
alkynylation,[14]
allylation,
[15]
arylation,[16]
borylation,[17]
amidation[18] and thiolation.
[19]
Introduction
Phosphorus-substituted heterocycles represent a vital class
of organophosphorus compounds, which have constantly
received attention from chemists in both academia and industry.
The phosphorus substituents can alter the physical and chemical
properties of compounds as well as regulate important biological
functions.[ A number of these compounds are known to exhibit
attractive prospects as pharmaceuticals, agrochemicals, and
materials.[2] Furthermore, considerable efforts have been devoted
to explore highly efficient methods for preparation of such
compounds.[ Over the past decades, direct carbon‒phosphorus
1]
3]
(
C‒P) bond coupling from parent heterocycles via cross-
dehydrogenative coupling (CDC)/C‒H bond functionalization
reactions have become promising strategies in modern synthetic
chemistry, as they could bypass the requirement for pre-
functionalization in both coupling partners.[4]
Due to their environmentally benign nature, high relative
abundance, low cost and versatile reactivity, manganese (Mn)
salts have been employed in radical phosphinoylation reactions
to generate phosphinoyl radical from related phosphine oxides.[5,6]
To date, many studies applied Mn-mediated oxidative C‒P bond
Scheme 1. Mn-Promoted phosphinoylation of 2-pyridones.
In the context of phosphinoylation, the only example for
direct introduction of phosphorus functionality into pyridone
substrates reported to date, Zou et al showed that the
phosphinoylated pyridones can be obtained through Mn(III)-
mediated radical oxidative coupling of pyridines with dialkyl
phosphite species (Scheme 1).[20] Despite good yields of
coupling procedures toward a preparation of phosphorylated
heterocycles.[
7]
Nonetheless, Mn-catalyzed regioselective
phosphinoylation process is still quite rare.[8]
2
-Pyridone scaffold is a privileged structural motif in natural
products, pharmaceuticals, ligands in catalysis, organic materials
and polymers.[9] A number of substituted 2-pyridone derivatives
products, requirement of a large excess amount of Mn(OAc)
3
under harsh acidic conditions, as well as the need of substituents
at specific position on pyridone ring could limit its synthetic utility
and future advancement in associated fields. Thus, simple, mild,
and cost- effective catalytic methods for the synthesis of
phosphinoylated pyridones still need to be developed.
possess diverse range of activities including anticancer, antiviral,
activities.[10]
antibacterial and anti-inflammatory
As
a
consequence of their great synthetic value in many areas of
science, synthetic and medicinal chemists have a longstanding
1
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European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
Results and Discussion
experiment as no reaction occurred in the absence of Mn (entry
10). The choices of the oxidant and base were also crucial to the
efficiency of the transformation, and a reduced quantity of product
On this basis, we investigated the direct phosphinoylation of
pyridone 1a with diphenyl phosphine oxide (2a) under metal
catalysis conditions. To our delight, the use of a substoichiometric
2 2 8 2 3
was obtained when replacing K S O or K CO by other reagents
amount of Mn(OAc)
2
(20%) in combination with K
2
S
2
O
8
was found
(entries 11‒15). Meanwhile, lower product yield was observed in
the absence of the base (entry 16). Nonetheless, when
conducting this reaction in the absence of the oxidant and under
inert atmosphere, no corresponding product was formed (entry
17), indicating the necessity of the oxidant in this transformation.
Lastly, similar yield of the product was obtained as the reaction
was conducted under Ar (entry 18), highlighting the role of
persulfate oxidant as well as proving that this reaction is air-stable.
With the optimal conditions in hands, we consequently
aimed to investigate the scope and limitation of this
established method by performing the Mn-promoted
phosphinoylation of a diverse array of 2-pyridones with
to facilitate the exclusive C3-phosphinoylation of pyridone 1a
under the aerobic atmosphere, thus highlighting the possibility of
catalytic regioselective transformation, which could avoid the
employment of an excessive and much more expensive Mn3
reagent under harsh conditions. Among the various solvents
screened (Table 1, entries 1‒7), the use of 1:1 v/v ratio of
MeOH:THF was the most effective in this reaction, and the
desired product was obtained in 87% yield (entry 1). A slight
decrease in yield was observed when employing other
+
2
+
3+
manganese salts (Mn and Mn ), indicating that the source of
Mn can be feasible (entries 8‒9). However, the necessity of Mn
catalyst for this transformation was confirmed in the control
2 2
diphenylphosphine oxide (2a). In general, Mn(OAc) 4H O
catalyst enable the successful site-selective C‒P bond
coupling, and gave fair to decent yields of phosphorylated
pyridone derivatives under the standard conditions; however,
Table 1. Optimization of reaction conditions.[a]
3 2
employing Mn(OAc) 2H O instead of Mn(II) could help
improve conversions and afforded slightly higher quantities
of the coupling products for some cases. As illustrated in
Table 2, many N-alkylated pyridones underwent the direct
phosphinoylation
phosphinoylated pyridone derivatives in moderate to high
yields (3aa 3ae). The reaction of N-alkyl ester protected
pyridone substrate also proceeded, though only modest
amount of product was obtained (3b). The N-aryl protected
pyridone substrates were viable to this oxidative coupling
reaction, affording good quantities of products (3ca and
smoothly,
furnishing
the
C3-
‒
Entry
Deviations from standard conditions
None
Yield[b] (%)
1
2
3
4
5
6
7
8
9
87 (82)[c]
76
55
20
0
THF instead of 1:1 MeOH:THF
MeOH instead of 1:1 MeOH:THF
3cb). Nevertheless, no reaction was found when employing
the N-arylated pyridone substrate bearing the nitro group at
the N1 position (3cd). This is likely to be a consequence of a
strong electron-withdrawing effect of the nitro group which
could dramatically suppress reactivity towards the
reaction.[21] For the N-pyridyl pyridone substrate, no effect
from pyridyl directing group was observed and only C3-
phophorylated product were obtained (3cc). In addition, we
surveyed the effect of substituents on carbon atoms of the
pyridone ring. In the case of electron rich group at C6
positions, both N-protected pyridones and NH-pyridones
substatres were converted to desired product in fair to good
yields (3d and 3e). Next, in the case of pyridone substrates
bearing a halogen substitution at C5 positions, the satisfied
quantities of products were achieved with the halogen
groups (chloro and bromo) remained intact (3fa and 3fb).
