Synthesis of Alkenylphosphonates through Palladium-Catalyzed Coupling of α-Diazo Phosphonates with Benzyl or Allyl Halides

Article abstract of DOI:10.1021/acs.joc.5b00629

An efficient method for the synthesis of organophosphonates through palladium-catalyzed coupling of α-diazo phosphonates with benzyl or allyl halides has been developed. Trisubstituted alkenylphosphonates bearing versatile functional groups can be easily accessed in good yields and with excellent stereoselectivity through this method. Moreover, with similar strategy α-substituted vinylphosphonates can also be attained by the palladium-catalyzed coupling reaction of N-tosylhydrazones and aryl bromides. Migratory insertion of palladium carbene is proposed as the key step in this reaction.

Full text of DOI:10.1021/acs.joc.5b00629

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Article
Synthesis of Alkenylphosphonates through Palladium-Catalyzed
Coupling of alpha-Diazo Phosphonates with Benzyl or Allyl Halides
Yujing Zhou, Fei Ye, Xi Wang, Shuai Xu, Yan Zhang, and Jianbo Wang
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 22 May 2015
Downloaded from http://pubs.acs.org on May 22, 2015
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Synthesis of Alkenylphosphonates through Palladium-Catalyzed
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Coupling of α-Diazo Phosphonates with Benzyl or Allyl Halides
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Yujing Zhou,† Fei Ye,*,† Xi Wang,† Shuai Xu,† Yan Zhang,† Jianbo Wang*,†,‡
†Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic
Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking
University, Beijing 100871, China
‡State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032,
China
Email: wangjb@pku.edu.cn
RECEIVED DATE (to be automatically inserted)
ABSTRACT. An efficient method for the synthesis of organophosphonates through palladium-
catalyzed coupling of α-diazo phosphonates with benzyl or allyl halides has been developed.
Trisubstituted alkenylphosphonates bearing versatile functional groups can be easily accessed in good
yields and with excellent stereoselectivity through this method. Moreover, with similar strategy α-
substituted vinylphosphonates can also be attained by the palladium-catalyzed coupling reaction of N-
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tosylhydrazones and aryl bromides. Migratory insertion of palladium carbene is proposed as the key step
in this reaction.
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■ INTRODUCTION
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Organophosphonates have attracted much attention for their important roles in biochemistry,
pharmaceuticals and agrochemicals.1 Among them, alkenylphosphonates are essential structural units as
well as synthetic precursors, which can undergo various transformations to afford biologically active
compounds and other functional molecules.2 Since their important applications in chemistry and biology,
significant efforts have been devoted to the development of synthetic methods toward this type of
compounds. Conventionally, alkenylphosphonates with defined stereochemistry can be prepared by
Wittig, Wittig-Horner or metal-catalyzed Michaelis-Arbusov reactions.3 Other strategies include Heck-
type reaction of alkenylphosphonates with various coupling partners,4 cross-coupling of P(O)H
compounds with vinyl halides,5 olefin metathesis6 and so on.7 However, these methods in general suffer
from the drawbacks such as relatively harsh reaction conditions and low yields of the products, along
with the need to prepare prefunctionalized alkenylphosphonates. Recently, transition-metal-catalyzed
addition of hydrogen phosphonates to alkynes has become an efficient way to synthesize
alkenylphosphonates,8 but in most cases only terminal alkynes are effective and the regioselectivity
remains a serious problem in the reaction of internal alkynes. In addition, methods to synthesize
trisubstituted alkenylphosphonates are still limited. Thus, the development of efficient and
complementary strategy with mild reaction conditions and easily accessible reagents remains a topic of
great interest.
Diazo compounds, which have been commonly utilized as carbene precursors, have recently emerged
as a novel type of coupling partners in organic synthesis.9 In particular, palladium-catalyzed cross-
coupling reaction via diazo compound has been established as a powerful method for the carbon-carbon
double bond formations.10-12 As a continuation of our own interests in the carbene involved cross-
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coupling reactions, we envisioned that alkenylphosphonates should be accessed by applying the strategy
with easily available α-diazo arylmethylphosphonates13 as the coupling partners. As shown in Scheme 1,
the coupling reaction is considered to follow similar pathway involving oxidative addition, palladium
carbene formation, migratory insertion and –hydride elimination. Herein we report the development of
an efficient synthesis of alkenylphosphonates with good yields and excellent stereoselectivity through
Pd-catalyzed coupling of α-diazo arylmethylphosphonates with benzyl and ally halides. The method can
also be extended to the coupling reaction of N-tosylhydrazones with aryl bromides.
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Scheme 1. Synthesis of Alkenylphosphonates through Palladium Carbene Coupling
■ RESULTS AND DISCUSSION
Our investigation began with the reaction between α-diazo benzylphosphonates 1a and benzyl
bromide 2a (Table 1). Various palladium catalysts with the combination of P(2-furyl)3 in toluene were
examined, and Pd(OAc)2 turned out to be more effective in this transformation (entries1-3). Switch of
the solvent from toluene to dioxane did not improve the yield (entry 4). It was observed that the main
difficulty was the oxidation of the P(2-furyl)3 ligand by the diazo substrate. Upon extensive experiments,
it was found that the problem could be solved simply by changing the reaction concentration. Thus,
when we decreased the reaction concentration from 0.2 M to 0.1 M, the yield was significantly
improved (entry 5). Then, the reaction temperature was examined and the reaction was found to proceed
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more efficiently at 80 C (entries 5-7). Further improvement was observed by adjusting the ratio of
substrates and the reaction with 1.25 equivalents of benzyl bromide was proved to afford the optimal
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result (entry 9). Finally, control experiment showed that no desired product could be detected in the
absence of palladium catalyst (entry 10).
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Table 1. Optimization of Reaction Conditionsa
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entry cat. (mol%) ligand (mol%)
conc. 1a:2a T (oC) yield (%)b
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Pd(PPh3)4 (5)
Pd2dba3 (2.5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
Pd(OAc)2 (5)
--
--
0.2 M 1:1
0.2 M 1:1
0.2 M 1:1
0.2 M 1:1
0.1 M 1:1
0.1 M 1:1
0.1 M 1:1
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P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
P(2-furyl)3 (20)
--
0.1 M 1.25:1 80
0.1 M 1:1.25 80
0.1 M 1:1.25 80
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aThe reaction was carried out with 1a (0.2 mmol) under an atmosphere of nitrogen for 5 h. (i-Pr)2NH
(0.4 mmol) was used as base. bIsolated yields. c1,4-Dioxane was used as solvent.
With the optimized reaction conditions established, the scope of benzyl halides was next examined.
As shown in Scheme 2, the benzyl bromides bearing various functional groups proceeded well to afford
the corresponding products with E stereoselectivity. Notably, chloro substituents are tolerated under the
reaction conditions (3d, 3h), which is beneficial as starting compounds for further coupling reactions.
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Besides, the relatively bulky methyl substituent at the ortho position did not hamper the reaction (3j).
For polycyclic substrates, the reaction also went smoothly to give the corresponding
alkenylphosphonates (3k, 3l) in excellent yields. Gratifyingly, benzyl chlorides showed good reactivity
under the same reaction conditions (3b, 3f, 3l).
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Scheme 2. The Substrate Scope of Benzyl Halidesa
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a The reaction conditions are as following: 1a (0.2 mmol), benzyl halides 2a-n (0.25 mmol), toluene (2.0
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mL). b Isolated yield. c E/Z ratio was determined by crude 1H NMR.
