Copper-Catalyzed Oxidative sp3-Carbon Radical Cross-Coupling with Trialkylphosphites Leading to α-Phosphonyl 1,3-Dicarbonyl Compounds

Article abstract of DOI:10.1021/acs.joc.8b03093

A copper-catalyzed radical C_sp³-H/P(OR)₃ cross-coupling reaction for the formation of C_sp³-P bonds is described. A range of 1,3-dicarbonyl compounds and trialkylphosphites were coupled in this fashion

Full text of DOI:10.1021/acs.joc.8b03093

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Note
Copper-catalyzed oxidative sp3-carbon radical cross-coupling with
trialkylphosphites leading to #-phosphonyl 1,3-dicarbonyl compounds
Jian-Ping Zou, Cheng-Kun Li, Ze-Kun Tao, Zhi-Hao Zhou, Xiaoguang Bao, and Shao-Fang Zhou
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 22 Jan 2019
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Copper-catalyzed oxidative sp3-carbon radical cross-coupling with
trialkylphosphites leading to α-phosphonyl 1,3-dicarbonyl compounds
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Cheng-Kun Li, Ze-Kun Tao, Zhi-Hao Zhou, Xiao-Guang Bao,* Shao-Fang Zhou,
Jian-Ping Zou*
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry and Chemical
Engineering, Soochow University, 199 Renai Street, Suzhou, Jiangsu 215123, China.
P(OR)3
CuBr (10 mol %)
LPO
O
O
O
O
O
R2
R2
AcOH, 110 o
0.5 h, air
C
R1
R1
P
RO
OR
Direct C(sp3)-H phosphonation
ABSTRACT: A copper-catalyzed radical Csp3-H/P(OR)3 cross-coupling reaction for the
formation of Csp3−P bonds is described. A range of 1,3-dicarbonyl compounds and
trialkylphosphites were coupled in this fashion to give the corresponding products in
moderate to good yields. This protocol provides direct access to α-phosphonyl 1,3-
dicarbonyl compounds.
The construction of carbon-phosphorus bonds have become a topic of immense interest
due to their importance as versatile intermediates in chemical synthesis.1 In recent years,
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significant efforts have been made towards the development of methods for the making of
this kind of bond. Among these, the transition-metal-catalyzed cross-coupling strategy for
Csp2-P bond formation has attracted attention due to its high efficiency.2 In line with this
strategy, some important methods including the coupling of Csp2-H/P-H bonds to form Csp3-
P bonds have emerged in recent times.1f,3 Nevertheless, the formation of Csp3-P bonds via
the direct cross coupling reaction of Csp3-H/P-H bonds still remains a great challenge.4 In
2015, Lei’s group reported a rare example involving the copper catalyzed radical Csp3-H/P-
H cross-coupling reaction between aryl ketone O-acetyloximes and phosphine oxides to
afford β-ketophosphonates.5 In continuation of our research on Csp2-P bond formation,2a, 6
we envisioned that the direct coupling of Csp3-H bonds with trialkylphosphite could lead to
the formation of Csp3-P bonds.7 Herein, we report the first example of copper-catalyzed
radical cross-coupling reaction of α-Csp3-H bond of 1,3-dicarbonyl compounds and
trialkylphosphites. This protocol provides a direct and convenient access to α-phosphonyl
1,3-dicarbonyl compounds.
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Initial studies began by investigating the reaction between 1,3-diphenylpropane-1,3-
dione (1a) and trimethylphosphite (2a) in the presence of copper iodide (CuI, 10 mol %)
and di-tert-butyl peroxide (DTBP, 6 equiv) in acetic acid (AcOH, 5 mL) at 100 C.
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Fortunately, the desired product 3a was formed after 6 hours, albeit in 10% yield (Table 1,
entry 1). This was likely due to the ease of oxidation of the trimethylphosphite 2a to
trimethylphosphate (PO(OMe)3) during the course of the reaction. Consequently, excess
amounts of DTBP (12 equiv) and 2a (12 equiv) were employed and this led to an increase
in the yield of 3a to 42% (Table 1, entry 2). However, when the reaction was carried out at
lower temperature, only trace amounts of the product 3a was observed (Table 1, entries 3-
4); whereas at a higher temperature (110 C), a better yield (48%) of 3a was obtained
(Table 1, entry 5). Other oxidants such as tert-butyl peroxybenzoate (TBPB) and tert-butyl
hydroperoxide (TBHP) were completely ineffective (Table 1, entries 6-7). However, the use
of lauroyl peroxide (LPO) did not only give a slightly better yield (50%), but the reaction was
also completed in 30 minutes (Table 1, entry 8). Next, attention was turned to the screening
of other catalysts with LPO as the oxidant. While the use of other CuI catalysts afforded
product 3a in good yields (Table 1, entries 9-10), CuBr proved to be the most effective
(85%). At this point, an attempt was made to improve the reaction output by further
increasing the amount of 2a; however this resulted in a dramatic lowering of the yield of 3a
to 30% (Table 1, entry 11). In order to avoid excessive use of reagents, the amounts of 2a,
LPO and AcOH were systematically reduced. After some trials (Table 1, entries 12-17), it
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was found that the use of 7 equiv. each of 2a and LPO in 1 mL AcOH could lead to an
optimal 84% yield of product 3a (Table 1, entry 16). Furthermore, CuII reagents such as
CuBr2, CuCl2 and CuI2 as catalyst were also explored; the results were not so effective as
CuBr (Table 1, entries 18-20). Interestingly, the desired product 3a could also be obtained
in 25% yield in the absence of copper catalyst (Table 1, entry 21). More importantly, the
yield of 3a increased to 56% when the reaction time was prolonged, and to 65% when the
amount of 2a and LPO were increased (Table 1, entries 22-23, supporting information
Tables S1). Therefore, the role of CuBr catalyst is probably to accelerate the decomposition
of LPO8 into radical intermediates in time for the next reaction cycle (see Scheme 5).
Finally, the screening of solvent confirmed AcOH to be the best reaction medium (see
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supporting information Table S2).