3
CH CN instead of 1:1 MeOH:THF
DCE instead of 1:1 MeOH:THF
DMSO instead of 1:1 MeOH:THF
45
0
H
2
O instead of 1:1 MeOH:THF
MnCl •4H O instead of Mn(OAc)
Mn(OAc) •2H O instead of Mn(OAc)
No Mn(OAc) •4H
Na instead of K
(NH instead of K
Na CO instead of K CO
NaOAc instead of K CO
NEt instead of K CO
No base
2
2
2
•4H
2
O
71
79
0
3
2
2 2
•4H O
1
1
1
1
1
1
1
1
1
0
1
2
3
4
5
6
7
8
2
2
O
2
S
2
O
8
2
S
2
O
8
42
55
68
57
69
37
0
4
)
2
S
2
O
8
2 2 8
S O
These results could be useful for
a
late-stage
2
3
2
3
functionalization of the compounds. We also found that the
electronic effect from the substrates was crucial for the Mn-
catalyzed oxidative C‒P bond formation. The substrates
with electron donating groups (such as methyl, phenyl and
aryl sulfide groups) provided moderate to excellent yields of
2
3
3
2
3
corresponding C‒P bond coupling products (3ga
the other hand, the electron poor nitro substituted pyridone
3j) was incompetent to be converted to the product under
‒3ib). On
No oxidant (reaction under Ar)
(
Reaction under Ar
87
the optimal conditions, suggesting the influence of electron
withdrawing group could impede substrate reactivity toward
the reaction. Remarkably, this method proved to be
amenable to the pyrimidinone and 2-quinolinol substrates,
[
a] Conditions: 1a (0.1 mmol, 1.0 equiv.), 2a (1.5 equiv.), catalyst (20 mol%),
additive (2.0 equiv.), oxidant (3.0 equiv.) in 0.4 mL of solvent at 70 °C under an
air atmosphere for 16 h. [b] NMR yield. [c] Isolated yield.
2
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European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
giving the products 3ka
‒
3kb and 3l in moderate to good
conditions (3ne). Unfortunately, no reaction was observed in the
quantities. Lastly, the developed Mn-induced direct C3-
phosphinoylation was applicable to transform pirfenidone
drug, which is used for a treatment of idiopathic pulmonary
fibrosis,[22] to the corresponding analogue (3m) in 66% yield
under the optimal conditions.
case of diarylphosphine oxide bearing
a strong electron
withdrawing CF group at the C4 position of the aryl ring (3nf),
3
suggesting the difficult-to-oxidize phosphine oxide could cause
the instability of the intermediate and have a critical impact in this
transformation. Lastly, the direct phosphinoylation was examined
with dibutylphosphine oxide and diethylphosphite (3ng and 3nh);
nonetheless, no reaction could be accomplished, probably owing
to the lack of  stabilization to P-centered radical intermediate.
In order to gain mechanistic insight, control experiments
were conducted and described in Scheme 2. Radical trapping
experiments using TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy)
or BHT (butylated hydroxytoluene) were conducted and a
significantly interruption of the phosphinoylation was observed,
supporting that the radical process is operative (Scheme 2a). In
addition, upon subjecting C3-substituted pyridone to the same
reaction condition, no other products or side reactions were found
which is indicative of the site-selectivity of this transformation
Table 2. Substrate scope for the C−H phosphinoylation of 2-pyridones.[a], [b]
(
Scheme 2b). When carrying out a reaction in the absence of the
oxidant under inert atmosphere of Ar, no reaction was observed
2
+
when using Mn ; however, the reaction still occurred when using
Mn3+ (Scheme 2c). These results implied that Mn3+ could be a
catalytically active species of this transformation, which induces a
radical oxidative phosphinoylation to proceed. Interestingly, the
oxidative C‒P bond coupling reaction still occurred (29%) under
air atmosphere in the absence of persulfate, suggesting that O
2
could possibly become an alternative source of oxidant, but it is
not as effective as the persulfate oxidant.
[
(
[
a] Conditions: 1 (1.0 mmol), 2 (1.5 mmol), Mn(OAc)
2.0 mmol), K (3.0 mmol), solvent (4 mL), 70 °C, 16 h. [b] Isolated yield.
c] Using Mn(OAc) •2H O instead of Mn(OAc) •4H O.
2 2 2 3
•4H O (20 mol%), K CO
2 2 8
S O
3
2
2
2
In terms of coupling partner, diarylphosphine oxide with
alkyl, methoxyl, and chloro substitutions at para-position all
exhibited moderate to good reactivities, providing the C3-
phosphinoylated products in moderate to good yields (3na‒3nc).
Diarylphosphine oxide bearing a 3,5 disubstituted methyl group
on the aryl ring afforded the product (3nd) in 55% isolated yield.
The phosphine oxide substrate with the inductive effect from the
Scheme 2. Control experiments.
3
-alkoxy group was also compatible under the established
3
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European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
CDCl
3
(7.26 ppm for H and 77.16 ppm for 13C). IR spectra were recorded
1
On the basis of the above experimental observations and
previous reports,[8,23] a plausible mechanism is proposed for the
Mn-promoted oxidative phosphinoylation as depicted in Scheme
on Bruker FT-IR Spectrometer Model ALPHA by neat method, and only
partial data are listed. Melting points were determined on Buchi Melting
Point M-565 apparatus. High resolution mass spectroscopy (HRMS) data
3
. Initially, a single electron transfer process is likely to generate
were analysed by
a high-resolution micrOTOF instrument with
Mn(III) active species and subsequently undergoes a hydrogen
abstraction from diphenylphosphine oxide to afford phosphinoyl
radical (I). The latter radical reacts with the pyridone substrate at
C3 position, which is controlled by resonance stabilization of the
intermediate, generating the intermediate II. Further oxidation
process, which might be associated to Mn(III)/Mn(II) system and
sulfate radical anion pathway, could give rise to the cation
intermediate III. Finally, the phoshinoylated product is formed
upon elimination.
electrospray ionization (ESI).
General Procedure for the Manganese-Promoted Regioselective
Direct C‒H Phosphinoylation of 2-Pyridones: Synthesis of
Compounds 3aa
2-pyridone (0.5 mmol, 1.0 equiv.), diarylphosphine oxide (0.75 mmol, 1.5
equiv.), Mn(OAc) 4H O (0.1 mmol, 20 mol%), K CO (1.0 mmol, 2.0
equiv.), K (1.5 mmol, 3.0 equiv.) and MeOH:THF (1:1 v/v, 2.0 mL)
were added, respectively. The reaction mixture was stirred at 70 °C for 16
h. Upon completion (as monitored by TLC), distilled deionized H O (10 mL)
was added, and the mixture was extracted with ethyl acetate (EtOAc) (2 ×
0 mL). The combined organic layer was washed with saturated NaCl,
̶ 3ne. To a 2-dram vial equipped with a magnetic stir bar,
2
2
2
3
2 2 8
S O
2
2
dried over anhydrous Na
product was purified by SiO
phosphinoylated pyridone product.
2 4
SO , and concentrated in vacuo. The crude
2
column chromatography to afford the 3-
1
-Benzyl-3-(diphenylphosphoryl)pyridin-2(1H)-one (3aa). Off-white
1
solid (158 mg, 82% yield); mp = 213.7–214.3 °C; H NMR (400 MHz,
CDCl
3
): δ 8.35 (ddd, J = 14.0, 7.0, 2.0 Hz, 1H), 7.90–7.85 (m, 4H), 7.53–
.46 (m, 3H), 7.45–7.40 (m, 4H), 7.31–7.29 (m, 3H), 7.21–7.19 (m, 2H),
.35 (td, J = 6.8, 2.3 Hz, 1H), 5.06 (s, 2H); 13C NMR (100 MHz, CDCl
): δ
7
6
3
1
1
1
61.0 (d, JCP = 12.7 Hz), 148.8 (d, JCP = 5.5 Hz), 141.9, 135.8, 132.1, 132.0,
31.9 (d, JCP = 108.8 Hz), 129.1, 128.4, 128.3 (d, JCP = 12.7 Hz), 128.2,
23.4 (d, JCP = 106.8 Hz), 106.4 (d, JCP = 12.1 Hz), 52.1; 31P NMR (162
-
1
MHz, CDCl
3
): δ 25.5; IR (neat, cm ): ν = 3058, 1642, 1586, 1534, 1435,
1
305, 1218, 1117, 942, 772, 691; HRMS (ESI): calcd for C24H20NO PNa
2
+
[M+Na] 408.1124, found 408.1126.