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Subsequently, a series of α-diazo arylmethylphosphonates were subjected to the reaction conditions
(Scheme 3). The substrates bearing electron-donating groups (1b-d) and halogen substituents (1e-g)
were found to undergo the desired transformation to afford the corresponding alkenylphosphonates in
good yields. We observed that the diazo compounds bearing electron-withdrawing groups showed a
slightly reduced reactivity because they are more reluctant to undergo dediazoniation to generate
palladium carbene intermediate. Notably, α-diazo arylmethylphosphonates containing N-tosyl protected
indole moiety was also successfully converted into the corresponding product.
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Scheme 3. The Substrate Scope of α-Diazo Arylmethylphosphonates a
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a
The reaction conditions are as following: α-diazo arylmethylphosphonates 1b-k (0.2 mmol), benzyl
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bromide 2a (0.25 mmol), toluene (2.0 mL). b Isolated yield.
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Since we have previously reported the palladium-catalyzed cross-coupling of allyl halides with
diazo compounds to afford 1,3-diene products,12b we thus conceived that the similar coupling reaction
should also be extended to the reaction with α-diazo arylmethylphosphonates. As we expected, the
coupling of α-diazo arylmethylphosphonates with both allyl bromides and allyl chloride proceeded well
to give the corresponding 1,3-diene products in moderate to good yields under the same reaction
conditions, as shown in Scheme 4.
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Scheme 4. The Substrate Scope of Allyl Halidesa
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The reaction conditions are as following: α-diazo arylmethylphosphonates 1 (0.2 mmol), allyl halides
5a-d (0.25 mmol), toluene (2.0 mL). b Isolated yield.
Furthermore, we turned our attention to the synthesis of α-substituted vinylphosphonates by the
coupling reaction of aryl bromides and α-diazo alkylphosphonates. However, α-diazo alkylphosphonates
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are not stable enough under conventional conditions for their preparation and purification, so we chose
their precursor N-tosylhydrazones as the substrates in the coupling reaction.11,9c The corresponding
diazo substrates are formed in situ under basic conditions. With slight modification of the standard
reaction conditions, we could obtain the coupling product 9a in 80% yield (Scheme 5). Then, a series of
aryl bromides and N-tosylhydrazones were investigated. Aryl bromides bearing electron-donating and -
withdrawing groups all proceeded well to give the desired coupling products in good yields. Various
functional groups are tolerated under the reaction conditions. Moreover, substrates containing polycyclic
aromatic rings and heterocycles also showed good reactivity in this transformation.
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Scheme 5. The Reaction of N-Tosylhydrazones with Aryl Bromidesa
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a The reaction conditions are as following: N-tosylhydrazones 7a-c (0.2 mmol), aryl bromides 8a-j (0.3
mmol), 1,4-dioxane (1.5 mL). b Isolated yield. c E/Z ratio was determined by crude 1H NMR.
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Finally, to illustrate the practical use of this synthetic method, a scale-up experiment was conducted.
To our delight, the corresponding coupling product could be obtained in gram scale without significant
effect in the yield (eq 1).
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(1)
The high stereoselectivity for (E)-olefin formation can be rationalized by the transition state which is
required for syn -H elimination process from the alkylpalladium intermediate generated from Pd
carbene migratory (Scheme 6). We propose that the aryl group Ar' is preferred to eclipse with the less
sterically bulky Ar group rather than the bulky phosphonate group, leading to (E)-olefin as the only
product in most cases.
Scheme 6. Rationalization of the Stereoselectivity
■ CONCLUSION
In summary, we have developed a highly efficient Pd-catalyzed cross-coupling reaction with α-
diazo phosphonates as the coupling partners, which constitutes a novel strategy to synthesize
alkenylphosphonates. This transformation uses easily accessible reagents as the starting materials, and
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could efficiently produce E-trisubstituted alkenes bearing versatile functional groups. Further efforts
concerning the application of α-diazo phosphonates in the synthesis of organophosphonate compounds
are underway in our group and the results will be reported in due course.
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■ EXPERIMENTAL SECTION
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The solvents were all distilled prior to use. MeCN, DCE and toluene were distilled from calcium
hydride. Dioxane was dried over Na with benzophenone ketyl intermediate as the indicator. 200-300
mesh silica gels for the chromatography (Qingdao, China) were used. Chemical shifts for 1H NMR (400
MHz) and 13C NMR (100 MHz) spectra were reported in ppm using tetramethylsilane (TMS) as the
internal standard. IR spectra are reported in wave numbers, cm−1. For HRMS measurements, the mass
analyzer is FT-ICR. p-ABSA: p-acetamidobenzenesulfonyl azide.
General procedure for the preparation of α-diazo arylmethylphosphonates 1a-k.13f The diazo
compounds 1a-k were prepared according to our previously reported method of palladium-catalyzed
cross-coupling of dimethyl (1-diazo-2-oxopropyl)phosphonate with aryl iodide. The dimethyl (1-diazo-
2-oxopropyl)phosphonate was prepared following a literature procedure.14 A solution of dimethyl 2-
oxopropylphosphonate (3.32 g, 20.0 mmol) in toluene (85 mL) and THF (18 mL) was stirred and cooled
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to 0 C by ice-water bath for 30 min, and sodium hydride (60% in oil, 0.88 g, 22.0 mmol) was slowly
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added into the flask. The mixture was stirred at 0 C under N2 for 1 hour, and p-ABSA (5.28 g, 22.0
mmol) was then added. The reaction was warmed to room temperature and stirring was continued
overnight under N2. The mixture was filtered through a celite pad, and the filtrate was evaporated in
vacuo to remove the volatile materials. The crude residue was purified by chromatography (silica gel,
petroleum ether:ethyl acetate = 1:1) to give the product as a yellow oil (2.38 g, 62%).
Pd(PPh3)4 (116 mg, 5 mol%), K2CO3 (552 mg, 4.0 mmol) and aryl iodide (2.0 mmol) were
suspended in methanol (5 mL) and toluene (5 mL) in a 25 mL flask under ambient atmosphere.
Dimethyl (1-diazo-2-oxopropyl)phosphonate (499 mg, 1.3 equiv) was then added, and the resulting
solution was stirred at room temperature for 5 h. The mixture was filtered through a short path of silica
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gel, eluting with ethyl acetate, and the filtrate was evaporated in vacuo to remove the volatile materials.
The crude residue was purified by column chromatography (silica gel, petroleum ether:ethyl acetate =
1:1) to afford the final products.
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Dimethyl (Diazo(phenyl)methyl)phosphonate (1a).13f Orange oil. yield 80% (360 mg). Rf = 0.45
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(petroleum ether:EtOAc =1:1); H NMR (400 MHz, CDCl3) δ 7.34-7.38 (m, 2H), 7.13-7.17 (m, 3H),
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3.81 (d, J = 11.9 Hz, 6H).
Dimethyl (Diazo(p-tolyl)methyl)phosphonate (1b).18 Orange oil. yield 72% (346 mg). Rf = 0.45
(petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.4
Hz, 2H), 3.80 (d, J = 11.6 Hz, 6H), 2.33 (s, 3H).
Dimethyl ([1,1'-Biphenyl]-4-yl(diazo)methyl)phosphonate (1c).Orange oil. yield 80% (483 mg). Rf =
0.45 (petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 8.4 Hz, 2H), 7.57 (d, J =
7.6 Hz, 2H), 7.42-7.45 (m, 2H), 7.32-7.36 (m, 1H), 7.23 (d, J = 8.4 Hz, 2H), 3.84 (d, J = 12.0 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 140.2, 138.1, 128.8, 127.9, 127.3, 126.7, 125.2 (d, J = 9.5 Hz), 122.9 (d,
J = 5.5 Hz), 53.2 (d, J = 5.1 Hz); IR (film) 2081, 1299, 1261, 1024, 839, 764 cm-1; HRMS (ESI) calcd
for C15H15N2NaO3P [(M+Na)+] 325.0713, found: 325.0712.
