Regioselective radical arylation: Silver-mediated synthesis of 3-phosphorylated coumarins, quinolin-2(1: H)-one and benzophosphole oxides

Article abstract of DOI:10.1039/c9ob01585j

A silver-mediated domino radical addition/cyclization reaction of diarylphosphine oxides with propynoic acid derivatives is described in this article. The reaction of diarylphosphine oxides with alkynoates or propynoic amide was regioselective, producing 3-phosphorylated coumarins and benzophosphole oxides in moderate to good isolated yield, respectively. The hydrogen bond between PO and N-H was proposed to assist the vinyl radical regioselective arylation process. The reaction conditions were also compatible with the conversion of dialkylphosphine oxides to 3-phosphorylated-coumarins and quinolin-2(1H)-one in good yields.

Full text of DOI:10.1039/c9ob01585j

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DOI: 10.1039/C9OB01585J
ARTICLE
Regioselective Radical Arylation: Silver-Mediated Synthesis of 3-
Phosphorylated-Coumarins,
Benzophosphole Oxides
Quinolin-2(1H)-one
and
Received 00th January 20xx,
Accepted 00th January 20xx
Hong Hou*, Yue Xu, Haibo Yang, Chaoguo Yan, Yaocheng Shi, and Shaoqun Zhu*
DOI: 10.1039/x0xx00000x
A silver-mediated domino radical addition/cyclization reaction of diarylphosphine oxides with propynoic acid derivatives
were described. The reaction products of diarylphosphine oxides with alkynoates or propynoic amide in different
regioselectivities, giving 3-phosphorylated coumarins and benzophosphole oxides in moderate to good isolated yields,
respectively. The hydrogen bond between the P=O and NH was proposed to assist the vinyl radical regioselective arylation
process. Dialkylphosphine oxides also compatible, and gave the 3-phosphorylated-coumarins and quinolin-2(1H)-one in
good yields.
different cyclic products would be formed via different regioselective
arylation of the vinyl radical intermediate. On the one hand,
intramolecular arylation of the vinyl radical of the phenol-derived
ring would give the 3-phosphorated coumarins (X = O) or quinolin-
2(1H)-one (X = NR) (Path a, SCHEME 1). On the other hand,
intramolecular arylation of the vinyl radical by the phenyl ring of the
diphenylphosphine oxide would lead to benzophosphole oxide
formation (Path b, SCHEME 1). To the best of our knowledge, the
investigation of the regioselectivity on this annulation reaction is rare.
Introduction
The oxidative annulation reaction of multiple unsaturated containing
substrate represents a powerful and efficient synthetic strategy to
access complex organic cyclic scaffolds. Alkynoates, derived from
propynoic acid, are widely used as radical acceptor for coumarin
formation, and various of multi-substituted coumarins could be
obtained via a radical addition/cyclization cascade approach.2-4
However, the using of propynoic amide as substrate for the
annulation reaction, especially trigger by a radical has not yet
attracted enough interest.5
1
O
O
P
Ar
X
The generation of phosphorus atom radicals by different radical
initiators or under different catalytic systems have been reported.
Ar
6
-
O
O
P
Ar1
R
O
P
O
Ar
Ar
a)
b)
8
Ar
Ar
Notably, the Wu group developed a radical approach to access 3-
phosphorated coumarins by using silver as the catalyst and dialkyl
X
X
Ar1 attacked
Radical
R
Arylation
Ar1
R
Ar1
1
9
phosphonates as radical precursors. The use of diarylphosphine
Ar Vs Ar
R
O
oxide as a radical precursor for the synthesis of 3-phosphorylated
coumarins was reported by Xu and co-workers, and a visible light
reaction conditions were utilized.10 The above two reactions were
proceeded via a similar reaction pathway, in which the vinyl radical
Vinyl Radical
Intermediate
XAr1
X = O or NR
Ar
P
O
Ar
Ar attacked
intermediate was generated by radical addition of the phosphorus SCHEME 1. Different regioselectivities in the oxidative annulation
atom to the alkyne moiety, followed by the arylation by the phenyl reaction.
ring of the ester group.
Unlike the previous reports, the Duan11 and Miura12 groups
reported a benzophosphole oxide synthesis protocol utilizing an
Results and discussion
To study the regioselectivity of the annulation reaction between
propynoic acid derivates and diarylphosphine oxide, the reaction of
phenyl 3-(3-methoxyphenyl)propiolate 1a and diphenylphosphine
internal alkyne as a radical acceptor and a silver salt as the oxidant.
Logically, the annulation reaction of diarylphosphine oxides with
alkynoates would have two different regioselectivities, and two
oxide 2a was carried out in the presence of 2.0 equivalents of AgNO
3
.
Different solvents, such as DMF, ClCH CH Cl, toluene, THF and MeCN
were tested, and all solvents could afford the desired product, 3-
2
2
School of Chemistry & Chemical Engineering, Yangzhou University
Yangzhou, 225002, China.
E-mail: hhou@yzu.edu.cn; shaoqun.zhu@hotmail.com
(diphenylphosphoryl)-4-(3-methoxyphenyl)-2H-chromen-2-one 3a
†Electronic Supplementary Information (ESI) available: [details of any
(entries 1-6, Table 1). When MeCN was used, an 88% NMR yield was
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
obtained, and 3a was isolated in a 71% yield by chromatographic
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
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ARTICLE
Journal Name
purification on silica gel, representing the best results for this esters were subjected to the reaction conditions, the pVrieowdAurctitcsle3Ogn-l3inke
reaction (entry 5, Table 1). Other silver sources, including AgOAc, were isolated in good yields and the structDuOreI:s10in.1d0i3c9a/tCed9OtBh0a1t58th5eJ
AgOTf, and Ag
2
CO
3
were tested next, and all afforded 3a in a lower methyl- group and tert-butyl- group were located on the meta-
also led position of the ester group (entries 7 and 8, Table 2). The structure
yield (entries 6-8, Table 1). Reducing of the amount of AgNO
3
to a reducing in the reaction yields (entries 9-11, Table 1). When 2.0 of 3i was determined by single-crystal X-ray diffraction (see the
equivalents of TEMPO were used as an additive under the best Supporting Information for details).13 Other di-aromatic phosphine
reaction conditions, 3a were not observed, which indicated the oxides, such as di-p-tolylphosphine oxide and bis(4-
present reaction might undergo a radical process (entry 12, Table 1). methoxyphenyl)phosphine oxide, were tested and the desired
products 3j and 3k were successfully obtained in good yields (62%
Table 1: Reaction condition screening for the oxidative annulation and 58%, respectively, entries 10 and 11, Table 2). An aliphatic
reactiona
phosphine oxide also proved to be compatible, dibutylphosphine
oxide afforded the corresponding product 3h in 47% isolated yield,
although the yield was slightly lower than that of the di-aromatic
phosphine oxide (entry 8, Table 2). The aromatic group on the
terminal position of the alkyne could also be changed, and when
phenyl but-2-ynoate reacted with 2a, the desired product 3l was
isolated in 73% yield (entry 12, Table 2).
O
O
P
O
Ph
Ph
O
O
[Ag]
(x equiv.)
MeO
+
P
O
H
Ph
solvent, Ar
Ph
0 o
6
C
MeO
1a
2a
3a
Entry
[Ag]
x
Solvent
DMF
Yield (%)b
20%
Table 2: Scope of alkynoates for the radical cyclizationa
1
2
3
4
5
6
7
8
9
AgNO
AgNO
AgNO
AgNO
AgNO
3
3
3
3
3
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.5
1.0
1.5
2.0
O
DCE
28%
O
O
R
O
P
O
AgNO3
+
P
Toluene
THF
45%
Ar
R1
R1
R
H
R1
MeCN, Ar
60 o
C
R1
Ar
56%
O
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
88% (71)c
10%
1a-1i
2
3
AgOAc
AgOTf
En
try
Yield
Product
3
13%
b
[%]
2
Ag CO
3
12%
O
O
P
Ph
Ph
AgNO
AgNO
AgNO
AgNO
3
65%
1
2
3a R = OMe
3b R = H
71
85
O
1
1
0
3
3
3
62%
1
69%
R
O
O
P
1
2d
< 5
Ph
Ph
a
Reaction conditions: 1a (0.1 mmol), 2a (0.12 mmol), silver salt,
3
3c
51
MeO
O
b
slovent (2 mL), under an Argon atmosphere, 24-48 h. NMR yield
using of 1,3,5-trimethoxybenzene as an internal standard.
c
d
isolated yield of 3a. 2.0 equivalents of TEMPO as an additive.
DMF = N,N-dimethylformamide; DCE = ClCH CH Cl; TEMPO =
,2,6,6-tetramethyl-1-piperidinyloxy.