3
-(Diphenylphosphoryl)-1-methylpyridin-2(1H)-one (3ab). White solid
1
(
8
3
68 mg, 44% yield); mp = 206.4
.40 (ddd, J = 14.0, 7.0, 2.2 Hz, 1H), 7.92
H), 7.45
̶
207.6 °C; H NMR (400 MHz, CDCl
3
): δ
7.47 (m,
7.41 (m, 4H), 6.38 (td, J = 6.8, 2.0 Hz, 1H), 3.49 (s, 3H); 13C
): δ 161.3 (d, JCP = 12.9 Hz), 148.9 (d, JCP = 5.4
Hz), 132.1 (d, JCP = 10.6 Hz), 143.0, 132.0 (d, JCP = 108.5 Hz), 131.9 (d,
CP = 2.7 Hz), 128.3 (d, JCP = 12.8 Hz), 123.1 (d, JCP = 107.0 Hz), 106.1
d, JCP = 12.0 Hz), 37.9; 31P NMR (162 MHz, CDCl ): δ 25.1; IR (neat, cm-
̶ 7.87 (m, 4H), 7.86 ̶
̶
NMR (100 MHz, CDCl
3
Scheme 3. Possible mechanism.
J
(
1
3
)
: ν = 3050, 2923, 1640, 1536, 1361, 1208, 1118, 939, 785, 696, 527;
+
Conclusion
HRMS (ESI): calcd for C18
H
16NO
2
PNa [M+Na] 332.0811, found 332.0810.
In conclusion, we have successfully established
a
3-(Diphenylphosphoryl)-1-ethylpyridin-2(1H)-one (3ac). Colorless
1
solid (71 mg, 44% yield); mp = 139.4
δ 8.32 (ddd, J = 14.0, 6.8, 2.2 Hz, 1H), 7.88
̶
140.1 °C; H NMR (400 MHz, CDCl
3
):
7.48 (m,
7.38 (m, 4H), 6.36 (td, J = 6.8, 2.4 Hz, 1H), 3.89 (q, J = 7.2 Hz,
H), 1.26 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl
): δ 160.6 (d, JCP
12.8 Hz), 148.5 (d, JCP = 5.6 Hz), 141.8, 131.9 (d, JCP = 10.9 Hz), 131.9
regioselective Mn-promoted oxidative C‒P bond coupling of
pyridones and secondary phosphine oxide. This method allows
C3-phosphinoylation to take place effectively under radical
process. The current protocol features simple and cheap catalytic
̶
7.83 (m, 4H), 7.50 ̶
3
2
=
H), 7.45 ̶
3
2
+
operation (using substoichiometric amount of Mn ), mild and
robust reaction conditions under air with a broad range of
substrate scope, which may lead towards further extension of the
synthetic utility as well as a discovery of potent bioactive
molecules and organic materials.
(
d, JCP = 108.5 Hz), 131.8, 128.2 (d, JCP = 12.6 Hz), 123.0 (d, JCP = 107.3
Hz), 106.2 (d, JCP = 12.1 Hz), 45.1, 14.6; 31P NMR (162 MHz, CDCl
): δ
25.5;IR (neat, cm ): ν = 3054, 2962, 1641, 1532, 1433, 1312, 1250, 1118,
1022, 980, 833, 700; HRMS (ESI): calcd for C19
PNa [M+Na]+
3
-
1
H
18NO
2
346.0967, found 346.0965.
3
-(Diphenylphosphoryl)-1-isopropylpyridin-2(1H)-one (3ad). White
160.0 °C; 1H NMR (400 MHz,
): δ 8.33 (ddd, J = 14.0, 6.8, 2.2 Hz, 1H), 7.91 7.86 (m, 4H), 7.57
.55 (m, 1H), 7.53 7.49 (m, 2H), 7.45 7.41 (m, 4H), 6.44 (td, J = 7.0, 2.1
Hz, 1H), 5.14 (sep, J = 6.8 Hz, 1H), 1.31 (d, J = 6.8 Hz, 6H); 13C NMR (100
MHz, CDCl ): δ 160.6 (d, JCP = 12.8 Hz), 147.9 (d, JCP = 5.5 Hz), 137.6,
32.2 (d, JCP = 108.5 Hz), 132.1 (d, JCP = 10.5 Hz), 131.9 (d, JCP = 2.4 Hz),
solid (136 mg, 81% yield); mp = 159.0
CDCl
7
̶
Experimental Section
3
̶
̶
̶
̶
General Information: Unless otherwise noted, all reagents were obtained
from commercial suppliers and used without further purification. All
experiments were carried out under air atmosphere, and oven-dried
glasswares were used in all cases. Column chromatography was
3
1
1
28.3 (d, JCP = 12.6 Hz), 122.9 (d, JCP = 107.3 Hz), 106.4 (d, JCP = 12.1
performed over silica gel (SiO
Mesh). 1H, 13C and 31P NMR spectra were recorded on Bruker-AV400
spectrometers in CDCl solution, at 400, 100 and 162 MHz, respectively.
NMR chemical shifts are reported in ppm, and were measured relative to
2
; 60 Å silica gel, Merck Grade, 70–230
Hz), 46.8, 22.1; 31P NMR (162 MHz, CDCl
-1
3
): δ 25.5; IR (neat, cm ): ν =
3
054, 1639, 1528, 1436, 1336, 1243, 1156, 1094, 1068, 992, 909, 694;
3
+
2
HRMS (ESI): calcd for C20H21NO P [M+H] 338.1304, found 338.1301.
4
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European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
3
(
-(Diphenylphosphoryl)-1-pentylpyridin-2(1H)-one (3ae). Colorless oil
100 mg, 55% yield); 1H NMR (400 MHz, CDCl
): δ 8.34 (ddd, J = 13.9,
.9, 2.3 Hz, 1H), 7.89 7.84 (m, 4H), 7.50 7.46 (m, 3H), 7.43
.35 (td, J = 6.8, 2.0 Hz, 1H), 3.84 (t, J = 7.4 Hz, 2H), 1.68
.33
60.7 (d, JCP = 12.8 Hz), 148.5 (d, JCP = 5.6 Hz), 142.2, 132.1 (d, JCP
132.1 (d, JCP = 10.5 Hz), 132.0 (d, JCP = 108.7 Hz), 131.9 (d, JCP = 2.0 Hz),
129.0, 128.3 (d, JCP = 12.7 Hz), 127.7, 126.6, 119.3 (d, JCP = 110.4 Hz),
3
6
6
1
1
1
=
2
3
̶
̶
̶
7.38 (m, 4H),
1.61 (m, 2H),
107.7 (d, JCP = 11.8 Hz), 47.3, 21.2; 31P NMR (162 MHz, CDCl
3
): δ 26.6;
-
1
̶
IR (neat, cm ): ν = 3066, 1674, 1570, 1436, 1340, 1232, 1084, 901, 712,
̶
1.18 (m, 4H), 0.83 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl
3
): δ
603, 515; HRMS (ESI): calcd for C25
400.1460.