Dimethyl (Diazo(4-Methoxyphenyl)methyl)phosphonate (1d).18 Orange oil. yield 58% (297 mg). Rf =
1
0.45 (petroleum ether:EtOAc =1:1); H NMR (400 MHz, CDCl3) δ 7.09-7.12 (m, 2H), 6.92-6.94 (m,
2H), 3.81 (d, J = 12.0 Hz, 6H), 3.80 (s, 3H).
Dimethyl (Diazo(4-fluorophenyl)methyl)phosphonate (1e).13f Orange oil. yield 50% (244 mg). Rf =
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0.45 (petroleum ether:EtOAc =1:1); H NMR (400 MHz, CDCl3) δ 7.12-7.16 (m, 2H), 7.05-7.09 (m,
2H), 3.82 (d, J = 11.9 Hz, 6H).
Dimethyl ((4-Chlorophenyl)(diazo)methyl)phosphonate (1f). Orange oil. yield 70% (365 mg). Rf =
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0.45 (petroleum ether:EtOAc =1:1); H NMR (400 MHz, CDCl3) δ 7.31-7.34 (m, 2H), 7.08-7.11 (m,
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2H), 3.82 (d, J = 12.0 Hz, 6H); C NMR (100 MHz, CDCl3) δ 130.0, 128.5, 124.0 (d, J = 9.5 Hz),
122.8 (d, J = 5.5 Hz), 52.2 (d, J = 5.1 Hz); IR (film) 2085, 1494, 1279, 1262, 1187, 1026, 837, 800 cm-1;
HRMS (ESI) calcd for C9H10ClN2NaO3P [(M+Na)+] 283.0010, found: 283.0009.
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Dimethyl ((4-Bromophenyl)(diazo)methyl)phosphonate (1g).13f Orange oil. yield 80% (488 mg). Rf =
0.45 (petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.6 Hz, 2H), 7.04 (d, J =
8.6 Hz, 2H), 3.81 (d, J = 11.9 Hz, 6H).
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Dimethyl (Diazo(4-(hydroxymethyl)phenyl)methyl)phosphonate (1h). Orange oil. yield 48% (246 mg).
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(d, J = 8.0 Hz, 2H), 4.67 (s, 2H), 3.81 (d, J = 12.0 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 138.4, 128.0,
125.2 (d, J = 9.5 Hz), 122.6 (d, J = 4.4 Hz), 64.5, 53.1 (d, J = 4.9 Hz); IR (film) 3425, 2082, 1297, 1259,
1187, 1024, 838 cm-1; HRMS (ESI) calcd for C10H13N2NaO4P [(M+Na)+] 279.0505, found: 279.0502.
Dimethyl (Diazo(4-nitrophenyl)methyl)phosphonate (1i).13f Orange oil. yield 80% (434 mg). Rf = 0.40
(petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 8.9 Hz, 2H), 7.29 (d, J = 8.9
Hz, 2H), 3.86 (d, J = 11.9 Hz, 6H).
Dimethyl (Diazo(3-methoxyphenyl)methyl)phosphonate (1j).13f Orange oil. yield 58% (297 mg). Rf =
0.45 (petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 7.27 (t, J = 7.9 Hz, 1H), 6.75 (d, J =
8.2 Hz, 1H), 6.68-6.71 (m, 2H), 3.81 (d, J = 11.9 Hz, 6H), 3.80 (s, 3H).
Dimethyl (Diazo(1-tosyl-1H-indol-5-yl)methyl)phosphonate (1k). Orange oil. yield 61% (511 mg). Rf
= 0.30 (petroleum ether:EtOAc =1:1); 1H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 8.8 Hz, 1H), 7.75 (d, J
= 8.4 Hz, 2H), 7.56 (d, J = 3.6 Hz, 1H), 7.34 (d, J = 1.6 Hz, 1H), 7.22 (d, J = 8.0 Hz, 2H), 7.11 (dd, J =
8.8, 2.0 Hz, 1H), 6.61 (d, J = 3.6 Hz, 1H), 3.80 (d, J = 11.6 Hz, 6H), 2.34 (s, 3H). 13C NMR (100 MHz,
CDCl3) δ 145.1, 135.0, 132.7, 131.7, 129.9, 127.2, 126.7, 121.2 (d, J = 9.6 Hz), 119.6 (d, J = 4.9 Hz),
115.5 (d, J = 4.2 Hz), 114.4, 108.7, 53.1 (d, J = 5.0 Hz), 21.5; IR (film) 2082, 1460, 1262, 1188, 1176,
1134, 1024, 735 cm-1; HRMS (ESI) calcd for C18H18N3NaO5PS [(M+Na)+] 442.0597, found: 442.0598.
General procedure for the palladium-catalyzed coupling reaction of α-diazo
arylmethylphosphonates and benzyl or allyl halides. Pd(OAc)2 (2.2 mg, 5 mol%), P(2-furyl)3 (9.3 mg,
20 mol%), dimethyl (diazo(phenyl)methyl) phosphonate (0.20 mmol) and benzyl or allyl halide (0.25
mmol) were suspended in toluene (2 mL) in a 10 mL Schlenk tube under a nitrogen atmosphere. (i-
o
Pr)2NH (40.4 mg, 0.40 mmol) was then added, and the resulting solution was stirred at 80 C for 5 h.
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The mixture was filtered through a short path of silica gel, eluting with ethyl acetate, and the filtrate was
evaporated in vacuo to remove the volatile materials. The crude residue was purified via preparative
thin-layer chromatography (SiO2, petroleum ether:ethyl acetate = 2:3) to give the final products.
Dimethyl (E)-(1,2-Diphenylvinyl)phosphonate (3a). Colorless oil. yield 88% (51 mg). Rf = 0.30
(petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 24.4 Hz, 1H), 7.35-7.37 (m,
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3H), 7.24-7.26 (m, 2H), 7.13-7.20 (m, 3H), 7.05 (d, J = 7.2 Hz, 2H), 3.74 (d, J = 10.8 Hz, 6H); C
NMR (100 MHz, CDCl3) δ 144.4 (d, J = 11.1 Hz), 135.3 (d, J = 7.6 Hz), 134.5 (d, J = 22.6 Hz), 130.3
(d, J = 1.0 Hz), 129.8 (d, J = 178.6 Hz), 129.1, 129.1 (d, J = 5.4 Hz), 128.9 (d, J = 1.4 Hz), 128.2, 127.9
(d, J = 2.4 Hz), 52.7 (d, J = 5.8 Hz); IR (film) 1738, 1249, 1053, 1026, 832, 772, 719, 696 cm-1; EI-MS
(m/z, relative intensity): 288 (35), 192 (10), 178 (100), 152 (7); HRMS (ESI) calcd for C16H17KO3P
[(M+K)+] 327.0547, found: 327.0545.