O
O
P
2
2
Ph
Ph
2
4
5
3d R = OMe
3e R = Cl
72
68
O
Under the best reaction conditions established above, different
phenyl 3-argiopropiolates were tested, the corresponding products
a-3e were obtained in satisfactory yields (51-85%, entry 1-5, Table
R
O
3
2
O
P
). Phenyl rings with different substituent groups, including electron-
Ph
Ph
donating, and electron-withdrawing groups were tested at different
positions and proved to be compatible. Different phenol ester
derivatives were tested next and all gave the corresponding products
f-3l in good yields (entries 6-12, Table 2). When o-cresol derived 3-
phenylpropynoic ester 1f was used as substrate, 3-
diphenylphosphoryl)-5-methyl-4-phenyl-2H-chromen-2-one 3f was
6
3f
50
Me
Me
O
O
O
3
R
a
7
8
3g R = C
3h R = Bu
6
H
5
57
47
P
O
R
(
n
isolated in 50% yield, and the molecular structure indicated that the
methyl group was located on the meta-position of the ester group
(entry 6, Table 2). When p-cresol and 4-(tert-butyl)phenol derived
2
| J. Name., 2012, 00, 1-3
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Journal Name
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tBu
O
O
P
decarboxylation to furnish reaction byproducts.15 The isomerization
of vinyl radical intermediate B could deliverDinOtIe:r1m0.1e0d3ia9/tCe9EOtBh0r1o5u8g5hJ
View Article Online
9
1
1
Ar
Ar
3i Ar = C
3j R = 4-MePh
3k R = 4-OMePh
6
H
5
61
62
58
0
1
the rotation of the σ bond, followed by an intramolecular radical
addition to the phenyl ring of the phosphine oxide, leading to the
formation of the p-tolyl 1,3-diphenyl-1H-phosphindole-2-
carboxylate 1-oxide 3g’. However, 3g’ was not observed at this stage.
It could be explained that the oxygen atoms with electronegativity
might be mutually exclusive on the intermediate E, which would
result in the shorter lifetime than the intermediate B.
O
O
O
Ph
1
2
3l
73
P
Me O
Ph
a
Reaction conditions: 1a-1i (0.4 mmol), 2 (0.48 mmol), AgNO
0.8 mmol), MeCN (2 mL), under an Argon atmosphere, 24-48
h. isolated yield of 3.
3
(
b
Table 3: Scope of propynoic alkyl ester and amide for the radical
cyclizationa
O
P
H
Ph
O
Ph
Ph
2
a
XR
O
O
P
AgNO3
AgNO3
O
+
P
O
Ar
XR
H
Ar
MeCN, Ar
O
Ar
O
60 o
Ph
C
Ar
Ph
Ph
P
Ph
A
1g
1j-1m or 4a-4e
2
5
Me
Yield
[%]
Me
O
O
P
Entry
Product
5
b
Ph O
Ph
O
Ph
Ph
P
O
O
OTol
O
Ph
1
2
3
4
5
5a R = Ph
95
60
60
84
87
O
Ph
3
g
Ph O
NHR
5b R = 2-MePh
5c R = 3-MePh
5d R = 4-MePh
Ph
P
Ph
P
O
ester
H+
-
B
migration
E
Me
Ph
O
5e R = 4-CF
3
Ph
Ph
Ph
O
Ph
ipso-
cyclization
P
O
P
O
O
Ph
O
O
Ph
O
NHPh
Ph
OTol
6
7
8
5f R = CH
5g R = OCH
5h R = F
3
53
50
48
Ph
P
O
O
R
3
D
P
C
AgNO3
Ph
Me
CO2
Me
Tol
O
3g'
R
-
O
by-product
Ph
Ph
O
Ph
Ph
P
NHPh
O
F
9
P
O
5i
48
OMe
SCHEME 2. Possible mechanisms for the radical cyclization of
alkynoates.
MeO
Me
O
Ph
Based on previous reports,8-10 and the fact that oxygen atom from
NHPh
Me
P
O
the para- or ortho- position of the phenol esters was migrated to the
meta- position of the products (3f-3k, entries 6-11, Table 2), a
possible reaction mechanism involved ipso-cyclization and 1,2-ester
migration was proposed in SCHEME 2. The treatment of
diphenylphosphine oxide 2a with silver salt lead to the formation of
electrophilic phosphorus atom radical A, which is well-known.8,11,14
Radical addition of A to the C≡C π bond would give the vinyl radical
intermediate B and an ipso-cyclization reaction could give the
cyclohexadienyl radical intermediate C. The cyclohexadienyl radical
C could be oxidized to the cyclohexadienyl carbon cation D by AgNO3,
which could undergo 1,2-ester migration, then deprotonative
aromatization to give the desired product 3g. On the other hand, the
cyclohexadienyl radical intermediate C could restore aromaticity to
afford the acid oxygen radical F, which could then undergo
10
5j
77
52
Me
Me
O
Ph
NHPh
OMe
1
1
P
O
O
5k
OMe
Ph
1
1
1
1
2
3
4
5
5l R = Me
5m R = Et
5n R = Pr
50
66
78
92
OR
P
O
i
2
5o R = CH Ph
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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aReaction conditions: 1j-1m or 4a-4e (0.4 mmol), 2 (0.48 mmol),
AgNO (0.8 mmol), MeCN (2 mL), under an Argon atmosphere, 24-
diffraction (see the Supporting Information for details).13 3-
View Article Online
3
b
Phenylpropiolic alkyl ester were next subjected to the reaction
conditions, and the desired products 5l-5o were obtained in good
yields (50-92%, entries 12-15, Table 3). It is surprised to found that 3-
phenylpropiolic acid was failed to give the desired product, it is might
be the decarboxylation reaction of the acid was occurred under the
silver catalysis.17
DOI: 10.1039/C9OB01585J
4
8 h. isolated yield of 5.
To expand the reaction scope, we switched our focus from
alkynoates to propynoic amides, and different propynoic amides, di-
aromatic phosphine oxides and dibutylphosphine oxide were
subjected to the reaction conditions without further optimization.
Unlike the reactions of alkynoates with di-aromatic phosphine oxides,
the reaction of propynoic amides with di-aromatic phosphine oxides
gave benzophosphole oxide products 5a-5k (Table 3).11,12,16 Various
aniline-derived propynoic amides were tested and successfully gave
the corresponding products 5a-5e (entries 1-5, Table 3). Different di-
aromatic phosphine oxides, containing both electron-donating- and
electron-withdrawing groups on the para- position of the
diphenylphosphine oxide were tested next, and the corresponding
products 5f-5h were obtained in moderate yields (53%, 50%, and
The switch of the diphenylphosphine oxide to dibutylphosphine
oxide also successful, and 3-(dibutylphosphoryl)-4-phenylquinolin-
2
(1H)-one 6 was isolated in 80% yield (SCHEME 3).
To understand the different regioselectivities on the reaction
mechanism between the alkynoates and propynoic amide. The
reaction of 1,3-diphenylprop-2-yn-1-one 6 with 2a was tested, and
the reaction gave an inseparable mixture 7 and 8, and 1:1 ratio was
determined by the 31P NMR analysis. The reaction indicated that the
two different phenyl rings (benzoyl- group and diphenylphosphine
oxide) could be attacked by the vinyl radical intermediate. When
tertiary amides, such as N-methyl-N,3-diphenylpropiolamide 5f and
N,N,3-triphenylpropiolamide 5g were introduced to the reaction
conditions, to our great surprise, no cyclic products were obtained,
and the two reactions all gave a mixture of various products (SCHEME
4
8%, respectively, entries 6-8, Table 3). A meta-substituted
diphenylphosphine oxide, bis(3-methoxyphenyl)phosphine oxide 2f
was tested and compatible, the desired product 6-methoxy-1-(3-
methoxyphenyl)-N,3-diphenyl-1H-phosphindole-2-carboxamide 1-
oxide 5i was isolated in 48% yield (entry 9, Table 3).
4
).
Me
H
O
H
P
Me
N
O
P
O
P
Me
Me
O
NH
2b (0.48 mmol)
Ar = 4-MePh
H
Ar
Ar
Ph
2
Ar
O
AgNO3 0.8 mmol
MeCN (2 mL), Ar
Ar
Ph O
P
AgNO3
NH
0 o
O
6
C
Ph
4
a (0.4 mmol)
6
O
P
,
80% yield
Ar
Ar
Ph
O
SCHEME 3. The reaction of dibutylphosphine oxide 2b with
propynoic amide 4a.
G
6f
N
Ph
4a H
Ar
O
O
Ph
H
Ar
O
Ph
P
O
H
2
a
O
P
Ph
O
N
N
O
Ph
Ph
O
Ph
(
0.48 mmol)
Ph
+
NHPh
P
O
Ar
Ph
Ph
P
P
Me
O
Ar
K
Ph
Ph
O
5f
H
Ph
Me
5
-trig
-exo
ipso-cyclization
6
(0.4 mmol)
O
- H+
7
8
7
:8 = 1:1
O
Ph
NH
O
5
8% combined yield
Ph
O
Ph
H
Ph
Ph
2
a
Ph
N
N
O
(
0.48 mmol)
P
P
H
Ph
mixture of various acyclic products
O
Ar
O
Ar
P
I
N
R
AgNO3
AgNO3
0.8 mmol
MeCN (2 mL),
Ar
Ph
Me
Me
L
J
Me
(0.4 mmol)
o
Ph
O
O
Ar, 60 C
R = Me, 5f; R = Ph, 5g
NHPh
SCHEME 4. The reaction of 1,3-diphenylprop-2-yn-1-one 6 and
tertiary amides 5f, 5g with 2a.
P
Ar
Me
5f'
Furthermore, the isomer from the different regioselectivity of the
vinyl radical addition to the 3-methoxyphenyl group was not
generated, and it might be due to the high steric hindrance. Bis(3,5-
SCHEME 5. Possible mechanisms for the radical cyclization of
propynoic amide.