H23NO
2
P [M+H]+ 400.1461, found
=
08.4 Hz), 131.9 (d, JCP = 10.5 Hz), 131.8 (d, JCP = 2.6 Hz), 128.2 (d, JCP
12.6 Hz), 123.1 (d, JCP = 107.1 Hz), 106.1 (d, JCP = 12.1 Hz), 50.0, 29.1,
3
-(Diphenylphosphoryl)-6-phenylpyridin-2(1H)-one (3e). Colorless
249.2 °C; 1H NMR (400 MHz,
solid (145 mg, 78% yield); mp = 248.1
8.7, 22.3, 14.0; 31P NMR (162 MHz, CDCl
059, 2928, 1640, 1535, 1435, 1309, 1213, 1117, 998, 854, 691; HRMS
): δ 25.4; IR (neat, cm ): ν =
-1
3
̶
CDCl ): δ 13.42 (s, 1H), 8.56 (dd, J = 13.6, 7,2 Hz, 1H), 7.76−7.71 (m, 4H),
3
+
(
ESI): calcd for C22
H
25NO
2
P [M+H] 366.1617, found 366.1614.
7.57 (d, J = 7.6 Hz, 2H), 7.46 (t, J = 7.0 Hz, 2H), 7.36 (t, J = 7.4 Hz, 1H),
7
.28−7.34 (m, 4H), 7.07 (t, J = 7.8 Hz, 2H), 6.72 (dd, J = 7.2, 1.2 Hz, 1H);
1
3C NMR (100 MHz, CDCl
Methyl 2-(3-(diphenylphosphoryl)-2-oxopyridin-1(2H)-yl)acetate (3b).
Off-white solid (68 mg, 37% yield); mp = 152.5
153.5 °C; 1H NMR (400
MHz, CDCl ): δ 8.38 (ddd, J = 14.0, 7.0, 2.1 Hz, 1H), 7.84 7.78 (m, 4H),
.50 7.44 (m, 3H), 7.42 7.37 (m, 4H), 6.39 (td, J = 6.8, 2.0 Hz, 1H), 4.56
s, 2H), 3.68 (s, 3H); C NMR (100 MHz, CDCl ): δ 167.6, 160.7 (d, JCP
2.8 Hz), 149.6 (d, JCP = 5.4 Hz), 142.8, 132.0 (d, JCP = 2.8 Hz), 131.9 (d,
CP = 10.6 Hz), 131.6 (d, JCP = 108.8 Hz), 128.3 (d, JCP = 12.7 Hz), 123.2
d, JCP = 106.5 Hz), 106.4 (d, JCP = 12.0 Hz), 52.7, 50.4; 31P NMR (162
3
): δ 164.2 (d, JCP = 12.7 Hz), 152.4, 150.6 (d,
̶
J
CP = 5.3 Hz), 132.6, 132.4 (d, JCP = 10.8 Hz), 132.1 (d, JCP = 108.7 Hz),
3
̶
131.9 (d, JCP = 2.0 Hz), 130.8, 129.1, 128.0 (d, JCP = 12.7 Hz), 127.5, 119.2
(d, JCP = 108.6 Hz), 106.0 (d, JCP = 11.1 Hz); 31P NMR (162 MHz, CDCl
δ 25.6; IR (neat, cm ): ν = 2915, 1714, 1629, 1550, 1436, 1331, 1156,
1050, 956, 781, 691, 530; HRMS (ESI): calcd for C23
7
(
1
J
̶
̶
3
):
13
-1
3
=
H
19NO
2
P [M+H]+
372.1148, found 372.1145.
(
-
1
3
MHz, CDCl ): δ 25.3; IR (neat, cm ): ν = 3068, 1755, 1649, 1537, 1437,
1
-Benzyl-5-chloro-3-(diphenylphosphoryl)pyridin-2(1H)-one
(3fa).
1
C
312, 1205, 1114, 1004, 905, 753, 697; HRMS (ESI): calcd for
H19NO P [M+H] 368.1046, found 368.1040.
20 4
1
White solid (178 mg, 85% yield); mp = 134.7 ̶ 135.8 °C; H NMR (400 MHz,
+
CDCl
m, 2H), 7.47−7.43 (m, 5H), 7.34−7.33 (m, 3H), 7.24−7.20 (m, 2H), 5.03
(s, 2H); 13C NMR (100 MHz, CDCl
): δ 159.5 (d, JCP = 11.9 Hz), 149.0 (d,
JCP = 6.0 Hz), 139.2, 135.1, 132.3 (d, JCP = 2.6 Hz), 132.1 (d, JCP = 10.7
3
): δ 8.37 (dd, J = 14.0, 3.2 Hz, 1H), 7.91−7.86 (m, 4H), 7.56−7.52
(
3
-(Diphenylphosphoryl)-1-phenylpyridin-2(1H)-one (3ca). Light yellow
solid (134 mg, 72% yield); mp = 183.4
184.5 °C; 1H NMR (400 MHz,
CDCl ): δ 8.52 (ddd, J = 14.0, 6.8, 2.0 Hz, 1H), 7.95 7.90 (m, 4H), 7.60
.58 (m, 1H), 7.53 7.47 (m, 2H), 7.46 7.39 (m, 7H), 7.32 7.30 (m, 2H),
.50 (td, J = 6.8, 2.0 Hz, 1H); C NMR (100 MHz, CDCl ): δ 160.6 (d, JCP
3
̶
3
̶
̶
Hz), 131.2 (d, JCP = 109.8 Hz), 129.3, 128.8, 128.5, 128.4 (d, JCP = 12.8
Hz), 125.1 (d, JCP = 102.7 Hz), 113.2 (d, JCP = 15.2 Hz), 52.4; 31P NMR
(162 MHz, CDCl
1436, 1182, 1071, 903, 724, 691, 521; HRMS (ESI): calcd for
C
7
6
=
1
̶
̶
̶
13
-1
3
3
): δ 24.5; IR (neat, cm ): ν = 3057, 2852, 1649, 1523,
12.9 Hz), 147.5 (d, JCP = 5.4 Hz), 142.6, 140.2, 132.1 (d, JCP = 10.6 Hz),
31.9 (d, JCP = 2.5 Hz), 131.7 (d, JCP = 108.7 Hz), 129.5, 128.9, 128.3 (d,
+
24
H
19ClNO
2
PNa [M+Na] 442.0734, found 442.0736.