Table 1. Optimization of the Reaction Conditionsa
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O
O
O
O
2
3
4
5
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9
Conditions
O
P(OMe)3
P
OMe
3a
yield (%)b
MeO
1a
2a
1a 2a
:oxi.
entry
catalyst
oxidant
:
temp.(oC)
1c
2c
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuBr
CuCl
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr
CuBr2
CuCl2
CuI2
--
DTBP
DTBP
DTBP
DTBP
DTBP
TBPB
TBHP
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
LPO
1:6:6
100
100
30
10
42
1:12:12
1:12:12
1:12:12
1:12:12
1:12:12
1:12:12
1:12:12
1:12:12
1:12:12
1:25:12
1:8:12
1:4:12
1:1:12
1:8:8
1:7:7
1:6:6
1:7:7
1:7:7
1:7:7
1:7:7
1:7:7
1:14:14
Trace
Trace
48
N.R.d
N.R.d
50
85
69
30
75
25
N.R.d
80
84
45
54
50
42
3
60
4
5c
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
110
6c
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7c
8e
9e
10e
11e
12e
13e
14e
15e,f
16e,f
17e,f
18e,f
19e,f
20e,f
21e,f
25
56
65
22e,f,g
23e,f,g
--
--
a
1a
Reaction conditions:
(0.25 mmol), catalyst (10 mol %),
and oxidant (di-tert-butyl peroxide (DTBP), tert-butyl
peroxybenzoate (TBPB), tert-butyl hydroperoxide (TBHP),
Lauroyl peroxide (LPO) in HOAc (5 mL) for 3 hours in air.
b Isolated yield. c reaction for 6 hours. d N.R. means no
1a
reaction. e reaction for 0.5 hours. f 0.25 mmol
AcOH. g reaction for 1.5 hours.
in 1 mL
With the optimized reaction conditions in hand (Table 1, entry 16), we focused on
investigating the scope and limitations of the reaction. The reaction proceeded smoothly
with a variety of 1,3-diketones, affording the products in moderate to good yields (Scheme
1, 3a-3l). In general, the reaction outcome was influenced by the electronic nature of the
substrates. For instance, diketones bearing electron-donating groups such as methyl and
methoxy gave high yields of corresponding products (3b-e). Meanwhile, substrates
containing halo-groups produced moderate to good yields of product (3g-j, 3l). However,
electron-deficient substrates such as those substituted by the strongly electron-withdrawing
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nitro and cyano groups either did not react or could only furnish trace amount of desired
product (3p and 3q). The reaction was also sensitive to steric hindrance as observed with
the ortho-substituted substrates (compare 3b vs 3f, 3d vs 3n, 3e vs 3o, 3h vs 3m).
Fortunately, the reaction of substrate 1k having an alkyl moiety at one end occurred
smoothly to afford product 3k in 68% yield. Unfortunately, no products were obtained with
aliphatic 1,3-diketone compounds including cyclic substrates possibly due to the instability
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of the formed radical intermediates (see supporting information Scheme S1).
Scheme 1. Scope of 1, 3-diketonesa,b
O
O
O
O
O
CuBr (10 mol %)
LPO
R1
+
R2
R1
R2
P(OMe)3
AcOH, 110 o
C
P
MeO OMe
0.5 h, air
2a
3
1
O
O
O
O
O
O
O
O
OMe
O
OMe
P
P
P
OMe
O
MeO
MeO
3c
MeO
3a
3b
73%
84%
77%
O
O
O
O
O
O
O
OMe
78%
O
P
O
OMe
P
P
O
OMe
O
MeO
MeO
MeO
3d
3f
3e
52%
80%
O
O
O
O
O
O
O
OMe
O
OMe
O
OMe
P
P
P
Cl
Br
O
Br
Br
MeO
MeO
MeO
3g
64%
3i
3h
43%
60%
O
O
O
O
O
O
Br
O
OMe
O
OMe
O
OMe
P
P
P
Br
MeO
3k
MeO
MeO
3l
68%
3j
63%
61%
O
O
R1
R2
O
OMe
P
MeO
, R1 = 2-Br; R2 = H (trace)
3m
3n
, R1 = 2-Me; R2 = 2-Me (trace)
, R1 = 2-OMe; R2 = 2-OMe (N.D.c)
, R1 = 4-NO2; R2 = H (N.D.c)
, R1 = 4-CN; R2 = H (trace)
3o
3p
3q
a Unless the otherwise noted, reactions were performed using
(0.50 mmol),
1a
(3.50 mmol), CuBr (10 mol %) and LPO (3.50 mmol) in HOAc (2 mL) at 110 oC
for 0.5 h in air. b Isolated yield. c N.D. means not detected. d N.R. means no
reaction.
2a
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Furthermore, we examined the scope of the reactions of β-ketoesters with
triethylphosphite (2b) (Scheme 2). Ethyl benzoylacetate reacted smoothly with 2b to give
73% yield of the expected product 5a. As observed with 1,3-diketones, the reactions of
ethyl benzoylacetate derivatives were sensitive to both steric and electronic effects. Notably,
electron-rich substrates provided the corresponding products in good yields (5b and 5c)
while the halo-containing substrates furnished moderate yields of product (5d and 5e). The
electronic effect was more pronounced with the nitro-containing β-ketoester which remained
unreactive (5f). As a result of steric hindrance, ortho-substituted β-ketoesters could only
afford trace to modest amounts of desired products (5g-k). The effect was more severe with
substrates containing two ortho-substituents as observed with products 5l and 5m.
Unfortunately, no reactions were observed with aliphatic substrates including cyclic β-
ketoesters probably due to the lower stability of the intermediate radicals. Meanwhile, the
electron-pulling effect of the O-atom of the phenoxy group might be responsible for the
inertness of phenyl 3-oxo-3-phenylpropanoate (4r) (see supporting information Scheme S2).