Dimethyl (E)-(1-Phenyl-2-(p-tolyl)vinyl)phosphonate (3b). Colorless oil. yield 80% (48 mg) for
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benzyl bromide and 52% (31 mg) for benzyl chloride. Rf = 0.30 (petroleum ether:EtOAc = 2:3); H
NMR (400 MHz, CDCl3) δ 7.62 (d, J = 24.8 Hz, 1H), 7.35-7.37 (m, 3H), 7.24-7.27 (m, 2H), 6.95 (m,
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4H), 3.74 (d, J = 10.8 Hz, 6H), 2.26 (s, 3H); C NMR (100 MHz, CDCl3) δ 144.6 (d, J = 11.1 Hz),
139.5, 135.6 (d, J = 7.8 Hz), 131.7 (d, J = 22.8 Hz), 130.4, 129.1 (d, J = 5.4 Hz), 129.0, 128.5 (d, J =
179.5 Hz), 127.9 (d, J = 2.2 Hz), 52.7 (d, J = 5.7 Hz), 21.3 (one peak is missing because of overlap); IR
(film) 1248, 1056, 1029, 910,827, 732, 699 cm-1; EI-MS (m/z, relative intensity): 302 (40), 207 (12),
192 (100), 178 (11), 165 (8), 115 (6); HRMS (ESI) calcd for C17H20O3P [(M+H)+] 303.1145, found:
303.1141.
Dimethyl (E)-(2-([1,1'-Biphenyl]-4-yl)-1-phenylvinyl)phosphonate (3c). Colorless oil. yield 76% (55
mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.68 (d, J = 24.4 Hz, 1H),
7.51-7.53 (m, 2H), 7.38-7.41 (m, 7H), 7.26-7.34 (m, 3H), 7.12 (d, J = 8.4 Hz, 2H), 3.76 (d, J = 11.2 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ 144.0 (d, J = 11.2 Hz), 141.7, 140.0, 135.5 (d, J = 7.4 Hz), 133.4 (d,
J = 22.9 Hz), 130.9, 129.6 (d, J = 178.9 Hz), 129.1, 129.0 (br), 128.8, 128.0 (d, J = 2.5 Hz), 127.6,
126.9, 126.8, 52.7 (d, J = 5.8 Hz); IR (film) 1249, 1055, 1028, 837, 765, 733, 698 cm-1; EI-MS (m/z,
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relative intensity): 364 (37), 254 (100), 239 (6), 207 (11); HRMS (ESI) calcd for C22H22O3P [(M+H)+]
365.1301, found: 365.1300.
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Dimethyl (E)-(2-(4-Chlorophenyl)-1-phenylvinyl)phosphonate (3d). Colorless oil. yield 65% (42 mg).
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Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.59 (d, J = 24.4 Hz, 1H),
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7.36-7.38 (m, 3H), 7.22-7.24 (m, 2H), 7.11-7.13 (m, 2H), 6.96-6.98 (m, 2H), 3.74 (d, J = 10.8 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 143.0 (d, J = 11.2 Hz), 135.0, 134.9, 132.9 (d, J = 22.8 Hz), 131.5,
130.5 (d, J =178.9 Hz), 129.0 (d, J = 1.7 Hz), 128.9 (d, J = 5.3 Hz), 128.4, 128.1 (d, J = 2.3 Hz), 52.8 (d,
J = 5.8 Hz); IR (film) 1490, 1249, 1057, 1030, 911,832, 730, 700 cm-1; EI-MS (m/z, relative intensity):
322 (37), 227 (5), 212 (100), 176 (22), 151 (9); HRMS (ESI) calcd for C16H17ClO3P [(M+H)+] 323.0598,
found: 323.0597.
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Dimethyl (E)-(2-(4-Cyanophenyl)-1-phenylvinyl)phosphonate (3e). Colorless oil. yield 81% (51 mg).
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Rf = 0.25 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 24.4 Hz, 1H),
7.43-7.45 (m, 2H), 7.37-7.39 (m, 3H), 7.19-7.23 (m, 2H), 7.13 (d, J = 8.4 Hz, 2H), 3.76 (d, J = 11.2 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ 141.8 (d, J = 11.2 Hz), 138.9 (d, J = 22.7 Hz), 134.3 (d, J = 7.2 Hz),
134.0 (d, J = 177.8 Hz), 131.8, 130.5, 129.1 (d, J = 1.4 Hz), 128.7 (d, J = 5.4 Hz), 128.4 (d, J = 2.2 Hz),
118.3, 112.1, 52.9 (d, J = 5.9 Hz); IR (film) 2229, 1250, 1055, 1027, 913, 836, 731, 700 cm-1; EI-MS
(m/z, relative intensity): 313 (60), 280 (11), 217 (17), 203 (100), 176 (15), 110 (21); HRMS (ESI) calcd
for C17H17NO3P [(M+H)+] 314.0941, found: 314.0937.
Dimethyl (E)-(2-(4-Nitrophenyl)-1-phenylvinyl)phosphonate (3f). Colorless oil. yield 68% (45 mg) for
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benzyl bromide and 70% (47 mg) for benzyl chloride. Rf = 0.25 (petroleum ether: EtOAc = 2:3); H
NMR (400 MHz, CDCl3) δ 8.00-8.02 (m, 2H), 7.68 (d, J = 24.0 Hz, 1H), 7.38-7.39 (m, 3H), 7.18-7.24
(m, 4H), 3.77 (d, J = 11.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 147.3, 141.3 (d, J = 11.3 Hz), 140.9
(d, J = 22.7 Hz), 134.7 (d, J = 177.6 Hz), 134.3 (d, J = 7.2 Hz), 130.8, 129.2 (d, J = 1.5 Hz), 128.7 (d, J
= 5.2 Hz), 128.6 (d, J = 2.2 Hz), 123.4, 53.0 (d, J = 5.9 Hz); IR (film) 1521, 1346, 1252, 1056, 1028,
827, 733, 701 cm-1; EI-MS (m/z, relative intensity): 333 (100), 316 (43), 223 (60), 207 (35), 176 (63),
110 (50); HRMS (ESI) calcd for C16H17NO5P [(M+H)+] 334.0839, found: 334.0838.
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Dimethyl (E)-(2-(3-Methoxyphenyl)-1-phenylvinyl)phosphonate (3g). Colorless oil. yield 72% (46 mg).
Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 24.4 Hz, 1H), 7.33-
7.40 (m, 3H), 7.25-7.28 (m, 2H), 7.10 (t, J = 8.0 Hz, 1H), 6.72-6.77 (m, 2H), 6.52 (m, 1H), 3.65 (d, J =
11.2 Hz, 6H), 3.46 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 159.0, 144.3 (d, J = 11.1 Hz), 135.6 (d, J =
22.8 Hz), 135.4, 129.8 (d, J = 178.4 Hz), 129.2, 129.1 (d, J = 5.2 Hz), 128.9 (d, J = 1.5 Hz), 127.9 (d, J
= 2.2 Hz), 123.4, 116.1, 114.1, 54.7, 52.7 (d, J = 5.8 Hz); IR (film) 1246, 1051, 1027, 827, 787, 730,
699 cm-1; EI-MS (m/z, relative intensity): 318 (44), 222 (7), 208 (100), 178 (14), 165 (25); HRMS (ESI)
calcd for C17H20O4P [(M+H)+] 319.1094, found: 319.1092.
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Dimethyl (E)-(2-(3-Chlorophenyl)-1-phenylvinyl)phosphonate (3h). Colorless oil. yield 73% (47 mg).