J
CP = 12.8 Hz), 126.5, 124.3 (d, JCP = 105.7 Hz), 106.2 (d, JCP = 12.1 Hz);
3
1P NMR (162 MHz, CDCl
-1
3
): δ 25.2; IR (neat, cm ): ν = 3056, 1650, 1528,
1
-Benzyl-5-bromo-3-(diphenylphosphoryl)pyridin-2(1H)-one
(3fb).
1
C
434, 1313, 1266, 1153, 1020, 749, 691; HRMS (ESI): calcd for
H18NO PNa [M+Na] 394.0967, found 394.0965.
23 2
169.0 °C; 1H NMR (400
Colorless solid (98 mg, 42% yield); mp = 168.2
MHz, CDCl
.52 (m, 3H), 7.47
̶
+
3
): δ 8.44 (dd, J = 14.0, 2.8 Hz, 1H), 7.91
̶
7.86 (m, 4H), 7.57
7.33 (m, 3H), 7.22 7.20 (m, 2H),
): δ 159.6 (d, JCP = 12.0 Hz), 151.1
̶
7
̶
7.43 (m, 4H), 7.34
̶
̶
13
3-(Diphenylphosphoryl)-1-(4-methoxyphenyl)pyridin-2(1H)-one (3cb).
5.03 (s, 2H); C NMR (100 MHz, CDCl
3
1
White solid (146 mg, 73% yield); mp = 174.5
CDCl ): δ 8.49 (ddd, J = 14.0, 6.8, 2.0 Hz, 1H), 7.95
J = 6.8 Hz, 1H), 7.49 7.47 (m, 2H), 7.44 7.39 (m, 4H), 7.21 (d, J = 9.2 Hz,
H), 6.94 (d, J = 8.8 Hz, 2H), 6.46 (td, J = 6.8, 2.0 Hz, 1H), 3.80 (s, 2H);
): δ 160.9 (d, JCP = 13.0 Hz), 159.7, 149.4 (d,
CP = 5.4 Hz), 142.9, 133.0, 132.1 (d, JCP = 10.6 Hz), 131.9 (d, JCP = 2.4
Hz), 131.8 (d, JCP = 108.7 Hz), 128.3 (d, JCP = 12.6 Hz), 127.6, 124.3 (d,
̶
175.6 °C; H NMR (400 MHz,
(d, JCP = 5.9 Hz), 141.5, 135.2, 132.3 (d, JCP = 2.7 Hz), 132.1 (d, JCP = 10.6
Hz), 131.2 (d, JCP = 109.3 Hz), 129.3, 128.8, 128.4 (d, JCP = 12.7 Hz),
128.3, 125.5 (d, JCP = 102.2 Hz), 98.5 (d, JCP = 14.9 Hz), 52.4; 31P NMR
(162 MHz, CDCl ): δ 24.4; IR (neat, cm ): ν = 3054, 2922, 1644, 1519,
3
1435, 1180, 998, 856, 690, 536; HRMS (ESI): calcd for C24
3
̶ 7.90 (m, 4H), 7.57 (d,
̶
̶
-
1
2
1
3C NMR (100 MHz, CDCl
3
H
19BrNO
2
PNa
+
J
[M+Na] 486.0229, found 486.0217.
J
CP = 105.9 Hz), 114.7, 106.1 (d, JCP = 12.2 Hz), 55.7; 31P NMR (162 MHz,
1-Benzyl-3-(diphenylphosphoryl)-5-methylpyridin-2(1H)-one
(3ga).
136.5 °C; H NMR (400 MHz,
7.87 (m, 4H), 7.54 7.50
7.29 (m, 3H), 7.25 (t, J = 1.2 Hz, 1H),
7.19 (m, 2H), 5.05 (s, 2H), 2.11 (s, 3H); 13C NMR (100 MHz, CDCl
):
-
1
CDCl
3
): δ 25.0; IR (neat, cm ): ν = 3058, 2837, 2218, 1650, 1508, 1246,
PNa [M+Na]+
1
White solid (184 mg, 92% yield); mp = 135.5
̶
1098, 909, 722, 691; HRMS (ESI): calcd for C24
H20NO
3
CDCl
m, 2H), 7.46
.21
3
): δ 8.31 (dd, J = 14.4, 2.6 Hz, 1H), 7.93
̶
̶
424.1073, found 424.1075.
(
̶
7.41 (m, 4H), 7.33
̶
7
̶
3
3
-(Diphenylphosphoryl)-2H-[1,2'-bipyridin]-2-one (3cc). Off-white solid
δ 160.3 (d, JCP = 12.9 Hz), 151.1 (d, JCP = 5.2 Hz), 139.7, 136.2, 132.2,
132.0, 131.8 (d, JCP = 108.9 Hz), 129.1, 128.3 (d, JCP = 12.6 Hz), 128.3,
128.2, 122.7 (d, JCP = 107.1 Hz), 115.8 (d, JCP = 11.8 Hz), 52.0, 17.2; 31P
1
(
114 mg, 61% yield); mp = 172.9
̶
173.7 °C; H NMR (400 MHz, CDCl
3
): δ
8
6
2
.54 (d, J = 4.8 Hz, 1H), 8.46 (ddd, J = 14.0, 6.8, 2.4 Hz, 1H), 8.12 (d, J =
.4 Hz, 1H), 7.93 7.88 (m, 4H), 7.77 (d, J = 4.0 Hz, 2H), 7.53 7.49 (m,
H), 7.46 7.43 (m, 4H), 7.32 7.29 (m, 1H), 6.55 (td, J = 6.8, 1.6 Hz, 1H);
C NMR (100 MHz, CDCl ): δ 160.6 (d, JCP = 12.6 Hz), 151.3, 150.0 (d,
CP = 5.5 Hz), 149.2, 141.0, 138.0, 132.1 (d, JCP = 10.6 Hz), 132.0 (d, JCP
2.6 Hz), 131.8 (d, JCP = 108.9 Hz), 128.4 (d, JCP = 12.8 Hz), 124.8 (d,
CP = 106.1 Hz), 123.7, 121.5, 106.6 (d, JCP = 12.2 Hz); 31P NMR (162 MHz,
-
1
̶
̶
3
NMR (162 MHz, CDCl ): δ 26.2; IR (neat, cm ): ν = 3044, 2920, 1684,
̶
̶
1507, 1380, 1208, 996, 877, 725, 636, 508; HRMS (ESI): calcd for
1
3
+
3
C
25
H
23NO
2
P [M+H] 400.1461, found 400.1460.
J
=
J
3
-(Diphenylphosphoryl)-5-methylpyridin-2(1H)-one (3gb). White solid
1
(
85 mg, 55% yield); mp = 179.4
̶
180.6 °C; H NMR (400 MHz, CDCl
3
): δ
-
1
CDCl
3
): δ 25.6; IR (neat, cm ): ν = 3056, 1661, 1586, 1472, 1311, 1236,
P [M+H]+
1
2
2.38 (s, 1H), 8.22 (d, J = 14.0 Hz, 1H), 7.87
H), 7.43
̶
7.82 (m, 4H), 7.52 ̶ 7.48 (m,
1119, 996, 691, 535; HRMS (ESI): calcd for C22
H
18
N
O
2 2
13
̶
7.38 (m, 4H), 6.90 (s, 1H), 2.06 (s, 3H); C NMR (100 MHz,
373.1100, found 373.1103.