Scheme 2. Scope of β-ketoestersa,b
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O
O
O
O
O
CuBr (10 mol %)
LPO
OEt
OEt
P(OEt)3
R1
+
R1
AcOH, 110 o
C
P
EtO
O
OEt
0.5 h, air
5
4
2b
O
O
O
O
O
O
O
O
PO(OEt)2
PO(OEt)2
5c
PO(OEt)2
5a
O
5b
73%
O
73%
O
71%
O
O
O
O
O
9
O
O
PO(OEt)2
5d
PO(OEt)2
PO(OEt)2
5f N.D.c
Br
10
11
12
13
14
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Cl
O2N
57%
5e
61%
O
O
O
O
Br
O
O
Cl
O
O
O
O
O
PO(OEt)2
5g
PO(OEt)2
PO(OEt)2
5i
49%
5h
50%
50%
O
O
O
O
O
O
O
O
O
PO(OEt)2
PO(OEt)2
5k
PO(OEt)2
O
trace
5l
5j
16%
trace
Cl
O
O
O
PO(OEt)2
Cl
5m
trace
a
4
Unless the otherwise noted, reactions were performed using (0.50
2b
mmol),
(3.50 mmol), CuBr (10 mol %) and LPO (3.50 mmol) in HOAc
(2 mL) at 110 oC for 0.5 h in air. b Isolated yield. c N.D. means not
detected. d N.R. means no reaction.
In a bid to extend the scope of this protocol, the reactions of a variety of trialkyl/triaryl
phosphites 2 were examined. As observed in Scheme 3, the reactions were largely
influenced by the bulkiness of the phosphites. The bulkier the size of the alkyl/aryl
component of phosphite 2 was, the lower the yield of the product obtained. For example,
the reaction of 1a with triethylphosphite (2b) gave the desired product 6ab in 72% yield
while triisopropylphosphite (2c) could only afford 36% yield of product 6ac. In fact, no
reaction occurred with triphenylphosphite (2d) due to the obvious steric hindrance (6ad).
In order to unravel the mechanism of this reaction, radical-trapping experiments were
conducted (Scheme 4). Although, the addition of 2 equivalents of the radical-scavenger,
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2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) partially inhibited the formation of 3a, the
reaction was completely shut down by simply increasing the amount to 4 equivalents
(Scheme 4a). While the suppressed formation of 3a might suggest the involvement of
radical species, no TEMPO-radical adduct was observed. Delightfully, the inclusion of N-
methyl-N-phenylmethacrylamide (7) in the standard reaction mainly furnished the
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undecanyl radical adduct 8 in 55% yield (Scheme 4b).
Scheme 3. Scope of trialkyl/triaryl phosphites a,b
O
O
O
O
O
CuBr (10 mol %)
LPO
+
P(OR)3
AcOH, 110 o
C
P
RO
OR
0.5 h, air
2
1a
6
O
O
O
O
O
O
O
O
O
P
P
P
O
O
iPr
36%
OEt
OPh
EtO
PhO
iPr
c
6ab
72%
6ad
N.R.
6ac
a
1a
2
(0.50 mmol), (3.50
Unless the otherwise noted, reactions were performed using
mmol), CuBr (10 mol %) and LPO (3.50 mmol) in HOAc (2 mL) at 110 oC for 0.5 h in
air. b Isolated yield. c N.R. means no reaction.
Scheme 4. Radical trapping experiments
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O
O
O
O
Standard
conditions
+
P(OMe)3
O
(a)
P
TEMPO
MeO
OMe
1a
0.5 mmol
2a
3a yield
7.0 equiv.
TEMPO (2 equiv) 21%
TEMPO (4 equiv) trace
5
O
O
6
7
8
9
Standard conditions
C11H23
+
P(OMe)3
(b)
3a
+
N
O
1a
0.5 mmol
2a
trace
N
O
7.0 equiv.
8
7
, 2 equiv.
55% yield
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On the basis of experimental results and previous studies, a mechanism for the copper-
catalyzed cross-coupling of 1,3-dicarbonyl compounds with trialkylphosphites is proposed
(Scheme 5). Upon heating, LPO rapidly decomposes in the presence of CuI to form radical
A and CuII. Meanwhile, CuI can be regenerated via the reduction of CuII by trialkylphosphite
2.8a Furthermore, A could abstract H-atom from 1,3-dicarbonyl compound 1 or 4 to form the
Csp3-centered radical B, which further reacts with trialkylphosphite 2 to generate the radical
intermediate C. This is followed by the β-scission of one of the alkoxy groups of
intermediate C to release the product 3 or 5 and alkyl radical.9
Scheme 5. Proposed Mechanism for the Reaction of 1,3-Dicarbonyl Compounds with
Trialkylphosphites
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P(OR)3
2
3
4
5
CuII
CuI
6
CO2
7
8
9
(n-C11H23COO)2
n-C11H23COO
LPO
n-C10H21CH2
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A
O
O
O
O
Ar
R2
Ar
R2
1
4
and
B
P(OR)3
2
O
O
O
O
- R
R2
Ar
R2
Ar
O
P
OR
OR
P
RO
RO
OR
3
5
C
and
In conclusion, we have developed a new method for the formation of Csp3−P bond
based on the Cu-catalyzed cross-coupling reaction of 1,3-dicarbonyl compounds with
trialkyl phosphites. The mechanistic study indicates that undecanyl radicals generated from
lauroyl peroxide (LPO) could oxidize 1,3-dicarbonyl compounds to produce α-Csp3 radical
species, which could selectively couple with trialkyl phosphites to form α-phosphonyl
dicarbonyl compounds. A variety of 1,3-diketones, β-ketoesters and trialkylphosphites were
shown to be compatible with this reaction. This protocol offers direct access to compounds,
which can be easily transformed to other important organic compounds and bioactive
molecules.