Based on the above experiment, as well as the previous reports,7-
a hydrogen bond assisted regioselective cyclization mechanism
dimethylphenyl)phosphine
methoxyphenyl)phosphine oxide were next subjected to the reaction
conditions, giving the corresponding products 5j and 5k in 77% and was proposed in SCHEME 5. The radical addition of G to the internal
2% isolated yield, respectively (entries 10 and 11, Table 3). The alkyne 4a leading to formation of vinyl radical intermediate H,
structure of 5g and 5j were determined by single-crystal X-ray single different from the cyclization step on the phenol derived ester
oxide
and
bis(2-
1
2
5
4
| J. Name., 2012, 00, 1-3
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ARTICLE
substrate, the vinyl radical attacked the phenyl ring of the phosphine Compounds 1a-1g, 4a-4f, were prepared accorVdieiwnAgrtictloe Ontlhinee
oxide undergo 5-exo trig cyclization results in intermediate I previous reported procedures.3l,19 2aD-2OhI: 10w.10e3r9e/C9pOrBe0p1a5r8e5dJ
formation, which could be then undergo oxidation and according to the previous reported procedures.20 6 was
deprotonative aromatization to afford the final benzophosphole prepared according to the previous reported procedures.21
oxides product 5f.16 The ipso-cyclization of intermediate H could give
intermediate L, then undergo the similar process to the alkynoate
substrate (oxidation/1,2-migration/deprotonative aromatization) to
General procedure for the hydrophosphinylative cyclization of
phenyl propiolate: Aryl alkynoates 1a-1i (0.40 mmol, 1.0 equiv),
arylphosphine oxide 2 (0.48 mmol, 1.2 equiv), AgNO (0.80
3
afford product 5f’.11,12 To account for the different regioselectivity
between the reaction of alkynoate and propynoic amide, we
proposed the isomerization step between intermediates H and K.
When using of an propynoic amide as the substrate, the hydrogen
bond between the P=O and NH enables a vinyl radical attack on the
phenyl ring of the phosphine oxide and gives the benzophosphole
oxide product 5f.18 It is appear that the hydrogen bond also
suppresses the ipso-cyclization of intermediate H, as 5f’ was not
observed under current reaction conditions. It should be mentioned
that although the intramolecular hydrogen bond of the P=O and NH
was not observed on 5g and 5j; the intermolecular hydrogen bond
information was detected by X-ray diffraction.
mmol, 2.0 equiv) and a stir bar were added to a sealed tube
under a nitrogen atmosphere, MeCN (2 mL) as solvent was then
added. The mixture was stirred for 24-48h at 60 C. After the
aryl alkynoates 1 was completely consumed (monitored by TLC),
the crude mixture was directly purified by flash column
chromatography on silica gel (EtOAc/petroleum ether 1:1) to
give the desired products 3a-3l.
o
3
-(diphenylphosphoryl)-4-(3-methoxyphenyl)-2H-chromen-
10
1
2
-one (3a) : Yellow oil (123 mg, 71% yield); H NMR (400 MHz,
CDCl ): δ 7.81–7.68 (m, 4H), 7.55 (s, 1H), 7.47–7.23 (m, 8H), 7.16
s, 2H), 6.91 (d, J = 8.3 Hz, 1H), 6.83 (d, J = 7.4 Hz, 1H), 6.70 (s,
H), 3.71 (s, 3H); 13C{ H} NMR (100 MHz, CDCl
.2 Hz), 159.5 (d, J = 13.1 Hz), 158.7, 154.2, 134.6 (d, J = 4.4 Hz),
33.7, 133.5 (d, J = 10.8 Hz), 132.4 (d, J = 10.8 Hz), 131.5, 131.4
3
(
1
1
5
1
3
): δ 165.3 (d, J =
Experimental
General Methods.
(
(
d, J = 3.0 Hz), 131.3 (d, J = 10.1 Hz), 128.9 (d, J = 22.3 Hz), 128.2
d, J = 4.0 Hz), 128.0 (d, J = 4.0 Hz), 124.3, 121.0, 120.5 (d, J = 9.3
3
1
All experiments were conducted under an argon atmosphere. Hz), 118.8 (d, J = 1.4 Hz), 116.7, 114.7, 114.0, 55.0; P NMR (243
DMF, DCE, Toluene, THF, and MeCN were dried and distilled by MHz, CDCl ): δ 23.8; IR (neat): ν = 3062, 2929, 1720, 1594, 1535,
the standard methods. Other commercially available 1481, 1437, 1335, 1241, 1194, 756 cm ; HRMS (ESI) Exact mass
compounds were used as provided without further purification. calculated for [C28
Solvents for chromatography were technical grade and distilled
3-(diphenylphosphoryl)-4-phenyl-2H-chromen-2-one (3b) :
prior to use. Analytical thin-layer chromatography (TLC) was White solid (143.5 mg, 85% yield); m.p. 81-82 C; H NMR (400
performed on Merck silica gel aluminium plates with F-254 MHz, CDCl ): δ 7.75 (t, J = 10.0 Hz, 4H), 7.59 (t, J = 7.6 Hz, 1H),
indicator, visualized by irradiation with UV light. Column 7.48 (d, J = 7.2 Hz, 2H), 7.42 (d, J = 7.3 Hz, 7H), 7.35 (d, J = 7.8
3
-1
+
+
22 3
H O P] [M+H] : 453.1250, found: 453.1256.
1
0
o
1
3
1
3
1
chromatography was performed using silica gel Merck 60 Hz, 1H), 7.24 (d, J = 6.4 Hz, 2H), 7.21 – 7.10 (m, 2H); C{ H} NMR
particle size 0.063–0.2 mm). Melting points were measured on (CDCl , 150 MHz): δ 165.9 (d, J = 5.2 Hz), 159.6 (d, J = 13.4 Hz),
(
3
1
13
19
a Yanaco Micro Melting Point Apparatus. H NMR, C NMR, F 154.3, 133.7, 133.6 (d, J = 4.3 Hz), 133.4, 132.3, 131.6 (d, J = 3.1
NMR and 31P NMR were recorded on a Variance VNMR 400 or Hz), 131.5, 128.9 (d, J = 15.6 Hz), 128.2 (d, J = 4.6 Hz), 128.0 (d,
Bruker AV-600 spectrometer in CDCl
. For H NMR spectra, data J = 29.2 Hz), 124.4, 120.8 (d, J = 9.4 Hz), 119.3, 118.3, 116.7; 31P
1
3
are quoted in the following order: chemical shift (δ) in parts per NMR (243 MHz, CDCl
million (ppm) downfield of tetramethylsilane, using residual 1719, 1598, 1536, 1485, 1440, 1198, 1114, 914, 746 cm ; HRMS
3
): δ 24.4; IR (neat): ν = 3061, 2924, 2856,
-1
+
+
protonated solvent as internal standard (CDCl
3
20 3
at 7.26 ppm). (ESI) Exact mass calculated for [C27H O P] [M+H] : 423.1145,
Multiplicities are indicated s (singlet), d (doublet), t (triplet), m found: 423.1153.
(
multiplet), dd (doublet of doublets), dt (doublet of triplets);
3-(diphenylphosphoryl)-4-(2-methoxyphenyl)-2H-chromen-
coupling constants (J) are in Hertz (Hz). For proton-decoupled 2-one (3c): Yellow oil (91.7 mg, 51% yield); H NMR (400 MHz,
1
13C NMR spectra, chemical shifts (δ) are also quoted in parts per
million (ppm) downfield of tetramethylsilane, using deuterated (m, 8H), 7.15 (t, J = 7.2 Hz, 2H), 7.11–7.00 (m, 2H), 6.83 (d, J =
3
CDCl ): δ 7.83-7.71 (m, 4H), 7.55 (t, J = 7.6 Hz, 1H), 7.51–7.30
1
3
1
solvent as internal standard (CDCl
3
3
at 77.0 ppm). IR spectra 8.3 Hz, 1H), 3.57 (s, 3H); C{ H} NMR (CDCl , 100 MHz): δ 163.4
were recorded on a Perkin Elmer Spectrum 100 FTIR (KBr disc) (d, J = 5.0 Hz), 159.6 (d, J = 13.6 Hz), 155.9, 154.2, 133.37, 133.35
-1
and are reported in terms of frequency of absorption (cm ). (d, J = 48.0 Hz), 132.3 (d, J = 48.0 Hz), 131.56 (d, J = 16.0 Hz),
High resolution mass spectra (HRMS) were obtained on AB 5800 131.57 (d, J = 4.0 Hz), 131.6 (d, J = 16.0 Hz), 131.3 (dd, J = 16.5,
MALDI-TOF/TOF and are recorded using electrospray ionization 2.8 Hz), 130.7, 129.4, 128.2 (d, J = 18.7 Hz), 127.9 (d, J = 7.1 Hz),
(
ESI). X-ray crystallographic data were collected using SMART 127.7, 124.2, 122.6 (d, J = 4.1 Hz), 120.5 (d, J = 11.7 Hz), 120.1,
3
1
APEX II X-ray diffractometer.