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Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 24.4 Hz, 1H),
7.37-7.38 (m, 3H), 7.22-7.25 (m, 2H), 7.16-7.18 (m, 1H), 7.07 (t, J = 8.0 Hz, 1H), 7.01 (m, 1H), 6.92 (d,
J = 8.0 Hz, 1H), 3.75 (d, J = 10.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 142.6 (d, J = 11.4 Hz), 136.2
(d, J = 22.9 Hz), 134.7 (d, J = 7.5 Hz), 134.0, 131.6 (d, J = 178.4 Hz), 130.1, 129.3, 129.0 (d, J = 1.7
Hz), 129.0, 128.8 (d, J = 5.2 Hz), 128.3, 128.2 (d, J = 2.2 Hz), 52.8 (d, J = 5.8 Hz); IR (film) 1247, 1057,
1030, 909, 830, 730, 700, 652 cm-1; EI-MS (m/z, relative intensity): 322 (50), 226 (11), 212 (100), 196
(10), 176 (32), 151 (11); HRMS (ESI) calcd for C16H17ClO3P [(M+H)+] 323.0598, found: 323.0597.
Dimethyl (E)-(2-(3-Cyanophenyl)-1-phenylvinyl)phosphonate (3i). Colorless oil. yield 80% (50 mg).
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Rf = 0.25 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 24.4 Hz, 1H),
7.46-7.49 (m, 1H), 7.38-7.39 (m, 3H), 7.27-7.29 (m, 3H), 7.21-7.23 (m, 2H), 3.76 (d, J = 11.2 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 141.3 (d, J = 11.4 Hz), 135.7 (d, J = 22.8 Hz), 134.2, 134.1 (br), 133.3,
133.2 (d, J = 178.3 Hz), 132.0, 129.1 (d, J = 1.3 Hz), 129.0, 128.6 (d, J = 5.2 Hz), 128.5 (d, J = 2.5 Hz),
118.0, 112.4, 52.8 (d, J = 5.9 Hz); IR (film) 2232, 1249, 1054, 1026, 829, 729, 700, 687 cm-1; EI-MS
(m/z, relative intensity): 312 (73), 280 (15), 217 (20), 203 (100), 176 (18), 110 (30); HRMS (ESI) calcd
for C17H17NO3P [(M+H)+] 314.0941, found: 314.0938.
Dimethyl (E)-(1-Phenyl-2-(o-tolyl)vinyl)phosphonate (3j). Colorless oil. yield 65% (39 mg). Rf = 0.30
(petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 24.4 Hz, 1H), 7.24-7.27 (m,
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3H), 7.18-7.20 (m, 2H), 7.08-7.14 (m, 2H), 6.82-6.86 (m, 1H), 6.76 (d, J = 8.0 Hz, 1H), 3.76 (d, J =
11.2 Hz, 6H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 143.7 (d, J = 10.7 Hz), 137.4, 135.1 (d, J =
9.2 Hz), 134.0 (d, J = 21.2 Hz), 130.8 (d, J = 177.9 Hz), 130.0, 129.5 (d, J = 2.3 Hz), 129.4 (d, J = 5.6
Hz), 125.3, 128.6, 128.5, 127.7 (d, J = 2.0 Hz), 52.8 (d, J = 5.8 Hz), 20.0; IR (film) 1248, 1057, 1030,
910, 731, 698 cm-1; EI-MS (m/z, relative intensity): 302 (13), 207 (23), 192 (100), 178 (15), 165 (13),
115 (12); HRMS (ESI) calcd for C17H20O3P [(M+H)+] 303.1145, found: 303.1142.
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Dimethyl (E)-(2-(Naphthalen-2-yl)-1-phenylvinyl)phosphonate (3k). Colorless oil. yield 92% (62 mg).
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Rf = 0.35 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.82 (d, J = 24.4 Hz, 1H),
7.71-7.72 (m, 1H), 7.63-7.65 (m, 2H), 7.53 (d, J = 8.4 Hz, 1H), 7.40-7.46 (m, 2H), 7.36-7.39 (m, 3H),
7.28-7.31 (m, 2H), 7.01 (dd, J = 8.4, 1.6 Hz, 1H), 3.77 (d, J = 11.2 Hz, 6H); 13C NMR (100 MHz,
CDCl3) δ 144.4 (d, J = 11.1 Hz), 135.4 (d, J = 7.6 Hz), 133.2, 132.8, 132.1 (d, J = 22.7 Hz), 131.3,
129.8 (d, J = 178.8 Hz), 129.2 (d, J = 5.2 Hz), 128.9 (d, J = 1.6 Hz), 128.4, 128.0 (d, J = 2.2 Hz), 127.5,
127.4, 127.0, 126.6 (d, J = 1.0 Hz), 126.2, 52.7 (d, J = 5.8 Hz); IR (film) 1248, 1056, 1028, 910, 827,
789, 731, 699 cm-1; EI-MS (m/z, relative intensity): 338 (34), 228 (100), 207 (15); HRMS (ESI) calcd
for C20H20O3P [(M+H)+] 339.1145, found: 339.1143.
Dimethyl (2-(Naphthalen-1-yl)-1-phenylvinyl)phosphonate (3l). Colorless oil. yield 65% (44 mg), E/Z
= 5:1. E/Z isomers are hard to separate. NMR data of the mixture were given. Rf = 0.30 (petroleum
ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 8.32 (d, J = 24.0 Hz, 1H), 8.13 (d, J = 8.4 Hz, 1H),
7.81-7.87 (m, 1.6H), 7.64-7.71 (m, 2.2H), 7.48-7.56 (m, 2.6H), 7.34-7.38 (m, 0.5H), 7.11-7.19 (m,
6.2H), 7.00 (d, J = 7.2 Hz, 1H), 3.81 (d, J = 10.8 Hz, 6H), 3.57 (d, J = 10.8 Hz, 0.6H), 3.42 (d, J = 10.4
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Hz, 0.6H); C NMR (100 MHz, CDCl3) δ 148.2 (d, J = 5.2 Hz), 143.1 (d, J = 10.9 Hz), 134.9 (d, J =
9.0 Hz), 133.3, 133.2, 132.0, 131.7, 131.4, 129.5, 129.3 (d, J = 5.5 Hz), 129.2, 128.8, 128.6, 128.5,
128.4, 128.2 (d, J = 5.1 Hz), 128.1 (d, J = 2.9 Hz), 127.8 (d, J = 2.6 Hz), 127.6 (d, J = 1.9 Hz), 126.9 (d,
J = 3.4 Hz), 126.7, 126.5, 126.0, 125.7, 124.9, 124.2, 124.0, 122.1, 121.4, 111.3 (d, J = 8.3 Hz), 54.0 (d,
J = 7.0 Hz), 53.4 (d, J = 7.2 Hz), 52.8 (d, J = 5.8 Hz); IR (film) 1737, 1245, 1054, 1027, 829, 781, 733,
699 cm-1; EI-MS (m/z, relative intensity): 338 (20), 228 (100), 202 (5); HRMS (ESI) calcd for
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C20H20O3P [(M+H)+] 339.1145, found: 339.1144.
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Dimethyl (E)-(2-Phenyl-1-(p-tolyl)vinyl)phosphonate (4b). Colorless oil. yield 76% (46 mg). Rf = 0.30
(petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 24.8 Hz, 1H), 7.15-7.20 (m,
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7H), 7.08 (d, J = 7.2 Hz, 2H), 3.73 (d, J = 10.8 Hz, 6H), 2.37 (s, 3H); C NMR (100 MHz, CDCl3)
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δ144.2 (d, J = 11.4 Hz), 137.6 (d, J = 2.5 Hz), 134.5 (d, J = 22.6 Hz), 132.1 (d, J = 7.7 Hz), 130.3, 129.6
(d, J = 1.4 Hz), 129.6 (d, J = 178.3 Hz), 129.0, 128.8 (d, J = 5.3 Hz), 128.1, 52.6 (d, J = 5.7 Hz), 21.2;
IR (film) 1247, 1056, 1028, 837, 760, 729 cm-1; EI-MS (m/z, relative intensity): 302 (45), 269 (8), 207
(19), 192 (100), 178 (15), 165 (13); HRMS (ESI) calcd for C17H20O3P [(M+H)+] 303.1145, found:
303.1141.