EXPERIMENTAL SECTION
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General Methods. 1H NMR (400 MHz) and 13C NMR (101 MHz) spectra were determined with
CDCl3 or DMSO-d6 as solvent and tetramethylsilane (TMS) as internal standard or 85% H3PO4 as
external standard for 31P NMR (162 MHz). Chemical shifts were reported in ppm from internal TMS
(δ), all coupling constants (J values) were reported in Hertz (Hz). High resolution mass spectra were
recorded on a TOF machine (ESI). Column chromatography was performed with 300-400 mesh
silica gel using flash column techniques. All of the reagents were used directly as obtained
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commercially unless otherwise noted. The substrates of 1a-1q, 4a-4m were synthesized
according to the reported procedures, the details are: 1a-1c,10 1g-1h,10 1k-1l,10 4a-4d,10
1d,11 1e,12 1f,13 1i-1m,14 1j,15 1n,16 1o,17 1p,18 1q,19 4e-4f,20 4i-4j,20 4k,21 4g,22 4l,22 4h,23
4m.24
Preparation of 1,3-Diketo phosphonates 3. Typical Procedure for the Preparation of Dimethyl
(1,3-dioxo-1,3-diphenylpropan-2-yl)phosphonate (3a). To a mixture of 1,3-diphenyl-propane-1,3-
dione (0.112 g, 0.5 mmol), trimethylphosphite (0.434 g，3.5 mmol), and CuBr (0.007 g, 0.05 mmol)
in AcOH (2 mL) was added lauroyl peroxide (LPO) (1.40 g，3.5 mmol). After the reaction mixture
was stirred at 110 °C in oil bath for 30 minutes in air, it was allowed to cool to room temperature,
and diluted with dichloromethane (5 mL). The mixture was filtered, and the filtrate was concentrated
under vacuum. The residue was purified by column chromatography on silica gel (petroleum
ether/dimethyl acetone 10:1 to 6:1) to afford the dimethyl (1,3-dioxo-1,3-diphenylpropan-2-
yl)phosphonate (3a).
Dimethyl (1,3-dioxo-1,3-diphenylpropan-2-yl)phosphonate (3a)
Yellow oil, 84% yield (139.4 mg); 1H NMR (400 MHz, DMSO-d6,): δ 8.05 (d, J = 7.4 Hz, 4H), 7.67
(t, J = 7.4 Hz, 2H), 7.54 (t, J = 7.7 Hz, 4H), 7.13 (d, J = 23.2 Hz, 1H), 3.67 (d, J = 11.3 Hz, 6H).
13C{1H} NMR (101 MHz, DMSO-d6): δ 190.6 (d, J = 6.4 Hz), 135.5 (d, J = 3.5 Hz), 134.1, 128.9
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(d, J = 3.5 Hz), 58.9, 57.6, 53.3 (d, J = 6.4 Hz). 31P{1H} NMR (162 MHz, DMSO-d6): δ 17.84;
HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C17H18O5P 333.0892, found 333.0894.
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Dimethyl(1,3-dioxo-1-phenyl-3-(p-tolyl)propan-2-yl)phosphonate (3b)
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Yellow oil, 73% yield (126.2 mg); 1H NMR (400 MHz, DMSO-d6): δ 7.99 (dd, J = 25.2, 7.9 Hz, 4H),
7.67 (t, J = 7.3 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 23.0 Hz, 1H),
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3.67 (d, J = 11.3 Hz, 6H), 2.37 (s, 3H). C{1H} NMR (101 MHz, DMSO-d6): δ 190.7 (d, J = 6.4
Hz), 190.0 (d, J = 6.3 Hz), 144.9, 135.5 (d, J = 3.8 Hz), 134.1, 133.0 (d, J = 3.3 Hz), 129.5, 129.1,
128.9, 128.8, 58.1 (d, J = 130.7 Hz), 53.3 (d, J = 1.0 Hz), 53.2 (d, J = 1.0 Hz), 21.2; 31P{1H} NMR
(162 MHz, DMSO-d6): δ 18.04; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C18H20O5P 347.1048,
found 347.1050.
Dimethyl(1-(4-methoxyphenyl)-1,3-dioxo-3-phenylpropan-2-yl)phosphonate (3c)
White solid, mp 128-129 °C, 77% yield (139.3 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.07 – 8.02
(m, 4H), 7.66 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H), 7.10-7.01 (m, 3H), 3.85 (s, 3H), 3.69 (d, J
= 11.3 Hz, 6H). 13C{1H} NMR (101 MHz, DMSO-d6): δ 190.7 (d, J = 6.4 Hz), 188.7 (d, J = 6.3 Hz),
163.9, 135.6 (d, J = 4.1 Hz), 134.0, 131.6, 128.9, 128.8, 128.3 (d, J = 3.1 Hz), 114.2, 58.0 (d, J =
131.0 Hz), 55.7, 53.3 (d, J = 0.9 Hz), 53.2 (d, J = 0.9 Hz); 31P{1H} NMR (162 MHz, DMSO-d6): δ
18.28; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C18H20O6P 363.0997, found 363.0998.
Dimethyl(1,3-dioxo-1,3-di-p-tolylpropan-2-yl)phosphonate (3d).
White solid, mp 163-165 °C, 78% yield (140.4 mg); 1H NMR (400 MHz, DMSO-d6): δ 7.94 (d, J =
8.0 Hz, 4H), 7.33 (d, J = 7.9 Hz, 4H), 7.02 (d, J = 22.8 Hz, 1H), 3.67 (d, J = 11.3 Hz, 6H), 2.36 (s,
13
6H); C{1H} NMR (101 MHz, DMSO-d6): δ 190.0 (d, J = 6.4 Hz), 144.8, 133.1 (d, J = 3.6 Hz),
129.5, 129.1, 58.0 (d, J = 131.0 Hz), 53.2 (d, J = 6.4 Hz), 21.2; 31P{1H} NMR(162 MHz, DMSO-d6):
δ 18.38; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C19H22O5P 361.1205, found 361.1206.
Dimethyl(1,3-bis(4-methoxyphenyl)-1,3-dioxopropan-2-yl)phosphonate (3e)
White solid, mp 165-166 °C, 80% yield (156.8 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.02 (d, J =
8.8 Hz, 4H), 7.05 (d, J = 8.8 Hz, 4H), 6.95 (d, J = 22.7 Hz, 1H), 3.84 (s, 6H), 3.67 (d, J = 11.2 Hz,
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6H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 188.8 (d, J = 6.4 Hz), 163.8, 131.4, 128.4 (d, J = 3.7
Hz), 114.2, 57.7 (d, J = 131.5 Hz), 55.7, 53.1 (d, J = 6.3 Hz); 31P{1H} NMR (162 MHz, DMSO-d6):
δ 18.66; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C19H22O7P 393.1103, found 393.1108.