3
116.6, 110.2, 55.0; P NMR (243 MHz, CDCl ): δ 24.4; IR (neat):
ν = 3061, 2924, 2854, 1738, 1591, 1487, 1439, 1338, 1250, 1193,
Preparation of substrates
-1
1
161, 793 cm ; HRMS (ESI) Exact mass calculated for
+
+
28 22 4
[C H O P] [M+H] : 453.1250, found: 453.1251.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 6 of 11
ARTICLE
Journal Name
3
-(diphenylphosphoryl)-4-(4-methoxyphenyl)-2H-chromen- (m, 2H), 2.01–1.87 (m, 2H), 1.66–1.53 (m, 2H), 1.49–1.31 (m,
View Article Online
-one (3d) : Yellow solid (130.0 mg, 72% yield); m.p. 114-115 6H), 0.86 (t, J = 7.2 Hz, 6H); 13C{ H} NMR (100 MHz, CDCl3): δ
1
0
1
DOI: 10.1039/C9OB01585J
2
o
1
C; H NMR (400 MHz, CDCl
3
): δ 7.74 (dd, J = 12.2, 7.7 Hz, 4H), 166.1 (d, J = 3.6 Hz), 160.4 (d, J = 14.5 Hz), 153.9, 145.2, 133.9
7
.56 (t, J = 7.4 Hz, 1H), 7.47–7.41 (m, 2H), 7.36 (dd, J = 21.2, 7.9 (d, J = 3.6 Hz), 128.4, 127.8, 127.5, 125.7, 118.9, 118.8, 116.7(d,
Hz, 5H), 7.24–7.10 (m, 4H), 6.87 (d, J = 7.9 Hz, 2H), 3.83 (s, 3H); J = 7.8 Hz), 115.8, 29.4 (d, J = 71.6 Hz), 24.1 (d, J = 16.1 Hz),, 23.7
1
3
1
): δ 165.8 (d, J = 5.3), 160.2, 159.7 (d, J = 4.3 Hz), 21.7 (d, J = 10.3 Hz), 13.6 (d, J = 4.4 Hz); 31P NMR
): δ 43.8; IR (neat): ν = 3053, 2947, 1709, 1609,
C{ H} NMR (100 MHz, CDCl
d, J = 13.4 Hz), 154.3, 133.7 (d, J = 13.9 Hz), 132.7, 131.41 (d, J (243 MHz, CDCl
10.0 Hz), 131.41 (d, J = 3.0 Hz), 130.1, 128.8, 128.1 (d, J = 12.7 1532, 1456, 1336, 1198, 1088, 906, 782 cm-1; HRMS (ESI) Exact
3
(
=
3
+
+
Hz), 125.7 (d, J = 4.4 Hz), 124.3, 122.0 (d, J = 9.3 Hz), 119.4, mass calculated for [C24
18.3, 116.8, 113.4, 55.2; 31P NMR (243 MHz, CDCl
): δ 24.2; IR 419.1746.
neat): ν = 3060, 2926, 1719, 1602, 1507, 1443, 1339, 1251, 6-(tert-butyl)-3-(diphenylphosphoryl)-4-phenyl-2H-
188, 854, 743 cm ; HRMS (ESI) Exact mass calculated for chromen-2-one (3i): Yellow solid (116 mg, 61% yield); m.p. 225-
3
H29NaO P] [M+Na] : 419.1747, found:
1
(
1
3
-1
+
+
o
1
[
C
28
H P] [M+H] : 453.1250, found: 453.1253.
-(4-chlorophenyl)-3-(diphenylphosphoryl)-2H-chromen-2-
O
22 4
3
228 C; H NMR (400 MHz, CDCl ): δ 7.81–7.71 (m, 4H), 7.46 (t,
4
J = 7.1 Hz, 2H), 7.37 (dd, J = 14.8, 7.9 Hz, 8H), 7.22 (dd, J = 12.6,
one (3e) : Yellow solid (125 mg, 68% yield); m.p. 242-243 C; H 6.6 Hz, 3H), 7.04 (d, J = 8.4 Hz, 1H), 1.32 (s, 9H); 13C{ H} NMR
1
0
o
1
1
3 3
NMR (400 MHz, CDCl ): δ 7.76 (dd, J = 12.4, 7.7 Hz, 4H), 7.59 (t, (100 MHz , CDCl ) : δ 165.8 (d, J = 5.3 Hz), 159. 9 (d, J = 13.5 Hz),
J = 7.7 Hz, 1H), 7.49 (t, J = 6.9 Hz, 2H), 7.45–7.32 (m, 7H), 7.17 158.6, 154.3, 133.7 (d, J = 4.3 Hz), 133.6, 132.5, 131.5 (d, J = 10.3
1
3
1
(
d, J = 8.2 Hz, 3H), 7.09 (d, J = 8.0 Hz, 1H); C{ H} NMR (100 MHz, Hz), 128.6 (d, J = 47.5 Hz), 128.2 (d, J = 6.7 Hz), 128.0, 127.7,
CDCl
): δ 164.6 (d, J = 5.0 Hz), 159.3 (d, J = 13.1 Hz), 154.3, 135.1, 122.0, 118.4 (d, J = 9.4 Hz), 117.9, 116.9, 113.4, 35.3, 30.8; 31
33.9, 133.1, 132.0, 131.9, 131.7 (d, J = 2.9 Hz), 131.5 (d, J = 10.3 NMR (243 MHz, CDCl ) : δ 24.6; IR (neat) : ν = 3062, 2962, 1719,
Hz), 129.6, 128.5, 128.3, 128.2, 124.5, 120.5 (d, J = 9.1 Hz), 1607, 1522, 1341, 1198, 1111, 1003, 915, 736 cm ; HRMS (ESI)
3
P
1
3
-1
16.8; 31P NMR (243 MHz, CDCl
927, 2225, 1721, 1599, 1536, 1486, 1193, 1105, 740 cm ; 479.1776.
+
+
1
2
3 28 3
): δ 24.8; IR (neat): ν = 3063, Exact mass calculated for [C31H O P] [M+H] : 479.1771, found:
-1
+
+
HRMS (ESI) Exact mass calculated for [C27
H
19ClO
3
P] [M+H] :
7-(tert-butyl)-3-(di-p-tolylphosphoryl)-4-phenyl-2H-
1
4
57.0755, found: 457.0767.
3
chromen-2-one (3j): Yellow oil (121.9 mg, 60% yield); H NMR
(400 MHz, CDCl ): δ 7.64 (dd, J = 12.4, 8.0 Hz, 4H), 7.42 – 7.35
-(diphenylphosphoryl)-8-methyl-4-phenyl-2H-chromen-2-
one (3f): Yellow oil (86 mg, 50% yield); H NMR (400 MHz, (m, 3H), 7.33 (d, J = 1.3 Hz, 1H), 7.22 (s, 1H), 7.19 (d, J = 8.3 Hz,
CDCl ): δ 7.88–7.69 (m, 4H), 7.60–7.29 (m, 9H), 7.22 (dd, J = 6H), 7.03(d, J = 8.5 Hz, 1H), 2.35 (s, 6H), 1.31 (s, 9H); C{ H} NMR
3
3
1
1
3
1
1
4.5, 6.5 Hz, 2H), 7.13 (dd, J = 15.0, 7.6 Hz, 1H), 7.03 (d, J = 7.4 (100 MHz, CDCl
3
): δ 165.3(d, J = 5.2 Hz), 159.8(d, J = 13.5 Hz),
Hz, 1H), 6.94 (d, J = 8.0 Hz, 1H), 2.12 (s, 3H); 13C{ H} NMR (100 158.3, 154.2, 141.7(d, J = 2.7 Hz), 133.8(d, J = 4.2 Hz), 131.5(q, J
1
MHz , CDCl
34.7, 133.7, 133.5 (d, J = 3.9 Hz), 133.0 (d, J = 8.0 Hz), 131.9 (d, = 8.8 Hz), 127.5, 121.8(d, J = 6.2 Hz), 118.3(t, J = 7.2 Hz), 117.2,
J = 9.3 Hz), 131.51, 131.50 (t, J = 20.0 Hz), 129.2 (d, J = 74.4 Hz), 113.3(d, J = 14.4 Hz), 35.2, 30.7(q, J = 7.3 Hz), 21.4(q, J = 12.0
3
): δ 166.1 (d, J = 5.3 Hz), 159.6 (d, J = 13.7 Hz), 154.1, = 10.9 Hz), 130.4, 129.7, 129.2, 128.6(q, J = 24.6 Hz), 127.6(d, J
1
3
1
1
9
28.0, 128.04 (d, J = 25.0 Hz), 127.5, 125.2, 124.5, 120.1 (d, J = Hz); P NMR (243 MHz, CDCl
3
): δ 25.1; IR (neat): ν = 3030, 2962,
.5 Hz), 118.6 (d, J = 101.0 Hz), 116.6, 20.0; 31P NMR (243 MHz, 2220, 1719, 1612, 1523, 1404, 1340, 916, 812, 731 cm ; HRMS
CDCl ): δ 24.5; IR (neat): ν = 3063, 2925, 1719, 1598, 1538, 1441, (ESI) Exact mass calculated for [C33H31NaO
3 3
P]+ [M+Na]+:
330, 1260, 1194, 1116, 915, 741 cm ; HRMS (ESI) Exact mass 529.1903, found: 529.1892.
-1
-1
1
+
+
calculated for [C28
H
22
O
3
P] [M+H] : 437.1301, found: 437.1307.