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Dimethyl (E)-(1-([1,1'-Biphenyl]-4-yl)-2-phenylvinyl)phosphonate (4c). Colorless oil. yield 70% (51
mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.60-7.72 (m, 5H), 7.43-
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7.46 (m, 2H), 7.32-7.35 (m, 3H), 7.11-7.21 (m, 5H), 3.77 (d, J = 11.2 Hz, 6H); C NMR (100 MHz,
CDCl3) δ 144.5 (d, J = 11.0 Hz), 140.5 (d, J = 2.6 Hz), 140.3, 134.4 (d, J = 22.4 Hz), 134.2 (d, J = 7.6
Hz), 130.3, 129.5 (d, J = 5.5 Hz), 129.3 (d, J = 178.8 Hz), 129.1, 128.7, 128.2, 127.5 (d, J = 1.7 Hz),
127.4, 126.9, 52.7 (d, J = 5.8 Hz); IR (film) 1249, 1054, 1026, 821, 751, 732, 696 cm-1; EI-MS (m/z,
relative intensity): 364 (48), 331 (6), 254 (100), 239 (8), 207 (23); HRMS (ESI) calcd for C22H22O3P
[(M+H)+] 365.1301, found: 365.1301.
Dimethyl (E)-(1-(4-Methoxyphenyl)-2-phenylvinyl)phosphonate (4d). Colorless oil. yield 79% (50 mg).
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Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 24.4 Hz, 1H),
7.14-7.20 (m, 5H), 7.08-7.10 (m, 2H), 6.89-6.91 (m, 2H), 3.82 (s, 3H), 3.74 (d, J = 11.2 Hz, 6H); 13C
NMR (100 MHz, CDCl3) δ 159.2 (d, J = 2.2 Hz), 144.2 (d, J = 11.8 Hz), 134.6 (d, J = 22.6 Hz), 130.2,
130.1 (d, J = 5.4 Hz), 129.2 (d, J = 178.8 Hz), 129.0, 128.1, 127.1 (d, J = 7.9 Hz) 114.4 (d, J = 1.3 Hz),
55.1, 52.6 (d, J = 5.8 Hz); IR (film) 1510, 1247, 1055, 1028, 828, 760 cm-1; EI-MS (m/z, relative
intensity): 318 (58), 208 (100), 193 (17), 165 (30); HRMS (ESI) calcd for C17H20O4P [(M+H)+]
319.1094, found: 319.1092.
Dimethyl (E)-(1-(4-Fluorophenyl)-2-phenylvinyl)phosphonate (4e). Colorless oil. yield 62% (38 mg).
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1
Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 24.4 Hz, 1H),
7.15-7.25 (m, 5H), 7.04-7.08 (m, 4H), 3.75 (d, J = 10.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 162.4
(dd, JC-F = 245.9 Hz, J C-P = 2.5 Hz), 144.8 (d, JC-P = 11.2 Hz), 134.2 (d, JC-P = 22.4 Hz), 131.1 (dd, JC-F
= 3.6 Hz, JC-P = 8.0 Hz), 130.9 (dd, JC-F = 8.0 Hz, JC-P = 5.3 Hz), 130.2, 129.2, 128.7 (d, JC-P = 180.4
Hz), 128.2, 116.0 (dd, JC-F = 21.6 Hz, JC-P = 1.5 Hz), 52.7 (d, JC-P = 5.9 Hz); IR (film) 1508, 1246, 1056,
1029, 846, 760, 730 cm-1; EI-MS (m/z, relative intensity): 306 (34), 210 (6), 196 (100), 170 (5); HRMS
(ESI) calcd for C16H17FO3P [(M+H)+] 307.0894, found: 307.0892.
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Dimethyl (E)-(1-(4-Chlorophenyl)-2-phenylvinyl)phosphonate (4f). Colorless oil. yield 57% (38 mg).
Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 24.4 Hz, 1H), 7.34
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(d, J = 8.0 Hz, 2H), 7.16-7.21 (m, 5H), 7.06 (d, J = 8.0 Hz, 2H), 3.74 (d, J = 11.2 Hz, 6H); C NMR
(100 MHz, CDCl3) δ 144.8 (d, J = 10.9 Hz), 134.1 (d, J = 22.4 Hz), 133.9 (d, J = 2.9 Hz), 133.8 (d, J =
8.0 Hz), 130.5 (d, J = 5.2 Hz), 130.2, 129.3, 129.2 (d, J = 1.1 Hz), 128.5 (d, J = 180.4 Hz), 128.3, 52.7
(d, J = 5.8 Hz); IR (film) 1490, 1251, 1092, 1054, 1026, 761, 744, 694 cm-1; EI-MS (m/z, relative
intensity): 322 (38), 226 (6), 212 (100), 176 (21), 151 (8); HRMS (ESI) calcd for C16H17ClO3P [(M+H)+]
323.0598, found: 323.0597.
Dimethyl (E)-(1-(4-Bromophenyl)-2-phenylvinyl)phosphonate (4g). Colorless oil. yield 50% (37 mg).
Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.65 (d, J = 24.4 Hz, 1H), 7.49
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(d, J = 8.4 Hz, 2H), 7.12-7.22 (m, 5H), 7.06-7.08 (m, 2H), 3.75 (d, J = 10.8 Hz, 6H); C NMR (100
MHz, CDCl3) δ 144.8 (d, J = 10.8 Hz), 134.3 (d, J = 8.0 Hz), 134.1 (d, J = 22.2 Hz), 132.2 (d, J = 1.4
Hz), 130.9 (d, J = 5.3 Hz), 130.3, 129.3, 128.6 (d, J = 180.7 Hz), 128.4, 122.2 (d, J = 3.0 Hz), 52.8 (d, J
= 5.8 Hz); IR (film) 1251, 1058, 1029, 839, 735 cm-1; EI-MS (m/z, relative intensity): 368 (42), 256
(100), 207 (26), 192 (15), 176 (42), 151 (14); HRMS (ESI) calcd for C16H17BrO3P [(M+H)+] 367.0093,
found: 367.0095.
Dimethyl (E)-(1-(4-(Hydroxymethyl)phenyl)-2-phenylvinyl)phosphonate (4h). Colorless oil. yield 44%
(26 mg). Rf = 0.20 (petroleum ether:EtOAc = 1:2); 1H NMR (400 MHz, CDCl3) δ 7.64 (d, J = 24.8 Hz,
1H), 7.37 (d, J = 8.0 Hz, 2H), 7.24-7.26 (m, 2H), 7.13-7.21 (m, 3H), 7.06-7.08 (m, 2H), 4.74 (s, 2H),
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3.74 (d, J = 11.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 144.6 (d, J = 11.0 Hz), 140.7 (d, J = 2.7 Hz),
134.5 (d, J = 7.8 Hz), 134.4 (d, J = 22.7 Hz), 130.3, 129.4 (d, J = 179.2 Hz), 129.2 (d, J = 5.3 Hz), 129.2,
128.2, 127.4 (d, J = 1.5 Hz), 64.9, 52.7 (d, J = 5.8 Hz); IR (film) 1236, 1056, 1028, 831, 762, 673 cm-1;
HRMS (ESI) calcd for C17H20O4P [(M+H)+] 319.1094, found: 319.1092.