Dimethyl(1,3-dioxo-1-phenyl-3-(o-tolyl)propan-2-yl)phosphonate (3f)
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Yellow oil, 52% yield (88.2 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 12.29 (s, 0.19H,
enol), 8.09-7.99 (m, 2H), 7.67 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.7 Hz, 2H), 7.43 (t, J = 7.1 Hz, 1H),
7.37-7.10 (m, 3H), 6.97 (d, J = 23.9 Hz, 0.77H, keto), 3.64 (dd, J = 11.3, 2.7 Hz, 6H), 2.34 (d, J =
16.2 Hz, 3H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 193.9 (d, J = 6.0 Hz), 191.1 (d, J = 5.8 Hz),
138.2, 136.7 (d, J = 3.4 Hz), 135.8 (d, J = 3.1 Hz), 134.0, 132.0, 131.8, 130.1, 128.9 (d, J = 2.8 Hz),
128.8, 128.4, 128.1, 125.8, 125.1, 60.5 (d, J = 129.3 Hz), 53.3 (d, J = 8.3 Hz), 53.2 (d, J = 8.3 Hz),
20.4, 19.4; P{1H} NMR (162 MHz, DMSO-d6): δ 17.84; HRMS (ESI-TOF) m/z: (M+Na)+ Calcd
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for C18H19NaO5P 369.0868, found 369.0853.
Dimethyl(1-(4-chlorophenyl)-1,3-dioxo-3-phenylpropan-2-yl)phosphonate (3g)
1
Yellow oil, 64% yield (117.1 mg); H NMR (400 MHz, DMSO-d6): δ 8.12-7.96 (m, 4H), 7.73-7.60
(m, 3H), 7.54 (t, J = 7.7 Hz, 2H), 7.12 (d, J = 23.3 Hz, 1H), 3.69 (d, J = 4.7 Hz, 3H), 3.66 (d, J = 4.8
Hz, 3H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 190.6 (d, J = 6.3 Hz), 189.76 (d, J = 6.06 Hz),
189.67 (d, J = 6.06 Hz), 139.3 (d, J = 4.2 Hz), 135.4 (d, J = 3.6 Hz), 134.2, 134.1 (d, J = 3.4 Hz),
130.8, 129.1, 129.0, 128.9, 58.34 (d, J = 130.29 Hz), 58.29 (d, J = 130.29 Hz), 53.42, 53.39, 53.36,
53.33, 53.27; 31P{1H} NMR (162 MHz, DMSO-d6): δ 17.38 (d, J = 50.8 Hz); HRMS (ESI-TOF) m/z:
(M+H)+ Calcd for C17H17ClO5P 367.0502, found 367.0516.
Dimethyl(1-(4-bromophenyl)-1,3-dioxo-3-phenylpropan-2-yl)phosphonate (3h)
Yellow oil, 60% yield (122.7 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.07-7.93 (m, 4H), 7.78 (d, J =
8.6 Hz, 2H), 7.68 (t, J = 7.4 Hz, 1H), 7.54 (t, J = 7.7 Hz, 2H), 7.11 (d, J = 23.3 Hz, 1H), 3.69 (d, J =
5.0 Hz, 3H), 3.66 (d, J = 5.0 Hz, 3H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 190.6 (d, J = 6.3 Hz),
190.0 (d, J = 6.4 Hz), 135.4 (d, J = 3.6 Hz), 134.5 (d, J = 3.3 Hz), 134.2, 132.1, 130.9, 128.9 (d, J =
8.8 Hz), 128.6, 58.3 (d, J = 130.1 Hz), 53.4 (d, J = 6.4 Hz), 53.3 (d, J = 6.4 Hz); 31P{1H} NMR (162
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MHz, DMSO-d6): δ 17.35 (d, J = 53.9 Hz); HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C17H17BrO5P
410.9997, found 410.9987.
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Dimethyl(1-(4-bromophenyl)-3-(4-methoxyphenyl)-1,3-dioxopropan-2-yl)phosphonate (3i)
White solid, mp 167-168 °C, 43% yield (94.6 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.01 (d, J =
8.9 Hz, 2H), 7.96 (d, J = 8.7 Hz, 2H), 7.76 (d, J = 8.6 Hz, 2H), 7.10-6.99 (m, 3H), 3.84 (s, 3H), 3.69
(d, J = 5.0 Hz, 3H), 3.66 (d, J = 5.0 Hz, 3H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 190.1 (d, J =
6.5 Hz), 188.6 (d, J = 6.2 Hz), 163.9, 134.6 (d, J = 3.9 Hz), 132.1, 131.5, 130.8, 128.4, 128.2 (d, J =
3.3 Hz), 114.2, 58.0 (d, J = 130.7 Hz), 55.7, 53.3 (d, J = 6.2 Hz), 53.2 (d, J = 6.2 Hz); 31P{1H} NMR
(162 MHz, DMSO-d6): δ 17.93; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C18H19BrO6P 441.0103,
found 441.0105.
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Dimethyl(1,3-bis(4-bromophenyl)-1,3-dioxopropan-2-yl)phosphonate (3j)
White solid, mp 165-166 °C, 61% yield (148.5 mg); 1H NMR (400 MHz, DMSO-d6): δ 7.96 (d, J =
8.6 Hz, 4H), 7.78 (d, J = 8.6 Hz, 4H), 7.11 (d, J = 23.5 Hz, 1H), 3.68 (d, J = 11.3 Hz, 6H); 13C{1H}
NMR (101 MHz, DMSO-d6): δ 189.9 (d, J = 6.4 Hz), 134.4 (d, J = 3.4 Hz), 132.1, 130.8, 128.6,
58.28 (d, J = 129.8 Hz), 53.4 (d, J = 6.5 Hz); 31P{1H} NMR (162 MHz, DMSO-d6): δ 17.17; HRMS
(ESI-TOF) m/z: (M+H)+ Calcd for C17H16Br2O5P 488.9102, found 488.9101.