3-(bis(4-methoxyphenyl)phosphoryl)-7-(tert-butyl)-4-
4
-(cyclohexa-2,4-dien-1-yl)-3-(diphenylphosphoryl)-6-
phenyl-2H-chromen-2-one (3k): Yellow oil (132.5 mg, 62%
1
methyl-2H-chromen-2-one (3g): Yellow solid (101mg, 58% yield); H NMR (400 MHz, CDCl
yield); m.p. 96-97 C; H NMR (400 MHz, CDCl
3
): δ 7.42 (dd, J = 12.0, 8.7 Hz,
o
1
3
): δ 7.81–7.71 (m, 4H), 7.14 (d, J = 6.4 Hz, 3H), 7.06 (s, 1H), 6.95 (d, J = 6.0 Hz, 2H),
4
H), 7.49–7.43 (m, 2H), 7.39 (d, J = 6.8 Hz, 7H), 7.21 (d, J = 6.6 6.92 (s, 1H), 6.76 (d, J = 8.5 Hz, 1H), 6.63 (dd, J = 8.5, 1.7 Hz, 4H),
1
3
1
13
1
Hz, 2H), 7.14 (s, 1H), 6.97 (s, 2H), 2.43 (s, 3H); C{ H} NMR (100 3.54 (s, 6H), 1.05 (s, 9H); C{ H} NMR (100 MHz, CDCl
MHz, CDCl ): δ 165.9 (d, J = 5.4 Hz), 159.8 (d, J = 13.7 Hz), 154.4, (d, J = 5.0 Hz), 162.0 (d, J = 2.5 Hz), 160.0 (d, J = 13.5 Hz), 158.3,
45.5, 133.7 (d, J = 4.5 Hz), 133.6, 132.5, 131.5, 131.4 (d, J = 2.6 154.2, 134.0 (d, J = 54.2 Hz), 133.3 (q, J = 11.8 Hz), 128.2, 128.1
Hz), 128.6 (d, J = 36.1 Hz), 128.2, 128.1, 128.0, 127.7, 125.6, (d, J = 14.9 Hz), 127.6 (d, J = 16 Hz), 125.1, 123.9, 121.8 (d, J =
3
): δ 165.0
3
1
1
2
1
18.4 (d, J = 9.2 Hz), 116.7, 21.7; 31P NMR (243 MHz, CDCl
4.4; IR (neat): ν =3059, 2924, 1718, 1614, 1526, 1439, 1341, (q, J = 18.1 Hz), 35.2, 30.88, 30.80, 30.7 (q, J = 7.8 Hz); 31P NMR
3
): δ 11.3 Hz), 118.5 (d, J = 9.9 Hz), 117.5, 113.4 (q, J = 15.6 Hz), 55.1
-1
264, 1196, 1114, 916, 734 cm ; HRMS (ESI) Exact mass (243 MHz, CDCl
3
): δ 24.3; IR (neat): ν = 3064, 2961, 2218, 1718,
+
+
-1
calculated for [C28
22 3
H O P] [M+H] : 437.1301, found: 437.1304. 1596, 1503, 1295, 1252, 1182, 1113, 731 cm ; HRMS (ESI) Exact
+
+
3
-(dibutylphosphoryl)-7-methyl-4-phenyl-2H-chromen-2-
mass calculated for [C33
5
H31NaO P] [M+Na] : 561.1801, found:
1
one (3h): Yellow oil (73.8 mg, 47% yield); H NMR (400 MHz, 561.1792.
CDCl
3
): δ 7.46–7.42 (m, 3H), 7.23–7.18 (m, 2H), 7.17 (s, 1H), 6.96
3-(diphenylphosphoryl)-4-methyl-2H-chromen-2-one (3l):
1
(d, J = 8.2 Hz, 1H), 6.87 (d, J = 8.2 Hz, 1H), 2.44 (s, 3H), 2.21–2.08 Yellow oil (105 mg, 73% yield); H NMR (400 MHz, CDCl
3
): δ
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 7 of 11
O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
7
4
2
.78–7.70 (m, 4H), 7.59 (d, J = 6.7 Hz, 1H), 7.54 (d, J = 7.5 Hz, 128.6, 128.2, 126.1, 126.0, 125.1, 120.6, 117.0, 2V1ie.4w;A 3r t1i cPleNOnMlinRe
H), 7.38 (t, J = 7.3 Hz, 2H), 7.10 (d, J = 7.7 Hz, 2H), 6.69 (d, J = (243 MHz, CDCl
3
): δ 40.0; IR (neat): ν = 30
D
6
O
2
I
,
: 1
2
0
9
.1
2
0
4
3
,
9
2
/C
3
9
1
O
6
B
,
0
1
1
6
58
73,
5
J
0.4 Hz, 1H), 2.35 (d, J = 13.5 Hz, 3H); 13C{ H} NMR (CDCl
1
, 100 1553, 1491, 1443, 1313, 1190, 1117, 732 cm ; HRMS (ESI) Exact
-1
3
+
+
MHz): δ 163.2 (d, J = 25.3 Hz), 152.4, 151.5, 150.2, 132.6 (d, J = mass calculated for [C28
.6 Hz), 132.0 (d, J = 10.0 Hz), 130.0, 129.9, 129.8, 129.5, 128.9 436.1466.
d, J = 12.1 Hz), 126.1, 121.4, 15.8 (d, J = 8.1 Hz); 31P NMR (243
3-(diphenylphosphoryl)-6-methyl-4-phenylquinolin-2(1H)-
2
H23NO P] [M+H] : 436.1461, found:
2
(
o
1
3
MHz, CDCl ): δ 31.4; IR (neat): ν = 3063, 2933, 2840, 1717, 1599, one (5d): Yellow solid (146.2 mg, 84% yield); m.p. 87-89 C; H
1
calculated for [C22
-1
3
539, 1335, 1192, 1114, 913, 743 cm ; HRMS (ESI) Exact mass NMR (400 MHz, CDCl ): δ 8.67 (s, 1H), 7.85–7.68 (m, 3H), 7.55–
+
+
H
18
O
3
P] [M+H] : 361.0988, found: 361.0991. 7.39 (m, 9H), 7.36–7.20 (m, 4H), 7.03 (t, J = 7.8 Hz, 2H), 2.24 (s,
1
3
1
H); 13C{ H} NMR (100 MHz, CDCl
3
): δ 160.0 (d, J = 12.4 Hz),
58.6 (d, J = 18.1 Hz), 142.7 (d, J = 26.0 Hz), 135.1, 133.9, 133.4
General procedure for the hydrophosphinylative cyclization of
propynoic acid amide: Aryl propargyl amide 4a-4e or propynoic
alkyl ester 1j-1m (0.40 mmol, 1.0 equiv), arylphosphine oxide 2
(d, J = 1.9 Hz), 132.8 (d, J = 2.9 Hz), 131.0, 130.9, 129.5, 129.4,
1
2
2
29.3, 129.2, 129.1, 129.0, 128.5, 128.2, 126.0, 125.9, 119.9,
0.8; 31P NMR (243 MHz, CDCl
): δ 39.8; IR (neat): ν = 3053,
924, 1667, 1601, 1526, 1319, 1251, 1191, 1115, 817, 705 cm ;
3
(0.48 mmol, 1.2 equiv), AgNO (0.80 mmol, 2.0 equiv) and a stir
3
bar were added to a sealed tube under a nitrogen atmosphere,
MeCN (2 mL) as solvent was then added. The mixture was
-
1
+
+
2
HRMS (ESI) Exact mass calculated for [C28H23NO P] [M+H] :
stirred for 24-48 h at 60 ℃ . After the 4 was completely
4
36.1461, found: 436.1469.
-(diphenylphosphoryl)-4-phenyl-6-
trifluoromethyl)quinolin-2(1H)-one (5e): Yellow solid (171.1
consumed (monitored by TLC), the crude mixture was directly
purified by flash column chromatography on silica gel
3
(
(EtOAc/petroleum ether 1:1) to give the desired products 5a-
o
1
mg, 87% yield); m.p. 101-103 C; H NMR (400 MHz, CDCl
3
): δ
5
o.
3
9
7
.01 (s, 1H), 7.76 (d = 12.4, 7.6 Hz, 3H), 7.52 (t, J = 10.0 Hz, 8H),
.50 (s, 6H), 7.26 (s, 1H); C{ H} NMR (100 MHz, CDCl ): δ 160.5
3
-(diphenylphosphoryl)-4-phenylquinolin-2(1H)-one (5a)16a:
13
1
o
1
Yellow solid (161.6 mg, 95% yield); m.p. 177-179 C; H NMR
(d, J = 12.8 Hz), 159.9 (d, J = 17.7 Hz), 142.7 (d, J = 25.9 Hz),
3
(400 MHz, CDCl ): δ 8.73 (s, 1H), 7.84–7.69 (m, 3H), 7.59–7.46
1
1
1
40.7, 133.6 (d, J = 1.8 Hz), 133.1 (d, J = 2.8 Hz), 132.5, 132.4,
31.5, 131.3, 131.2, 131.0, 130.9, 129.7, 129.54, 129.45, 129.3,
29.1, 128.6, 128.2, 126.4, 126.3, 126.1 (q, J = 3.7 Hz), 119.6; 31P
(m, 8H), 7.44 (t, J = 7.3 Hz, 4H), 7.22 (dd, J = 14.4, 6.7 Hz, 3H),
.03 (t, J = 7.4 Hz, 1H); 13C{ H} NMR (100 MHz, CDCl
1
): δ 160.2
7
3
(d, J = 12.7 Hz), 158.9 (d, J = 14.8 Hz), 142.7 (d, J = 26.2 Hz),
): δ 40.0; 19F NMR (565 MHz, CDCl
NMR (243 MHz, CDCl ): δ -
6
1
3
3
1
1
1
37.6, 133.4 (d, J = 2.0 Hz), 132.9 (d, J = 2.8 Hz), 131.0, 130.9,
2.2; IR (neat): ν = 3049, 2929, 1674, 1604, 1541, 1411, 1323,
29.5, 129.4, 129.3, 129.1, 129.0, 128.7, 128.6, 128.2, 127.6,
-1
181, 1117, 1067, 841, 732 cm ; HRMS (ESI) Exact mass
3
1
26.1, 126.0, 124.3, 120.0; P NMR (243 MHz, CDCl
3
): δ 39.9; IR
P]+ [M+H] : 490.1178, found:
+
calculated for [C28
90.1182.