3
CDCl ): δ 162.4 (d, JCP = 11.8 Hz), 152.3 (d, JCP = 5.0 Hz), 137.4, 132.1,
1
32.0, 131.9 (d, JCP = 108.4 Hz), 128.3 (d, JCP = 12.6 Hz), 121.8 (d, JCP
=
1
-Benzyl-3-(diphenylphosphoryl)-6-methylpyridin-2(1H)-one
(3d).
106.9 Hz), 116.2 (d, JCP = 10.9 Hz), 16.9; 31P NMR (162 MHz, CDCl
3
): δ
1
-1
White solid (106 mg, 53% yield); mp = 200.4
CDCl
̶
201.8 °C; H NMR (400 MHz,
25.5; IR (neat, cm ): ν = 3006, 2852, 1653, 1619, 1456, 1321, 1158, 1040,
994, 703, 518; HRMS (ESI): calcd for C18
+
3
): δ 8.31 (dd, J = 14.0, 7.2 Hz, 1H), 7.92−7.87 (m, 4H), 7.51 (td, J =
.4, 1.2 Hz, 2H), 7.45−7.41 (m, 4H), 7.27−7.25 (m, 3H), 7.05−7.03 (m, 2H),
.29 (d, J = 6.0 Hz, 1H), 5.27 (s, 2H), 2.34 (s, 3H); 13C NMR (100 MHz,
): δ 162.2 (d, JCP = 13.0 Hz), 152.6, 148.2 (d, JCP = 5.3 Hz), 135.7,
H
17NO
2
P [M+H] 310.0991, found
7
6
310.0995.
CDCl
3
5
This article is protected by copyright. All rights reserved.

European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
1
-Benzyl-3-(diphenylphosphoryl)-5-phenylpyridin-2(1H)-one
(3h).
124.7 (d, JCP = 104.9 Hz), 123.3, 119.5 (d, JCP = 11.5 Hz), 116.1; 31P NMR
1
-1
White solid (180 mg, 78% yield); mp = 189.4
CDCl
̶
190.2 °C; H NMR (400 MHz,
(162 MHz, CDCl
3
): δ 24.8; IR (neat, cm ): ν = 3144, 2891, 1654, 1563,
3
): δ 8.72 (dd, J = 14.0, 2.6 Hz, 1H), 7.97−7.92 (m, 4H), 7.69 (d, J =
.4 Hz, 1H), 7.56−7.52 (m, 2H), 7.48−7.43 (m, 4H), 7.42−7.36 (m, 4H),
.34−7.31 (m, 4H), 7.27−7.25 (m, 2H), 5.16 (s, 2H); 13C NMR (100 MHz,
): δ 160.4 (d, JCP = 12.6 Hz), 148.3 (d, JCP = 5.6 Hz), 138.9 (d, JCP
.2 Hz), 135.7 (d, JCP = 25.4 Hz), 132.2, 132.1, 132.0 (d, JCP = 108.7 Hz),
29.2 (2C), 128.5, 128.4, 128.3, 128.2, 127.8, 126.1, 123.7 (d, JCP = 105.4
): δ 25.7; IR
neat, cm ): ν = 3056, 1648, 1524, 1435, 1273, 1118, 1027, 962, 869, 691,
1358, 1245, 1100, 1031, 953, 842, 689; HRMS (ESI): calcd for
+
2
7
C
21
H
17NO
2
P [M+H] 346.0991, found 346.0990.
CDCl
3
=
3
-(Diphenylphosphoryl)-5-methyl-1-phenylpyridin-2(1H)-one
(3m).
1
1
61.5 °C; 1H NMR (400
Colorless solid (127 mg, 66% yield); mp = 60.5
MHz, CDCl
̶
3
): δ 8.44 (dd, J = 14.4, 2.8 Hz, 1H), 7.97
̶
7.91 (m, 4H), 7.52
7.36 (m, 3H), 7.31 7.29 (m, 2H),
): δ 160.0 (d, JCP = 13.2 Hz), 151.8
̶
Hz), 120.9 (d, JCP = 11.7 Hz), 52.5; 31P NMR (162 MHz, CDCl
3
7
2
.48 (m, 2H), 7.44
̶
7.42 (m, 5H), 7.41
̶
̶
-
1
(
.20 (s, 3H); 13C NMR (100 MHz, CDCl
3
5
4
30; HRMS (ESI): calcd for C30
84.1436.
H24NO
2
PNa [M+Na]+ 484.1437, found
(
d, JCP = 5.0 Hz), 140.5, 140.3, 132.2 (d, JCP = 10.6 Hz), 132.0 (d, JCP =
1
1
08.5 Hz), 131.9 (d, JCP = 2.4 Hz), 129.5, 128.7, 128.3 (d, JCP = 12.7 Hz),
26.6, 123.9 (d, JCP = 105.2 Hz), 115.4 (d, JCP = 11.8 Hz), 17.0; 31P NMR
-
1
3
-(Diphenylphosphoryl)-1-methyl-5-(p-tolylthio)pyridin-2(1H)-one
172.6 °C; 1H NMR
): δ 8.47 (dd, J = 14.0, 2.4 Hz, 1H), 7.90−7.85 (m, 4H),
.74 (d, J = 1.6 Hz, 1H), 7.55−7.51 (m, 2H), 7.47−7.42 (m, 4H), 7.17 (d, J
8.0 Hz, 2H), 7.09 (d, J = 8.0 Hz, 2H), 3.49 (s, 3H), 2.31 (s, 3H); 13C NMR
): δ 160.5 (d, JCP = 12.9 Hz), 154.0 (d, JCP = 5.5 Hz),
3
(162 MHz, CDCl ): δ 25.1; IR (neat, cm ): ν = 3056, 2924, 1657, 1523,
(
(
3ia). Yellow solid (104 mg, 48% yield); mp = 171.9
400 MHz, CDCl
̶
1436, 1265, 1118, 918, 777, 690, 537; HRMS (ESI): calcd for C24
[M+H] 386.1304, found 386.1302.
H
2
21NO P
+
3
7
=
1
-Benzyl-3-(di-p-tolylphosphoryl)pyridin-2(1H)-one (3na). White solid
(
100 MHz, CDCl
3
1
(
8
1
149 mg, 72% yield); mp = 158.7
̶
159.5 °C; H NMR (400 MHz, CDCl
.34 (ddd, J = 13.9, 6.9, 2.1 Hz, 1H), 7.79 7.74 (m, 4H), 7.46
7.20 (m, 6H), 6.34 (td, J = 6.8, 2.0 Hz, 1H),
3
): δ
1
1
3
2
47.2, 137.4, 132.2, 132.2 (d, JCP = 5.5 Hz), 132.1, 130.7, 130.3, 129.7,
28.4 (d, JCP = 12.8 Hz), 124.7 (d, JCP = 87.5 Hz), 112.2 (d, JCP = 13.0 Hz),
8.1, 21.2; P NMR (162 MHz, CDCl
919, 2850, 1642, 1516, 1184, 1071, 999, 862, 691; HRMS (ESI): calcd
̶
̶ 7.44 (m,
H), 7.35
̶
7.30 (m, 3H), 7.25 ̶
31
-1
3
): δ 24.6; IR (neat, cm ): ν = 3052,
13
3
5.08 (s, 2H), 2.38 (s, 6H); C NMR (100 MHz, CDCl ): δ 161.0 (d, JCP =
1
1
1
2.7 Hz), 148.5 (d, JCP = 5.5 Hz), 142.3 (d, JCP = 2.4 Hz), 141.6, 135.9,
32.1 (d, JCP = 10.9 Hz), 129.4, 129.1, 129.0 (d, JCP = 10.6 Hz), 128.4,
28.3, 124.1 (d, JCP = 106.4 Hz), 106.4 (d, JCP = 11.9 Hz), 52.0, 21.8; 31P
+
for C25
H
23NO
2
PS [M+H] 432.1182, found 432.1181.