Dimethyl (1,3-dioxo-1-phenylpentan-2-yl)phosphonate (3k)
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Yellow oil, 68% yield (96.6 mg); H NMR (400 MHz, DMSO-d6):δ 8.04-7.98 (m, 2H), 7.75 (t, J =
7.4 Hz, 1H), 7.61 (t, J = 7.7 Hz, 2H), 6.22 (d, J = 23.3 Hz, 1H), 3.72 (d, J = 1.7 Hz, 3H), 3.70 (d, J
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= 1.7 Hz, 3H), 2.75 (qd, J = 7.2, 2.8 Hz, 2H), 0.98 (t, J = 7.2 Hz, 3H); C{1H} NMR (101 MHz,
DMSO-d6): δ 200.2 (d, J = 5.7 Hz), 190.5 (d, J = 6.2 Hz), 136.0 (d, J = 3.9 Hz), 134.1, 128.9, 128.8,
61.6 (d, J = 126.8 Hz), 53.4 (d, J = 2.9 Hz), 53.3 (d, J = 2.9 Hz), 36.0, 7.6. 31P{1H} NMR (162 MHz,
DMSO-d6): δ 17.84; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C13H18O5P 285.0892, found
285.0890.
Dimethyl(1-(3-bromophenyl)-1,3-dioxo-3-phenylpropan-2-yl)phosphonate(3l)
Yellow oil, 63% yield (135.7 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.28 (t, J = 1.7 Hz, 1H), 8.09
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(d, J = 8.0 Hz, 3H), 7.96-7.86 (m, 1H), 7.73 (t, J = 7.4 Hz, 1H), 7.64-7.53 (m, 3H), 7.20 (d, J = 23.4
Hz, 1H), 3.74 (d, J = 3.4 Hz, 3H), 3.72 (d, J = 3.4 Hz, 3H); 13C{1H} NMR (101 MHz, DMSO-d6): δ
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131.4, 131.1, 129.0, 128.9, 127.8, 122.3, 58.34 (d, J = 129.8 Hz), 53.4 (d, J = 4.4 Hz), 53.3 (d, J =
4.4 Hz); 31P{1H} NMR (162 MHz, DMSO-d6): δ 15.14; HRMS (ESI-TOF) m/z: (M+Na)+ Calcd for
C17H16BrNaO5P 432.9816, found 432.9806.
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Ethyl 2-(diethoxyphosphoryl)-3-oxo-3-phenylpropanoate (5a)
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Yellow oil, 73% yield (119.7 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 8.03 (d, J = 7.4
Hz, 2H), 7.69 (t, J = 7.4 Hz, 1H), 7.55 (t, J = 7.7 Hz, 2H), 5.83 (d, J = 23.1 Hz, 0.82H, enol), 4.23-
3.95 (m, 6H), 3.11 (d, J = 21.4 Hz, 0.18H, keto), 1.29-1.10 (m, 9H); 13C{1H} NMR (101 MHz,
DMSO-d6): δ 189.9 (d, J = 5.8 Hz), 164.5 (d, J = 5.3 Hz), 135.9 (d, J = 3.0 Hz), 134.0 128.9, 128.7,
62.8 (d, J = 0.9 Hz), 62.7 (d, J = 0.9 Hz), 61.6, 55.1 (d, J = 130.5 Hz), 16.04 (d, J = 6.06 Hz), 13.8;
31P{1H} NMR (enol+ keto) (162 MHz, DMSO-d6): δ 20.13, 14.25; MS (ESI-TOF) m/z: (M+H)+
Calcd for C15H22O6P 329.1, found 329.1.
Ethyl2-(diethoxyphosphoryl)-3-oxo-3-(p-tolyl)propanoate (5b)
Yellow oil, 73% yield (124.8 mg); 1H NMR (400 MHz, DMSO-d6): δ 7.92 (d, J = 8.3 Hz, 2H), 7.35
(d, J = 8.1 Hz, 2H), 5.76 (d, J = 22.9 Hz, 1H), 4.17-4.01 (m, 6H), 2.39 (s, 3H), 1.20-1.11(m, 9H);
13C{1H} NMR (101 MHz, DMSO-d6): δ 189.3 (d, J = 5.8 Hz), 164.6 (d, J = 5.3 Hz), 144.7, 133.4 (d,
J = 3.1 Hz), 129.3, 129.1, 62.73 (d, J = 6.2 Hz), 62.67 (d, J = 6.2 Hz), 61.5, 55.0 (d, J = 130.7 Hz),
21.2, 16.1 (d, J = 1.2 Hz), 16.0 (d, J = 1.2 Hz), 13.8; 31P{1H} NMR (162 MHz, DMSO-d6): δ 14.41;
HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C16H24O6P 343.1311, found 343.1301.
Ethyl2-(diethoxyphosphoryl)-3-(4-methoxyphenyl)-3-oxopropanoate (5c)
Yellow oil, 71% yield (127.0 mg); 1H NMR (400 MHz, DMSO-d6): δ 8.03 (d, J = 8.9 Hz, 2H), 7.07
(d, J = 8.9 Hz, 2H), 5.74 (d, J = 22.8 Hz, 1H), 4.18-4.04 (m, 6H), 3.86 (s, 3H), 1.22-1.12 (m, 9H);
13C{1H} NMR (101 MHz, DMSO-d6): δ 188.0 (d, J = 5.7 Hz), 164.7 (d, J = 5.2 Hz), 163.8, 131.6,
128.7 (d, J = 3.0 Hz), 114.0, 62.7 (d, J = 6.2 Hz), 62.6 (d, J = 6.2 Hz), 61.5, 55.7, 54.8 (d, J = 131.1
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Hz), 16.12 (d, J = 1.7 Hz), 16.06 (d, J = 1.7 Hz), 13.8; P{1H} NMR (162 MHz, DMSO-d6): δ
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14.61; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C16H24O7P 359.1260, found 359.1265.
Ethyl3(4-bromophenyl)-2-(diethoxyphosphoryl)-3-oxopropanoate (5d)
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Yellow oil, 57% yield (115.7 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 7.96 (d, J = 8.7
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Hz, 2H), 7.78 (d, J = 8.7 Hz, 2H), 5.85 (d, J = 23.3 Hz, 0.81H, enol), 4.18-3.99 (m, 6H), 3.10 (d, J =
21.4 Hz, 0.22H, keto), 1.30-1.10 (m, 9H); 13C{1H} NMR (101 MHz, DMSO-d6): δ 189.3 (d, J = 5.8
Hz), 164.4 (d, J = 5.2 Hz), 134.9 (d, J = 3.0 Hz), 131.9, 131.7, 131.0, 130.9, 128.4, 62.92 (d, J = 1.8
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Hz), 62.86 (d, J = 1.8 Hz), 61.7, 55.2 (d, J = 130.2 Hz), 16.14, 16.08, 13.8; P{1H} NMR (enol+
keto) (162 MHz, DMSO-d6): δ 20.12, 13.95; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C15H21BrO6P
407.0259, found 407.0245.