-(di-p-tolylphosphoryl)-4-phenylquinolin-2(1H)-one (5f):
H F NO
20 3 2
(neat): ν = 3236, 3057, 2924, 1666, 1599, 1544, 1441, 1319,
4
-1
1
190, 1117, 742 cm ; HRMS (ESI) Exact mass calculated for
P] [M+H] : 422.1304, found: 422.1315.
-(diphenylphosphoryl)-8-methyl-4-phenylquinolin-2(1H)-
3
+
+
[
C
27
H
21NO
2
o
1
Yellow solid (95.2 mg, 53% yield); m.p. 281-283 C; H NMR (400
MHz, CDCl ): δ 8.83 (s, 1H), 7.73–7.58 (m, 3H), 7.48 (dd, J = 19.1,
1.4 Hz, 7H), 7.31 (s, 1H), 7.25–7.19 (m, 3H), 7.10–6.97 (m, 3H),
3
3
o
one (5b): Yellow solid (104.4 mg, 60% yield); m.p. 115-116 C;
1
2
1H NMR (400 MHz, CDCl
.86–7.69 (m, 3H), 7.62–7.42 (m, 10H), 7.14–6.93 (m, 4H), 2.19
): δ 8.68 (s, 1H), 7.93 (d, J = 8.0 Hz, 1H),
3
13
1
3
.37 (s, 6H); C{ H} NMR (100 MHz, CDCl ) : δ 160.3 (d, J = 12.7
7
(
Hz), 158.7 (d, J = 18.0 Hz), 144.3 (d, J = 2.1 Hz), 143.6 (d, J = 2.9
Hz), 143.2, 143.0, 137.7, 131.6, 131.5, 131.1, 131.0, 129.9,
s, 3H); 13C{ H} NMR (100 MHz, CDCl
1
): δ 160.2 (d, J = 12.6 Hz),
59.3 (d, J = 17.8 Hz), 143.9 (d, J = 26.2 Hz), 135.9, 133.5 (d, J =
3
1
2
1
1
1
2
3
9
29.8, 129.4, 128.7, 128.5, 128.2, 126.9, 126.8, 124.2, 120.0,
1.9, 21.6; 31P NMR (243 MHz, CDCl
): δ 40.0; IR (neat) : ν =
.0 Hz), 132.9 (d, J = 4.0 Hz), 131.12, 131.08, 131.01, 131.00,
30.3, 129.5, 129.4, 129.3, 129.2, 129.1, 128.6, 128.3, 126.5,
26.15, 126.06, 124.6, 122.0, 17.7; 31P NMR (243 MHz, CDCl
3
049, 2926, 2859, 1670, 1599, 1544, 1391, 1319, 1253, 1186,
3
):
-1
12, 740 cm ; HRMS (ESI) Exact mass calculated for
δ 40.0; IR (neat): ν = 3205, 3059, 2924, 2855, 1669, 1530, 1450,
+
+
[
C
29
H
25NO
2
P] [M+H] : 450.1617, found: 450.1620.
-1
1
308, 1190, 1117, 914, 741 cm ; HRMS (ESI) Exact mass
calculated for [C28
P]+ [M+H]+: 436.1461, found:
36.1466.
-(diphenylphosphoryl)-7-methyl-4-phenylquinolin-2(1H)-
3
-(bis(4-methoxyphenyl)phosphoryl)-4-phenylquinolin-
H23NO
2
2
(1H)-one (5g): Yellow solid (95 mg, 50% yield); m.p. 210-212
4
o
1
C; H NMR (400 MHz, CDCl
3
): δ 8.88 (s, 1H), 7.66 (dd, J = 19.1,
3
9
=
3
.8 Hz, 3H), 7.52–7.40 (m, 7H), 7.22 (t, J = 8.6 Hz, 2H), 7.03 (t, J
o
1
one (5c): Yellow solid (104.5 mg, 60% yield); m.p. 68-69 C; H
NMR (400 MHz, CDCl ): δ 8.71 (s, 1H), 7.87–7.70 (m, 3H), 7.51
dt, J = 16.1, 7.6 Hz, 10H), 7.34 (s, 1H), 7.23–7.09 (m, 3H), 6.86
7.2 Hz, 1H), 6.94 (t, J = 9.5 Hz, 3H), 6.74 (s, 1H), 3.79 (s, 3H),
3
.78 (s, 3H); 13C{ H} NMR (100 MHz, CDCl
1
3
): δ 164.0 (d, J = 1.8
(
(
1
Hz), 163.3 (d, J = 3.0 Hz), 160.3 (d, J = 12.2 Hz), 157.6 (d, J = 17.4
Hz), 145.4 (d, J = 28.0 Hz), 137.7, 133.0 (td, J =26.7 Hz, J =5.8 Hz),
1
3
1
d, J = 7.5 Hz, 1H), 2.26 (s, 3H); C{ H} NMR (100 MHz, CDCl
60.1 (d, J = 13.8 Hz), 159.0 (d, J = 18.1 Hz), 142.9 (d, J = 26.2
Hz), 138.8, 137.6, 133.5 (d, J = 32.0 Hz), 132.9 (d, J = 2.9 Hz),
32.8, 132.7, 131.1, 130.1, 129.52, 129.48, 129.4, 129.2, 129.1,
3
): δ
1
1
31.0, 130.9, 129.4, 128.7, 128.5, 128.2, 124.2, 120.0, 114.8,
14.6, 114.1, 114.0, 113.4, 113.3, 55.6, 55.3; P NMR (243 MHz,
31
1
3
CDCl ): δ 38.9; IR (neat): ν = 3051, 2939, 2844, 1667, 1592, 1499,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Page 8 of 11
ARTICLE
Journal Name
-
1
1
1
315, 1254, 1183, 1115, 910, 740 cm ; HRMS (ESI) Exact mass 1H), 6.85–6.75 (m, 2H), 3.82 (s, 3H), 3.53 (s, 3H); 13C{ H} NMR
View Article Online
calculated for [C29
82.1525.
-(bis(4-fluorophenyl)phosphoryl)-4-phenylquinolin-2(1H)-
H25NO
4
P]+ [M+H]+: 482.1516, found: (100 MHz, CDCl ): δ 160.9 (d, J = 4.6 Hz), 160.5 (d, J = 3.0 Hz),
DOI: 10.1039/C9OB01585J
3
4
160.8, 157.5, 157.3, 145.1 (d, J = 24.6 Hz), 138.1, 135.1, 135.05,
134.5 (d, J = 1.9 Hz), 133.5 (d, J = 14.0 Hz), 129.0, 128.7, 128.3
(d, J = 5.9 Hz), 123.9, 121.1 (d, J = 12.2 Hz), 119.8, 118.6 (d, J =
1.5 Hz), 116.9, 116.6, 115.8, 113.5 (d, J = 6.3 Hz), 111.1(d, J =
3
.9 Hz), 56.1, 55.5; P NMR (243 MHz, CDCl ) δ 42.2; IR (neat) :
3
o
1
one (5h): Yellow solid (90 mg, 49% yield); m.p. 119-121 C; H
NMR (400 MHz, CDCl ): δ 8.65 (s, 1H), 7.86 –7.60 (m, 3H), 7.55
s, 2H), 7.49 (s, 2H), 7.40 (d, J = 7.5 Hz, 2H), 7.26–7.20 (m, 2H),
1
6
3
3
1
(
ν = 3056, 2932, 2849, 1670, 1587, 1472, 1266, 1181, 911, 743
7
.17 (d, J = 8.2 Hz, 2H), 7.06 (d, J = 7.3 Hz, 1H), 6.95 (d, J = 7.0
-
1
+
Hz, 3H); 13C{ H} NMR (100 MHz, CDCl
1
cm ; HRMS (ESI) Exact mass calculated for [C29
[
H25NO
4
P]
3
): δ 167.3 (d, J = 48.5 Hz),
+
M+H] : 482.1516, found: 482.1523.