-
1
1
(
(
7
-Benzyl-3-(diphenylphosphoryl)-5-(p-tolylthio)pyridin-2(1H)-one
3ib). Yellow solid (104 mg, 42% yield); mp = 175.6
176.8 °C; 1H NMR
400 MHz, CDCl ): δ 8.40 (dd, J = 14.0, 2.8 Hz, 1H), 7.89 7.83 (m, 4H),
.67 (d, J = 2.8 Hz, 1H), 7.55 7.51 (m, 2H), 7.46 7.41 (m, 4H), 7.34 7.32
7.19 (m, 2H), 7.12 7.05 (m, 4H), 5.05 (s, 2H), 2.31 (s, 3H);
): δ 160.2 (d, JCP = 11.7 Hz), 153.7 (d, JCP = 5.5
3
NMR (162 MHz, CDCl ): δ 25.4; IR (neat, cm ): ν = 3026, 2919, 1643,
̶
1586, 1533, 1375, 1214, 1093, 958, 806, 672; HRMS (ESI): calcd for
+
3
̶
C
26
H
25NO
2
P [M+H] 414.1617, found 414.1619.
̶
̶
̶
(
1
m, 3H), 7.22
̶
̶
1
(
-Benzyl-3-(bis(4-methoxyphenyl)phosphoryl)pyridin-2(1H)-one
3
C NMR (100 MHz, CDCl
3
3nb). Colorless oil (160 mg, 72% yield); 1H NMR (400 MHz, CDCl
3
): δ
Hz), 145.7, 137.3, 135.4, 132.3, 132.1, 132.0 (d, JCP = 10.2 Hz), 131.1,
8
1
=
.32 (ddd, J = 14.0, 6.4, 1.8 Hz, 1H), 7.81 ̶ 7.76 (m, 4H), 7.44 (d, J = 6.8,
1
=
30.2, 129.6, 129.2, 128.6, 128.4 (d, JCP = 12.7 Hz), 128.3, 124.7 (d, JCP
H), 7.32
̶
7.26 (m, 3H), 7.19
̶
7.17 (m, 2H), 6.93
̶
6.90 (m, 4H), 6.32 (td, J
):
103.6 Hz), 112.6 (d, JCP = 12.6 Hz), 52.4, 21.1; 31P NMR (162 MHz,
13
6.8, 1.6 Hz, 1H), 5.05 (s, 2H), 3.79 (s, 6H); C NMR (100 MHz, CDCl
3
-
1
CDCl
3
): δ 24.8; IR (neat, cm ): ν = 3029, 2850, 1646, 1515, 1436, 1328,
δ 162.4 (d, JCP = 2.7 Hz), 161.0 (d, JCP = 12.5 Hz), 148.3 (d, JCP = 5.4 Hz),
1
210, 1152, 1069, 999, 802, 689; HRMS (ESI): calcd for C31H26NO PSNa
2
1
41.6, 135.8, 133.9, 133.8, 128.6 (d, JCP = 81.9 Hz), 128.3, 124.2 (d, JCP
107.3 Hz), 123.5 (d, JCP = 115.2 Hz), 113.8 (d, JCP = 13.7 Hz), 106.3 (d,
+
[M+Na] 530.1314, found 530.1315.
=
J
CP = 12.0 Hz), 55.3, 52.0; 31P NMR (162 MHz, CDCl
3
): δ 24.7; IR (neat,
-
1
5
-(Diphenylphosphoryl)-3-ethylpyrimidin-4(3H)-one (3ka). Colorless
138.0 °C; 1H NMR (400 MHz,
): δ 8.70 (d, J = 8.8 Hz, 1H), 8.36 (d, J = 1.2 Hz, 1H), 7.89 7.83 (m,
H), 7.57 7.53 (m, 2H), 7.48 7.44 (m, 4H), 3.95 (q, J = 7.2 Hz, 2H), 1.34
t, J = 7.2 Hz, 3H); C NMR (100 MHz, CDCl ): δ 161.4 (d, JCP = 7.7 Hz),
59.3 (d, JCP = 10.7 Hz), 154.3, 132.4 (d, JCP = 2.4 Hz), 131.9 (d, JCP
0.7 Hz), 131.2 (d, JCP = 109.2 Hz), 128.5 (d, JCP = 12.8 Hz), 120.0 (d, JCP
101.8 Hz), 43.0, 14.7; 31P NMR (162 MHz, CDCl ): δ 23.3; IR (neat, cm-
cm ): ν = 3066, 2838, 1643, 1592, 1500, 1251, 1117, 1022, 800, 700, 540;
HRMS (ESI): calcd for C26
+
solid (101 mg, 62% yield); mp = 137.5
CDCl
4
(
1
1
̶
H
25NO
4
P [M+H] 446.1516, found 446.1515.
3
̶
̶
̶
1-Benzyl-3-(bis(4-chlorophenyl)phosphoryl)pyridin-2(1H)-one (3nc).
13
3
1
White solid (109 mg, 48% yield); mp = 186.3
MHz, CDCl ): δ 8.38 (ddd, J = 14.2, 6.9, 1.9 Hz, 1H), 7.84
̶
187.2.8 °C; H NMR (400
7.79 (m, 4H),
=
3
̶
7.52 (d, J = 6.4, 1H), 7.43
̶
7.40 (m, 4H), 7.34
̶
7.33 (m, 3H), 7.26 ̶ 7.19 (m,
=
3
13
2H), 6.41 (td, J = 6.8, 2.0 Hz, 1H), 5.08 (s, 2H); C NMR (100 MHz,
1
)
: ν = 3055, 2851, 1700, 1657, 1512, 1437, 1176, 1101, 878, 788, 538;
CDCl
3
): δ 160.9 (d, JCP = 13.2 Hz), 149.1 (d, JCP = 5.5 Hz), 142.3, 138.8
+
HRMS (ESI): calcd for C18
H
18
N
2 2
O
P [M+H] 325.1100, found 325.1101.