Ethyl3-(4-chlorophenyl)-2-(diethoxyphosphoryl)-3-oxopropanoate (5e)
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Yellow oil, 61% yield (110.4 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 8.04 (d, J = 8.7
Hz, 2H), 7.63 (d, J = 8.7 Hz, 2H), 5.86 (d, J = 23.3 Hz, 0.79H, enol), 4.20-3.80 (m, 6H), 3.10 (d, J =
21.4 Hz, 0.25H, keto), 1.27-1.10 (m, 9H); 13C{1H} NMR (101 MHz, CDCl3-d6): δ 189.1 (d, J = 5.8
Hz), 164.4 (d, J = 5.2 Hz), 139.1, 134.6 (d, J = 2.9 Hz), 130.9, 128.9, 62.9, 62.8, 61.7, 55.2 (d, J =
130.0 Hz), 16.06 (d, J = 6.06 Hz), 13.8. 31P{1H} NMR (enol+ keto) (162 MHz, DMSO-d6): δ 20.12,
13.96; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C15H21ClO6P 363.0764, found 363.0761.
Ethyl2-(diethoxyphosphoryl)-3-(2-methoxyphenyl)-3-oxopropanoate (5g)
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Yellow oil, 49% yield (87.7 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 13.38 (s, 0.2H,
enol), 7.66 -7.38 (m, 2H), 7.32-7.15 (m, 1H), 7.11-6.97 (m, 1H), 5.33 (d, J = 22.4 Hz, 0.72H, keto),
4.22-3.92 (m, 6H), 3.86 (s, 2.48H, keto), 3.73 (s, 0.64H, enol), 1.28 (t, J = 7.0 Hz, 1.45H, enol), 1.21
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-1.14 (m, 6.64H, keto), 0.88 (t, J = 7.1 Hz, 0.67H, enol); C{1H} NMR (101 MHz, DMSO-d6): δ
189.9 (d, J = 6.4 Hz), 164.0 (d, J = 5.9 Hz), 158.3, 155.9, 134.9, 131.4, 130.2, 128.4, 126.5 (d, J =
3.2 Hz), 120.7, 120.0, 112.5, 111.1, 62.63 (d, J = 6.3 Hz), 62.57 (d, J = 6.3 Hz), 61.4, 59.2 (d, J =
127.8 Hz), 55.8, 16.08 (d, J = 6.06 Hz, keto), 15.93 (d, J = 6.06 Hz, enol), 13.9 (keto), 13.6 (enol);
31P{1H} NMR (enol+ keto) (162 MHz, DMSO-d6): δ 24.24, 14.72; HRMS (ESI-TOF) m/z: (M+H)+
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Calcd for C16H24O7P 359.1260, found 359.1268.
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Ethyl3-(2-bromophenyl)-2-(diethoxyphosphoryl)-3-oxopropanoate (5h)
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Yellow oil, 50% yield (101.5 mg); H NMR (enol+keto) (400 MHz, DMSO-d6): δ 13.82 (s, 0.72H,
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enol), 7.84-7.64 (m, 1H), 7.54-7.34 (m, 3H), 5.60 (d, J = 24.1 Hz, 0.14H, keto), 4.23-4.10 (m, 3.31H,
enol), 4.09-3.99 (m, 0.8H, keto), 3.85 (q, J = 7.1 Hz, 1.65H, enol), 1.30 (t, J = 7.0 Hz, 4.71H, enol),
1.23-1.08 (m, 2.25H, keto), 0.86 (t, J = 7.1 Hz, 2.35H, enol); 13C{1H} NMR (enol+keto) (101 MHz,
DMSO-d6): δ 191.4 (d, J = 5.9 Hz), 180.5 (d, J = 6.9 Hz), 163.9 (d, J = 4.6 Hz), 163.6 (d, J = 9.8 Hz),
138.7, 138.0 (d, J = 15.8 Hz), 133.9, 133.1, 132.1, 130.9, 130.1, 128.7, 127.5 (d, J = 11.2 Hz), 119.5,
119.1, 93.38, 91.64, 63.3, 63.0 (d, J = 6.3 Hz), 62.9 (d, J = 6.5 Hz), 61.7, 59.8, 58.7 (d, J = 127.2
Hz), 16.04 (d, J = 6.06 Hz), 13.8, 13.5; 31P{1H} NMR (enol+keto) (162 MHz, DMSO-d6): δ 23.50,
13.21; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C15H21BrO6P 407.0259, found 407.0265.
Ethyl3-(2-chlorophenyl)-2-(diethoxyphosphoryl)-3-oxopropanoate (5i)
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Yellow oil, 50% yield (90.5 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 13.80 (s, 0.6H,
enol), 7.82 (t, J = 7.4 Hz, 0.29H), 7.60-7.36 (m, 4H), 5.59 (d, J = 24.1 Hz, 0.17H, keto), 4.25-3.94
(m, 4.48H), 3.91-3.78 (m, 1.86H), 1.30 (t, J = 7.0 Hz, 4.58H), 1.22-1.08 (m, 2.41H), 0.87 (t, J = 7.1
Hz, 2.24H); 13C{1H} NMR (enol+ keto) (101 MHz, DMSO-d6): δ 193.8 (d, J = 6.4 Hz), 190.8 (d, J
= 5.9 Hz), 179.1 (d, J = 6.9 Hz), 163.9 (d, J = 4.7 Hz), 163.7 (d, J = 9.7 Hz), 137.8 (d, J = 1.9 Hz),
137.0 (d, J = 2.1 Hz), 136.0, 135.8, 133.0, 132.7, 130.8, 130.2 (d, J = 3.9 Hz), 130.0, 129.0, 128.8,
127.2 (d, J = 1.4 Hz), 127.0, 93.7, 92.0, 63.3 (d, J = 5.0 Hz), 62.98 (d, J = 6.3 Hz), 62.83 (d, J = 6.4
Hz), 61.84 (d, J = 6.2 Hz), 61.64, 59.8, 58.8 (d, J = 127.3 Hz), 15.97 (d, J = 6.06 Hz), 13.7, 13.5;
31P{1H} NMR (enol+ keto) (162 MHz, DMSO-d6): δ 23.35, 19.32, 13.22; HRMS (ESI-TOF) m/z:
(M+H)+ Calcd for C15H21ClO6P 363.0764, found 363.0758.