1
64.8 (d, J = 44.9 Hz), 159.8 (d, J = 12.2 Hz), 156.9 (d, J = 19.1
Hz), 146.0 (d, J = 8.7 Hz), 145.7 (d, J = 8.9 Hz), 137.4, 133.7,
33.66 (d, J = 3.6 Hz), 133.5, 131.9, 131.8, 131.5 (d, J = 3.0),
31.4 (d, J = 1.0), 130.0, 128.9, 128.8, 128.1, 124.5, 120.0, 118.0
methyl 1,3-diphenylphosphindole-2-carboxylate 1-oxide
5l): Yellow oil (72.5 mg, 50% yield); H NMR (600 MHz, CDCl
δ7.81–7.70 (m, 3H), 7.58–7.50 (m, 6H), 7.46 (s, 2H), 7.39 (s, 2H),
1
(
3
):
1
1
(
1
3
1
7
.22 (s, 1H), 3.59 (s, 3H); C{ H} NMR (150 MHz, CDCl
d, J = 18.5 Hz), 163.0 (d, J = 12.3 Hz), 142.1 (d, J = 24.9 Hz),
33.1, 133.0, 132.9 (d, J = 8.1 Hz), 132.5 (d, J = 2.7 Hz), 131.8 (d,
J =10.7 Hz), 131.0 (d, J = 11.0 Hz), 129.5 (d, J = 9.6 Hz), 129.4,
3
): δ 164.5
d, J = 12.0 Hz), 117.8 (d, J = 12.0 Hz), 116.9 (d, J = 14.0 Hz), 116.7
(
1
(
d, J = 14.0 Hz), 114.3 (d, J = 12.0), 114.0 (d, J = 12.0); 31P NMR
(243 MHz, CDCl
) : δ 37.1; 19F NMR (565 MHz, CDCl
): δ -103.0,
3 3
-
1
104.4; IR (neat) : ν = 3060, 1667, 1593, 1548, 1499, 1444, 1321,
195, 1112, 910, 740 cm ; HRMS (ESI) Exact mass calculated for
1
1
3
28.8 (d, J = 12.9 Hz), 128.3, 127.9, 126.5 (d, J = 10.5 Hz), 126.1,
-1
31
25.5, 52.0; P NMR (243 MHz, CDCl
3
) δ 35.8; IR (neat) : ν =
+
+
[
C
27
H F
19 2
NO
-(bis(3-methoxyphenyl)phosphoryl)-4-phenylquinolin-
(1H)-one (5i): Colorless solid (101 mg, 52% yield); m.p. 152– 361.0988, found: 361.0992.
2
P] [M+H] : 458.1116, found: 458.1124.
059, 2925, 2849, 1720, 1561, 1487, 1314, 1219, 1077, 758, 703
-1
+
+
3
22 18 3
cm ; HRMS (ESI) Exact mass calculated for [C H O P] [M+H] :
2
1
7
o
1
54 C; H NMR (400 MHz, CDCl
3
):δ 8.50 (s, 1H), 7.51 (s, 3H),
ethyl 1,3-diphenylphosphindole-2-carboxylate 1-oxide
1
.47 (s, 2H), 7.39 (d, J = 7.8 Hz, 3H), 7.31 – 7.23 (m, 3H), 7.20 (t, (5m): Yellow gum (99.1 mg, 66% yield); H NMR (600 MHz,
CDCl
3
): δ 7.83–7.70 (m, 3H), 7.58–7.48 (m, 6H), 7.46 (s, 2H), 7.39
J = 7.4 Hz, 2H), 7.14 (d, J = 8.6 Hz, 1H), 7.09 – 6.98 (m, 2H), 6.96
(
d, J = 8.6 Hz, 1H), 3.83 (s, 3H), 3.79 (s, 3H); 1 C{ H} NMR (100
3
1
(s, 2H), 7.23 (s, 1H), 4.11–3.94 (m, 2H), 0.97 (d, J = 4.4 Hz, 3H);
1
3
1
3
C{ H} NMR (150 MHz, CDCl ): δ 163.8 (d, J = 18.3 Hz), 162.4 (d,
MHz, CDCl
d, J = 15.7 Hz), 159.6 (d, J = 17.9 Hz), 137.7, 134.8 (d, J = 25.9
Hz), 134.0, 133.0, 132.9, 130.4, 130.3, 129.5, 128.8, 128.6,
3
): δ 162.2 (d, J = 13.8 Hz), 160.3 (d, J = 12.6 Hz), 159.8
J = 12.3 Hz), 142.2 (d, J = 24.9 Hz), 133.0, 132.9, 132.8, 132.3 (d,
J = 2.6 Hz), 131.6 (d, J =10.7 Hz), 131.0 (d, J = 11.0 Hz), 129.4 (d,
J = 9.6 Hz), 129.2, 128.6 (d, J = 12.8 Hz), 128.2, 127.8, 126.6,
(
1
1
1
28.1, 127.5 (d, J = 12.8 Hz), 124.2, 122.7 (d, J = 11.2 Hz), 119.9,
18.8 (d, J = 2.5 Hz), 118.76, 118.5 (dd, J = 66.7 Hz, J = 2.5 Hz)),
15.6 (dd, J = 78.8 Hz, J = 10.9 Hz)), 55.81, 55.40; 31P NMR (243
3
1
1
26.3 (d, J = 10.5 Hz), 125.9, 60.7, 13.5; P NMR (243 MHz,
CDCl ) δ 35.8; IR (neat) : ν = 3060, 2984, 1714, 1562, 1444, 1311,
217, 1079, 758, 703 cm ; HRMS (ESI) Exact mass calculated for
3
-1
1
3
MHz, CDCl ): δ 39.07; IR (neat): ν = 3060, 2923, 2851, 1748,
+
+
[
23
C H
20
O
3
P] [M+H] : 375.1145, found: 375.1149.
1
8
662, 1596, 1548, 1480, 1432, 1315, 1242, 1185, 1036, 912,
isopropyl 1,3-diphenylphosphindole-2-carboxylate 1-oxide
-1
54, 743 cm ; HRMS (ESI) Exact mass calculated for
o
1
(
5n): Yellow solid (120.3 mg, 78% yield); m.p. 142-144 C; H
): δ7.82–7.69 (m, 3H), 7.52 (m, 6H), 7.45
s, 2H), 7.38 (s, 2H), 7.21 (s, 1H), 4.85 (d, J = 5.8 Hz, 1H), 1.08 (d,
+
+
[
C
29
H
25NO
4
P] [M+H] : 482.1516, found: 482.1527.
NMR (600 MHz, CDCl
(
3
3
-(bis(3,5-dimethylphenyl)phosphoryl)-4-phenylquinolin-
2
(1H)-one (5j): Yellow solid (147 mg, 77% yield); m.p. 254-256
13
1
J = 25.7 Hz, 3H), 0.82 (d, J = 64.4 Hz, 3H); C{ H} NMR (150 MHz,
o
1
C; H NMR (400 MHz, CDCl
3
): δ 8.55 (s, 1H), 7.50 (d, J = 7.5 Hz,
CDCl ): δ 163.2 (d, J = 18.3 Hz), 162.0 (d, J = 12.5 Hz), 142.2 (d, J
3
4
9
H), 7.41 (s, 1H), 7.36 (d, J = 8.7 Hz, 4H), 7.30 (s, 1H), 7.18 (d, J = = 25.1 Hz), 133.1 (d, J =13.0 Hz), 133.0, 132.2 (d, J = 2.6 Hz),
.6 Hz, 3H), 7.06–6.94 (m, 2H), 2.31 (s, 12H); 13C{ H} NMR (100 131.5 (d, J =10.5 Hz), 131.0 (d, J = 11.0 Hz), 129.4 (d, J = 9.6 Hz),
1
MHz, CDCl
3
): δ 161.5 (d, J = 17.7 Hz), 160.4 (d, J = 12.0 Hz), 141.6, 129.1, 128.7 (d, J = 28.2 Hz), 128.5, 128.1, 127.8, 127.1, 126.5,
41.5, 138.9, 138.7, 138.2 (d, J = 1.9 Hz), 137.8, 137.6, 137.4, 126.2 (d, J = 10.4 Hz), 68.6, 21.3, 21.2; P NMR (243 MHz, CDCl )
3
3
1
1
1
1
1
3
1
δ 35.7; IR (neat) : ν = 3061, 2981, 1711, 1560, 1446, 1307, 1217,
36.8 (d, J = 13.3 Hz), 134.7 (d, J = 3.0 Hz), 129.2, 128.8, 128.7,
28.4 (d, J = 10.9 Hz), 128.2 (d, J = 10.1 Hz), 127.9, 126.3, 124.0,
-1
1
076, 756, 705 cm ; HRMS (ESI) Exact mass calculated for
+
+
19.9, 21.3, 21.14, 21.07, 20.98; 31P NMR (243 MHz, CDCl
22 3
[C24H O P] [M+H] : 389.1301, found: 389.1305.
3
): δ
benzyl 1,3-diphenylphosphindole-2-carboxylate 1-oxide
6.0; IR (neat): ν = 3045, 2926, 2857, 1671, 1601, 1545, 1443,
1
-1
(5o): Yellow oil (160.6 mg, 92% yield); H NMR (600 MHz, CDCl
3
):
318, 1257, 1183, 909, 743 cm ; HRMS (ESI) Exact mass
P]+ [M+H]+: 478.1930, found:
δ7.75–7.67 (m, 3H), 7.49 (m, 6H), 7.37 (s, 4H), 7.21 (s, 2H), 7.17
calculated for [C31H29NO
2
(
1
1
d, J = 6.7 Hz, 2H), 6.90 (d, J = 6.0 Hz, 2H), 5.12 (d, J = 12.6 Hz,
4
78.1926.