(
d, JCP = 3.1 Hz), 135.5, 133.5 (d, JCP = 11.6 Hz), 130.1 (d, JCP = 110.6
Hz), 129.2, 128.8 (d, JCP = 13.3 Hz), 128.6, 128.3, 122.5 (d, JCP = 109.1
3
(
-Benzyl-5-(diphenylphosphoryl)pyrimidin-4(3H)-one (3kb). Yellow oil
126 mg, 65% yield); 1H NMR (400 MHz, CDCl
): δ 8.68 (d, J = 8.4 Hz,
7.53 (m, 2H), 7.47 7.43 (m,
7.23 (m, 2H), 5.05 (s, 2H); C NMR (100
): δ 161.8 (d, JCP = 7.3 Hz), 159.5 (d, JCP = 10.0 Hz), 154.4,
Hz), 106.7 (d, JCP = 12.3 Hz), 52.3; 31P NMR (162 MHz, CDCl
3
): δ 24.3; IR
-1
3
(neat, cm ): ν = 3064, 2923, 1643, 1478, 1301, 1178, 1083, 956, 772, 671,
+
1H), 8.29 (s, 1H), 7.87
̶
7.82 (m, 4H), 7.56
̶
̶
555; HRMS (ESI): calcd for C24
H
18Cl
2
NO
2
PNa [M+Na] 476.0344, found
13
4H), 7.35 7.33 (m, 3H), 7.25
̶
̶
476.0342.
MHz, CDCl
3
1
1
1
3
34.4, 132.4 (d, JCP = 2.2 Hz), 132.0 (d, JCP = 10.6 Hz), 131.2 (d, JCP
=
=
1
-Benzyl-3-(bis(3,5-dimethylphenyl)phosphoryl)pyridin-2(1H)-one
09.1 Hz), 129.4, 128.9, 128.5 (d, JCP = 12.8 Hz), 128.4, 120.1 (d, JCP
1
(
3nd). Colorless solid (121 mg, 55% yield); mp = 178.0
400 MHz, CDCl ): δ 8.30 (ddd, J = 13.8, 6.8, 2.2 Hz, 1H), 7.50
7.29 (m, 3H), 7.25 7.23 (m, 2H), 7.13 (s, 2H), 6.36 (td, J = 6.8,
.0 Hz, 1H), 5.10 (s, 2H), 2.31 (s, 12H); 13C NMR (100 MHz, CDCl
): δ
61.0 (d, JCP = 12.0 Hz), 148.6 (d, JCP = 5.5 Hz), 141.7, 137.9 (d, JCP
3.4 Hz), 136.2, 133.8 (d, JCP = 2.5 Hz), 131.7 (d, JCP = 107.9 Hz), 129.5
̶
179.2 °C; H NMR
02.0 Hz), 50.1; 31P NMR (162 MHz, CDCl
): δ 23.5; IR (neat, cm ): ν =
-1
3
(
3
̶
7.46 (m,
056, 2852, 1665, 1511, 1435, 1336, 1213, 1118, 905, 882, 690, 527;
PNa [M+Na]+ 409.1076, found
5
2
1
1
H), 7.35
̶
̶
HRMS (ESI): calcd for
23 19 2 2
C H N O
3
409.1079.
=
3
5
1
7
=
1
-(Diphenylphosphoryl)quinolin-2(1H)-one (3l). White solid (90 mg,
(d, JCP = 10.6 Hz), 129.1, 128.4, 128.2, 124.1 (d, JCP = 105.9 Hz), 106.4
(d, JCP = 12.0 Hz), 52.3, 21.5; 31P NMR (162 MHz, CDCl
): δ 26.1; IR (neat,
1
2% yield); mp = 298.1
H), 8.96 (d, J = 14.8 Hz, 1H), 8.00
.55 (t, J = 7.2 Hz, 2H), 7.48 7.44 (m, 5H), 7.26
8.4 Hz, 1H); 13C NMR (100 MHz, CDCl
): δ 163.1 (d, JCP = 11.9 Hz),
51.2 (d, JCP = 5.0 Hz), 140.4, 132.8, 132.2 (d, JCP = 10.6 Hz), 132.1 (d,
CP = 2.0 Hz), 131.9 (d, JCP = 109.0 Hz), 129.5, 128.4 (d, JCP = 12.8 Hz),
̶
299.0 °C; H NMR (400 MHz, CDCl
3
): δ 12.5 (s,
7.95 (m, 4H), 7.70 (d, J = 7.6 Hz, 1H),
7.22 (m, 1H), 6.84 (d, J
3
-
1
̶
cm ): ν = 3197, 1652, 1536, 1371, 1185, 1130, 1058, 954, 687, 567;
+
̶
̶
HRMS (ESI): calcd for C28
H
29NO
2
P [M+H] 442.1930, found 442.1938.
3
1
(
-Benzyl-3-(bis(3-methoxyphenyl)phosphoryl)pyridin-2(1H)-one
3ne). Colorless oil (116 mg, 52% yield); 1H NMR (400 MHz, CDCl
3
): δ
J
6
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European Journal of Organic Chemistry
10.1002/ejoc.202100336
FULL PAPER
8
5
5
.30 (ddd, J = 14.4, 7.4, 2.2 Hz, 1H), 7.50
H), 7.23 7.21 (m, 2H), 7.06 7.03 (m, 2H), 6.36 (td, J = 6.8, 2.1 Hz, 1H),
.09 (s, 2H), 3.76 (s, 6H); C NMR (100 MHz, CDCl ): δ 161.1, 159.4 (d,
CP = 15.6 Hz), 148.8 (d, JCP = 5.9 Hz), 142.0, 135.8, 133.3 (d, JCP = 108.5
Hz), 129.6 (d, JCP = 15.0 Hz), 129.1, 128.4, 128.3, 124.4 (d, JCP = 10.5 Hz),
̶
7.43 (m, 5H), 7.38
̶
7.30 (m,
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̶
̶
13
3
J
1
1
23.6 (d, JCP = 106.8 Hz), 118.5 (d, JCP = 2.4 Hz), 116.4 (d, JCP = 11.9 Hz),
06.4 (d, JCP = 12.1 Hz), 55.5, 52.3; 31P NMR (162 MHz, CDCl
): δ 25.4;
3
-
1
IR (neat, cm ): ν = 3065, 2943, 1643, 1534, 1375, 1235, 1111, 1035, 856,
7
4
72, 688; HRMS (ESI): calcd for C26
46.1519.
H25NO
4
P [M+H]+ 446.1516, found
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Acknowledgements
This work was supported by Thailand Research Fund
(
RSA6280024), Thailand Toray Science Foundation (TTSF)
Science and Technology Reseach Grant, the Center of
Excellence for Innovation in Chemistry (PERCH-CIC), Ministry of
Higher Education, Science, Research and Innovation, Central
Instrument Facility (CIF), Faculty of Science, Mahidol University
and the Science Achievement Scholarship of Thailand (to T. K.).
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Keywords: Pyridone • Manganese • Phosphinoylation • Metal
catalysis • Synthetic method
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European Journal of Organic Chemistry
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European Journal of Organic Chemistry
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FULL PAPER
Entry for the Table of Contents
A Manganese-promoted direct oxidative C‒P bond coupling of 2-pyridones with secondary phosphine oxides has been developed
under mild and experimental simple conditions. This protocol enables the C3-phosphinoylation to take place effectively under a radical
process using substoichiometric amount of Mn(II).
9
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