Ethyl2-(diethoxyphosphoryl)-3-(2,6-dimethoxyphenyl)-3-oxopropanoate (5l)
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Yellow oil, 16% yield (31.0 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 13.44 (s, 0.78H,
enol), 7.43-7.27 (m, 1H), 6.80-6.62 (m, 2H), 4.87 (d, J = 23.2 Hz, 0.21H), 4.18-3.77 (m, 6H), 3.76 –
3.66 (m, 6H), 1.29 (t, J = 7.0 Hz, 4.31H), 1.21-1.04 (m, 2.87H), 0.84 (t, J = 7.1 Hz, 2.1H); 13C{1H}
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NMR (enol+ keto) (101 MHz, CDCl3): δ 194.2 (d, J = 6.4 Hz), 189.4 (d, J = 6.2 Hz), 178.0 (d, J =
7.4 Hz), 164.1 (d, J = 10.5 Hz), 163.6 (d, J = 4.7 Hz), 157.3, 156.7, 156.4, 132.5, 131.6, 130.7, 115.1
(d, J = 14.7 Hz), 104.2 (d, J = 28.6 Hz), 94.0, 92.1, 63.0 (d, J = 5.1 Hz), 62.8 (d, J = 6.3 Hz), 62.5 (d,
J = 6.4 Hz), 59.3, 55.9, 18.6, 15.9 (d, J = 6.1 Hz), 13.9, 13.5. 31P{1H} NMR (enol+ keto) (162 MHz,
DMSO-d6): δ 24.50, 13.49; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C17H26O8P 389.1365, found
389.1362.
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Diethyl (1,3-dioxo-1,3-diphenylpropan-2-yl)phosphonate (6ab)
Yellow oil, 72% yield (129.6 mg); 1H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 12.74 (s, 0.04H,
enol), 8.07 (d, J = 7.3 Hz, 4H), 7.67 (t, J = 7.4 Hz, 2H), 7.54 (t, J = 7.7 Hz, 4H), 7.08 (d, J = 23.2 Hz,
13
0.93H, keto), 4.16-4.02 (m, 4H), 1.09 (t, J = 7.0 Hz, 6H); C{1H} NMR (enol+ keto) (101 MHz,
DMSO-d6): δ 190.9 (d, J = 6.3 Hz), 135.7 (d, J = 3.4 Hz), 134.0, 128.94, 128.85, 62.41 (d, J = 7.07
Hz), 58.6 (d, J = 130.3 Hz), 15.95 (d, J = 6.06 Hz) ; 31P{1H} NMR (enol+ keto) (162 MHz, DMSO-
d6): δ 22.50, 14.94; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C19H22O5P 361.1205, found 361.1206.
Diisopropyl(1,3-dioxo-1,3-diphenylpropan-2-yl)phosphonate (6ac)
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Yellow oil, 36% yield (69.8 mg); H NMR (enol+ keto) (400 MHz, DMSO-d6): δ 12.90 (s, 0.07H,
enol), 8.06 (d, J = 7.4 Hz, 4H), 7.66 (t, J = 7.4 Hz, 2H), 7.53 (t, J = 7.7 Hz, 4H), 6.99 (d, J = 23.3 Hz,
0.90H, keto), 4.83-4.67 (m, 2H), 1.11 (dd, J = 5.9, 4.8 Hz, 12H); 13C{1H} NMR (101 MHz, DMSO-
d6): δ 191.0 (d, J = 6.2 Hz), 135.8 (d, J = 3.4 Hz), 133.9, 129.0, 128.8, 71.1 (d, J = 6.7 Hz), 59.1 (d, J
31
= 131.5 Hz), 23.7 (d, J = 3.0 Hz), 23.2 (d, J = 5.9 Hz); P{1H} NMR (162 MHz, DMSO-d6): δ
12.88; HRMS (ESI-TOF) m/z: (M+H)+ Calcd for C21H26O5P 389.1518, found 389.1519.
3-Dodecyl-1,3-dimethylindolin-2-one (8)
Colorless oil, 55% yield (43 mg); 1H NMR (400 MHz, CDCl3): δ 7.12 -7.16 (m, 1H), 7.11 - 7.07 (m,
1H), 7.02 - 6.96 (m, 1H), 6.78 - 6.74 (m, 1H), 3.14 (s, 3H), 1.91 - 1.74 (m, 1H), 1.69 - 1.58 (m, 1H),
1.27 (s, 3H), 1.22 – 1.02 (m, 20H), 0.80 (t, J = 6.9 Hz, 3H). 13C{1H} NMR (101 MHz, CDCl3): δ
181.01, 143.46, 134.47, 127.67, 122.59, 122.52, 107.96, 48.59, 38.68, 32.05, 29.89, 29.74, 29.70,
29.68, 29.47, 29.45, 26.23, 24.60, 23.92, 22.82, 14.26. HRMS (ESI-TOF) m/z: (M+Na)+ Calcd for
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C22H35NNaO 352.2616, found 352.2612.
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ASSOCIATED CONTENT
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Supporting Information
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1H, 13C, and 31P NMR spectra for compounds 3, 5, 6 and 8. This material is available free of charge
via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: jpzou@suda.edu.cn
ORCID
Jian-Ping Zou: 0000-0002-8092-9527
Notes
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
We acknowledges the grants from the National Natural Science Foundation of China (Nos.
21172163, 21472133), the Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD), Key Laboratory of Organic Synthesis of Jiangsu Province
(KJS1749) for their financial support.
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