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Dimethyl (E)-(1-(4-Nitrophenyl)-2-phenylvinyl)phosphonate (4i). Colorless oil. yield 50% (33 mg). Rf
= 0.25 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 8.22 (d, J = 8.4 Hz, 2H), 7.74 (d,
J = 24.4 Hz, 1H), 7.44-7.46 (m, 2H), 7.20-7.27 (m, 3H), 7.30 (d, J = 7.6 Hz, 2H), 3.78 (d, J = 10.8 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ 147.4 (d, J = 1.9 Hz), 145.8 (d, J = 9.6 Hz), 142.8 (d, J = 7.9 Hz),
133.6 (d, J = 21.5 Hz), 130.4 (d, J = 5.1 Hz), 130.2, 129.8, 128.5, 128.1 (d, J = 181.6 Hz), 124.1, 52.9 (d,
J = 5.8 Hz); IR (film) 1521, 1348, 1251, 1055, 1029, 910, 827, 789, 731, 699 cm-1; EI-MS (m/z, relative
intensity): 333 (100), 223 (65), 207 (51), 176 (48), 165 (32), 110 (55); HRMS (ESI) calcd for
C16H17NO5P [(M+H)+] 334.0839, found: 334.0838.
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Dimethyl (E)-(1-(3-Methoxyphenyl)-2-phenylvinyl)phosphonate (4j). Colorless oil. yield 55% (35 mg).
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Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 24.8 Hz, 1H),
7.28-7.30 (m, 1H), 7.17-7.21 (m, 3H), 7.08-7.10 (m, 2H), 6.87-6.90 (m, 1H), 6.81-6.84 (m, 2H), 3.76 (s,
3H), 3.75 (d, J = 11.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 159.8 (d, J = 1.3 Hz), 144.4 (d, J = 11.1
Hz), 136.6 (d, J = 7.8 Hz), 134.4 (d, J = 22.5 Hz), 130.3, 129.9 (d, J = 1.5 Hz), 129.4 (d, J = 176.5 Hz),
129.1, 128.2, 121.3 (d, J = 5.6 Hz), 114.5 (d, J = 5.1 Hz), 113.4 (d, J = 2.2 Hz), 55.1, 52.7 (d, J = 5.8
Hz); IR (film) 1240, 1053, 1029, 909, 826, 758, 733 cm-1; EI-MS (m/z, relative intensity): 318 (55), 285
(8), 208 (100), 178 (16), 165 (32), 139 (5); HRMS (ESI) calcd for C17H20O4P [(M+H)+] 319.1094,
found: 319.1092.
Dimethyl (E)-(2-Phenyl-1-(1-tosyl-1H-indol-5-yl)vinyl)phosphonate (4k). Colorless oil. yield 70% (67
mg). Rf = 0.30 (petroleum ether:EtOAc = 1:2); 1H NMR (400 MHz, CDCl3) δ 7.95-7.98 (dd, J = 8.4, 0.4
Hz, 1H), 7.77-7.79 (m, 2H), 7.64 (d, J = 24.4 Hz, 1H), 7.57 (d, J = 3.6 Hz, 1H), 7.45-7.46 (m, 1H), 7.25
(d, J = 8.0 Hz, 2H), 7.15-7.19 (m, 2H), 7.04-7.08 (m, 2H), 6.95 (d, J = 7.6 Hz, 1H), 6.54 (dd, J = 3.6,
0.4 Hz, 1H), 3.65 (d, J = 10.8 Hz, 6H), 2.30 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 145.1, 144.6 (d, J =
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11.5 Hz), 135.1, 134.3 (d, J = 22.5 Hz), 134.3 (d, J = 2.0 Hz), 131.2, 130.3, 130.1 (d, J = 8.0 Hz), 129.8,
129.4 (d, J = 179.4 Hz), 129.1, 128.1, 126.8, 126.7, 125.7 (d, J = 5.4 Hz), 121.8 (d, J = 5.4 Hz), 114.1,
109.1, 52.7 (d, J = 5.8 Hz), 21.5; IR (film) 1372, 1246, 1173, 1139, 1126, 1054, 1028, 911, 833, 761,
733, 674 cm-1; HRMS (ESI) calcd for C25H25NO5PS [(M+H)+] 482.1186, found: 482.1181.
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Dimethyl (E)-(1-Phenylbuta-1,3-dien-1-yl)phosphonate (6a). Colorless oil. yield 50% (24 mg) for
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allyl bromide and yield 57% (27 mg) for allyl chloride. Rf = 0.30 (petroleum ether:EtOAc = 2:3); H
NMR (400 MHz, CDCl3) δ 7.23-7.40 (m, 6H), 6.31-6.41 (m, 1H), 5.62-5.67 (m, 1H), 5.41-5.44 (m, 1H),
3.72 (d, J = 10.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 145.0 (d, J = 10.2 Hz), 134.5 (d, J = 8.7 Hz),
132.4 (d, J = 21.1 Hz), 130.1 (d, J = 181.0 Hz), 129.3 (d, J = 5.5 Hz), 128.4, 127.9 (d, J = 1.9 Hz), 125.7,
52.6 (d, J = 5.8 Hz); IR (film) 1252, 1057, 1030, 910, 830, 733, 702 cm-1; EI-MS (m/z, relative
intensity): 237 (100), 205 (45), 128 (81), 109 (10); HRMS (ESI) calcd for C12H16O3P [(M+H)+]
239.0832, found: 239.0829.
Dimethyl (E)-(4-Methyl-1-phenylpenta-1,3-dien-1-yl)phosphonate (6b). Colorless oil. yield 60% (32
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mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.54 (dd, J = 22.4, 11.6
Hz), 7.39-7.31 (m, 3H), 7.25-7.23 (m, 2H), 5.84-5.87 (m, 1H), 3.70 (d, J = 11.2 Hz, 6H), 1.93 (s, 3H),
1.77 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 146.3, 141.2 (d, J = 11.0 Hz), 135.1 (d, J = 9.2 Hz), 129.5
(d, J = 5.5 Hz), 128.2, 127.4 (d, J = 1.8 Hz), 125.6 (d, J = 183.5 Hz), 121.1 (d, J = 20.8 Hz), 52.4 (d, J =
5.6 Hz), 26.6, 19.0; IR (film) 1248, 1056, 1027, 912, 826, 784, 731, 699 cm-1; EI-MS (m/z, relative
intensity): 266 (38), 251 (19), 219 (9), 156 (100), 141 (30), 128 (11), 115 (22); HRMS (ESI) calcd for
C14H20O3P [(M+H)+] 267.1145, found: 267.1142.
Dimethyl ((1E,3E)-1,4-Diphenylbuta-1,3-dien-1-yl)phosphonate (6c). Colorless oil. yield 48% (30
mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.49-7.25 (m, 11H), 6.96
(d, J = 15.6 Hz, 1H), 6.81-6.74 (m, 1H), 3.73 (d, J = 11.2 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ144.8
(d, J = 10.5 Hz), 140.5, 136.1 (d, J = 1.9 Hz), 134.9 (d, J = 8.8 Hz), 129.5 (d, J = 5.5 Hz), 128.9 (d, J =
182.0 Hz), 128.9, 128.6, 128.4, 127.9 (d, J = 1.9 Hz), 127.2, 123.8 (d, J = 21.3 Hz), 52.5 (d, J = 5.5 Hz);
IR (film) 1246, 1055, 1028, 967, 912, 827, 779, 764, 733, 700 cm-1; EI-MS (m/z, relative intensity): 314
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(35), 281 (6), 237 (40), 204 (100), 189 (6); HRMS (ESI) calcd for C18H20O3P [(M+H)+] 315.1145,
found: 315.1142.