1
3
1
H), 4.96 (d, J = 12.6 Hz, 1H); C{ H} NMR (150 MHz, CDCl
3
): δ
3
-(bis(2-methoxyphenyl)phosphoryl)-4-phenylquinolin-
(1H)-one (5k): Yellow solid (91.8 mg, 48% yield); m.p. 185-186
64.2 (d, J = 18.2 Hz), 162.2 (d, J = 12.3 Hz), 142.0 (d, J = 24.8
2
o
Hz), 135.1, 133.0, 132.9, 132.8, 132.2, 131.7 (d, J =10.7 Hz),
1
3
C; H NMR (400 MHz, CDCl ): δ 8.95 (s, 1H), 8.10 (dd, J = 14.4,
1
1
31.0 (d, J = 11.0 Hz), 129.4 (d, J = 9.6 Hz), 129.3, 128.6 (d, J =
2.9 Hz), 128.1 (d, J = 22.2 Hz), 127.8, 127.65, 127.60, 126.4 (d,
7
7
.6 Hz, 1H), 7.45 (dd, J = 19.6, 7.7 Hz, 9H), 7.21 (t, J = 7.4 Hz, 2H),
.08 (t, J = 7.4 Hz, 1H), 7.00 (t, J = 7.3 Hz, 1H), 6.94 (t, J = 7.0 Hz,
3
1
3
J = 10.4 Hz), 126.2, 125.5, 66.3; P NMR (243 MHz, CDCl ) δ
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 9 of 11
O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
Journal Name
ARTICLE
3
1
5.7; IR (neat) : ν = 3061, 2931, 1719, 1559, 1446, 1310, 1215,
Conflicts of interest
There are no conflicts to declare.
View Article Online
DOI: 10.1039/C9OB01585J
-1
161, 1076, 753, 702 cm ; HRMS (ESI) Exact mass calculated for
+
+
28 22 3
[C H O P] [M+H] : 437.1301, found: 437.1300.
Procedure for the phosphinylative cyclization of N,3-
diphenylpropiolamide with dibutylphosphine oxide: N,3-
Acknowledgements
This project was supported by the National Natural Science
Foundation of China (21702179); the Priority Academic
Program Development of Jiangsu Higher Education Institutions,
diphenylpropiolamide
dibutylphosphine oxide 2h (0.48 mmol, 1.2 equiv), AgNO
5
(0.40 mmol, 1.0 equiv),
(0.80
3
mmol, 2.0 equiv) and a stir bar were added to a sealed tube
under a nitrogen atmosphere, MeCN (2 mL) as solvent was then
added. The mixture was stirred for 48 h at 60℃. After the 5 was the Project supported by the Natural Science Foundation of the
completely consumed (monitored by TLC), the crude mixture Jiangsu Higher Education Institutions of China (17KJB150042),
was directly purified by flash column chromatography on silica and the Lvyangjinfeng Talent Program of Yangzhou. We also
gel (EtOAc/petroleum ether 1:1) to give the desired products 3- thank the Testing Centre of Yangzhou University for the sample
(
dibutylphosphoryl)-4-phenylquinolin-2(1H)-one (6) as Yellow analysis.
1
oil (122 mg, 80% yield); H NMR (400 MHz, CDCl
3
): δ 7.73 (s, 1H),
7
.64 (d, J = 18.2 Hz, 1H), 7.48 (s, 2H), 7.35 (s, 2H), 7.30 (d, J = 2.8
Hz, 3H), 7.13 (d, J = 5.7 Hz, 1H), 2.06 (s, 1H), 1.97 (dd, J = 17.6, Notes and references
9
6
1
7
1
.4 Hz, 3H), 1.60 (m, 4H), 1.44–1.35 (m, 4H), 0.87 (t, J = 7.1 Hz,
H); C{ H} NMR (100 MHz, CDCl ): δ 165.4 (d, J = 16.1 Hz),
3
45.2 (d, J = 3.7 Hz), 137.1, 133.6 (d, J = 13.8 Hz), 132.0 (d, J =
8.2 Hz), 130.2, 129.3, 129.0, 128.9, 127.4 (d, J = 38.1 Hz), 125.0,
24.0, 120.3, 28.4 (d, J = 68.9 Hz), 24.1 (d, J = 15.0 Hz), 23.5 (d,
1
(a) X. Zeng, Chem. Rev., 2013, 113, 6864–6900; (b) Q. Liao, X.
Yang and C. Xi, J. Org. Chem., 2014, 79, 8507–8515.
For selected recent reviews, see: (a) J. Chen, D. Yan, Q. Wei
and W. Xiao, ChemPhotoChem, 2017, 1, 148–158; (b) J. Xuan
and A. Studer, Chem. Soc. Rev. 2017., 46, 4329–4346; (c) Y. H
Budnikova and O G Sinyashin, Russ. Chem. Rev., 2015, 84,
1
3
1
2
3
1
J = 34.5 Hz), 13.6; P NMR (243 MHz, CDCl
3
): δ 42.1; IR (neat): ν
=
3030, 2953, 1664, 1602, 1543, 1448, 1314, 1162, 906, 752 cm-
HRMS (ESI) Exact mass calculated for [C23
9
2
17– 951; (d) Y. H. Budnikova, Chem. Heterocycl. Compd.,
018, 54, 269–279.
1
+
;
2
H28NNaO P]
+
[
M+Na] : 404.1750, found: 404.1687.
3
For selected recent examples of transition metal mediated
radical cyclization for the synthesis of 3-substituded
coumarins, see: (a) Y. Li, Y. Lu, G. Qiu and Q. Ding, Org. Lett.
Procedure for the reaction of 1,3-diphenylprop-2-yn-1-one 6 with
a: The reaction of 1,3-diphenylprop-2-yn-1-one 6 with 2a gave
an inseparable mixture 7 and 8 in 58% combined yield in a 1:1
ratio. 1H NMR (600 MHz, CDCl
) δ 7.75–7.70 (m, 2H), 7.67 (d, J = 7.6
Hz, 2H), 7.46 (s, 0H), 7.41 (d, J = 7.8 Hz, 2H), 7.34 (d, J = 8.0 Hz, 1H),
2
2
014, 16, 4240–4243; (b) X. Mi, C. Wang, M. Huang, Y. Wu and
Y. Wu, J. Org. Chem., 2015, 80, 148–155; (c) K. Yan, D. Yang,
W. Wei, F. Wang, Y. Shuai, Q. Li and H. Wang, J. Org. Chem.,
3
2
015, 80, 1550–1556; (d) T. Liu, Q. Ding, Q. Zong and G. Qiu,
7
=
1
1
1
1
1
.28 (d, J = 6.9 Hz, 2H), 7.23 (d, J = 4.6 Hz, 1H), 7.19 (s, 1H), 7.13 (t, J
6.9 Hz, 1H); 13C NMR (151 MHz, CDCl
) δ 194.93, 194.86, 193.17,
Org. Chem. Front., 2015, 2, 670–673; (e) W. Wei, J. Wen, D.
Yang, M. Guo, Y. Wang, J. You and H. Wang, Chem. Commun.,
2015, 768–771; (f) Y. Zeng, D. Tan, Y. Chen, W. Lv, X. Liu, Q. Li
and H. Wang, Org. Chem. Front., 2015, 2, 1511–1515; (g) W.
Yang, S. Yang, P. Li and L. Wang, Chem. Commun., 2015, 7520-
3
93.12, 173.45, 173.41, 156.09, 155.98, 144.49, 144.40, 141.77,
41.61, 136.86, 133.57, 133.22, 133.12, 133.07, 132.55, 132.53,
32.50, 131.47, 131.40, 131.23, 131.16, 131.11, 130.63, 130.56,
30.35, 129.57, 129.49, 128.82, 128.74, 128.53, 128.16, 128.08,
7
523; (h) W. Fu, M. Zhu, G. Zou, C. Xu, Z. Wang and B. Ji, J. Org.
27.94, 125.33, 125.26, 123.31, 123.25; 31P NMR (243 MHz, CDCl
Chem., 2015, 80, 4766-4770; (i) C. Pan, R. Chen, W. Sha and J.
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):
P]+
δ 18.3, 38.2; HRMS (ESI) Exact mass calculated for [C27
19
H O
2
+
[
M+Na] : 429.1020, found: 429.1008.
Conclusions
In conclusion, we have described a silver-mediated domino
radical addition/cyclization reaction of diarylphosphine oxides
with propynoic acid derivatives. The structure of substrate was
found to control the regioselectivities on the product formation.
3
-Phosphorylated coumarins and benzophosphole oxides were
obtained by using of alkynoates and propynoic amide as
substrate, respectively. The hydrogen bond between the P=O
and NH was proposed to assist the vinyl radical regioselective
arylation process. Dialkylphosphine oxides also compatible on
the reaction conditions, yielding 3-phosphorylated-coumarins
and quinolin-2(1H)-one in good yields.
4
019–4024.
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J. Name., 2013, 00, 1-3 | 9
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O rP gl ea na si ce &d Bo i on mo to al e dc juu l sa tr mC ha er mg i ins ts ry
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0 | J. Name., 2012, 00, 1-3
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Organic & Biomolecular Chemistry
View Article Online
DOI: 10.1039/C9OB01585J
O
O
P
R
X
R
R
O
P
R
Ar1
O
H
R
X
X = O; R = Alkyl or Aryl;
X = NH; R = Alkyl;
R
[
Ag]
Ar
R
O
X = O or NH
XAr1
Ar
P
O
Ar
X = NH, R = Aryl
A silver-mediated domino radical addition/cyclization reaction of diaryl- or dialkyl-
phosphine oxides with propynoic acid derivatives delivers 3-phosphorylated coumarins,
quinolin-2(1H)-one and benzophosphole oxides is presented.