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Dimethyl (E)-(1-([1,1'-Biphenyl]-4-yl)-4-methylpenta-1,3-dien-1-yl)phosphonate (6d). Colorless oil.
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yield 57% (39 mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.53-7.63
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(m, 5H), 7.43-7.46 (m, 2H), 7.32-7.37 (m, 3H), 5.94 (d, J = 12.0 Hz, 1H), 3.73 (d, J = 10.8 Hz, 6H),
1.95 (s, 3H), 1.80 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 146.5, 141.3 (d, J = 11.0 Hz), 140.5, 140.2 (d,
J = 2.1 Hz), 134.1 (d, J = 9.3 Hz), 129.9 (d, J = 5.6 Hz), 128.7, 127.3, 126.9, 125.2 (d, J = 183.3 Hz),
121.2 (d, J = 20.6 Hz), 52.4 (d, J = 5.5 Hz), 26.7, 19.0 (One peak is missing because of overlap.); IR
(film) 1633, 1490, 1248, 1092, 1057, 1028, 910, 826, 732 cm-1; EI-MS (m/z, relative intensity): 342 (43),
327 (50), 232 (100), 217 (25), 202 (18), 191 (15); HRMS (ESI) calcd for C20H24O3P [(M+H)+] 343.1458,
found: 343.1457.
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Dimethyl (E)-(1-(4-Chlorophenyl)-4-methylpenta-1,3-dien-1-yl)phosphonate (6e). Colorless oil. yield
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67% (40 mg). Rf = 0.30 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.53 (dd, J =
22.4, 11.6 Hz, 1H), 7.33-7.35 (m, 2H), 7.17-7.20 (m, 2H), 5.80-5.83 (m, 1H), 3.70 (d, J = 10.8 Hz, 6H),
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1.94 (s, 3H), 1.79 (s, 3H); C NMR (100 MHz, CDCl3) δ 147.1, 141.5 (d, J = 10.7 Hz), 133.6 (d, J =
9.5 Hz), 133.4 (d, J = 2.4 Hz), 130.9 (d, J = 5.5 Hz), 128.5, 124.4 (d, J = 185.0 Hz), 120.9 (d, J = 20.8
Hz), 52.4 (d, J = 5.6 Hz), 26.7, 19.0; IR (film) 1633, 1487, 1248, 1056, 1027, 823, 732 cm-1; EI-MS
(m/z, relative intensity): 300 (35), 285 (10), 190 (100), 175 (11), 155 (29); HRMS (ESI) calcd for
C14H19ClO3P [(M+H)+] 301.0755, found: 301.0752.
General procedure for the preparation of α-Ketoalkylphosphonate N-tosylhydrazones
α-Ketoalkylphosphonate N-tosylhydrazones 7a-c are prepared based on the previously reported
procedure.19 A solution of pure TsNNH2 (20 mmol) in 20 mL of THF in a 50 mL flask was chilled to 0
oC and 1.8 mL of concentrated HCl was added. The resulting solution was stirred in an ice bath while 20
mmol of appropriate dimethyl α-ketoalkylphosphonate was added over a 5-min period. The mixture was
stirred at room temperature for 6 h. The resulting heavy white precipitate was filtered and dried to give
the final product.
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Dimethyl (1-(2-Tosylhydrazono)ethyl)phosphonate (7a).19 White solid. yield 80% (5.12 g). Rf = 0.30
(petroleum ether:EtOAc =1:3); E/Z isomers are hard to separate. NMR data of the mixture were given.
1H NMR (400 MHz, CDCl3) δ 8.72 (s, 1H), 7.82 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 3.72-3.75
(m, 6H), 2.43 (s, 3H), 2.02 (d, J = 9.6 Hz, 0.4H), 1.95 (d, J = 10.8 Hz, 2.6H); IR (film) 1234, 1171,
1058, 1045, 844, 783, 668 cm-1; HRMS (ESI) calcd for C12H20N2O5PS [(M+H)+] 335.0825, found:
335.0823.
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Dimethyl (1-(2-Tosylhydrazono)propyl)phosphonate (7b).White solid. yield 70% (4.68 g). m.p.: 199-
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201 oC. Rf = 0.30 (petroleum ether:EtOAc =1:3); H NMR (400 MHz, d6-DMSO) δ 11.46 (s, 1H), 7.73
(d, J = 8.4 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 3.53 (d, J = 10.8 Hz, 6H), 2.34-2.43 (m, 5H), 0.97 (t, J =
7.6 Hz, 3H). 13C NMR (100 MHz, d6-DMSO) δ 151.7 (d, J = 212 Hz), 143.8, 135.6, 129.6, 127.3, 53.2
(d, J = 6.5 Hz), 21.3 (d, J = 20.3 Hz), 21.0, 9.3; IR (film) 1234, 1171, 1058, 1045, 844, 783, 668 cm-1;
HRMS (ESI) calcd for C12H20N2O5PS [(M+H)+] 335.0825, found: 335.0823.
Dimethyl (2-Methyl-1-(2-tosylhydrazono)propyl)phosphonate (7c).19 White solid. yield 74% (5.15 g).
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Rf = 0.30 (petroleum ether:EtOAc =1:3); H NMR (400 MHz, d6-DMSO) δ 11.48 (s, 1H), 7.73 (d, J =
8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 3.50 (d, J = 11.2 Hz, 6H), 3.00-3.14 (m, 1H), 2.38 (s, 3H), 1.05 (d,
J = 6.8 Hz, 3H).
General Procedure for the Reaction of N-Tosylhydrazones and Aryl Bromides. Pd(PPh3)4 (12
mg, 5 mol%), K2CO3 (69 mg, 0.50 mmol), N-tosylhydrazone (0.20 mmol) and aryl bromide (0.30 mmol)
were suspended in 1,4-dioxane (1.5 mL) in a 10 mL Schlenk tube under a nitrogen atmosphere. The
resulting solution was stirred at 90 oC for 3 h. The mixture was filtered through a short path of silica gel,
eluting with ethyl acetate, and the filtrate was evaporated in vacuo to remove the volatile materials. The
crude residue was purified by column chromatography (silica gel, petroleum ether:ethyl acetate = 1:1) to
afford the final products.
Dimethyl (1-Phenylvinyl) phosphonate (9a).15 Colorless oil. yield 80% (34 mg). Rf = 0.35 (petroleum
ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.50-7.52 (m, 2H), 7.31-7.38 (m, 3H), 6.34 (dd, J =
22.0, 1.6 Hz, 1H), 6.19 (dd, J = 46.0, 1.2 Hz, 1H), 3.74 (d, J = 10.8 Hz, 6H); 13C NMR (100 MHz,
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CDCl3) δ 138.4 (d, J = 174.0 Hz), 136.2 (d, J = 11.7 Hz), 132.2 (d, J = 7.8 Hz), 128.3, 128.2, 127.4 (d, J
= 5.8 Hz), 52.5 (d, J = 5.8 Hz).
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Dimethyl (1-(p-Tolyl)vinyl)phosphonate (9b).16 Colorless oil. yield 75% (34 mg). Rf = 0.30 (petroleum
ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.40-7.42 (m, 2H), 7.16-7.18 (m, 2H), 6.31 (dd, J =
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22.0, 1.6 Hz, 1H), 6.18 (dd, J = 46.0, 1.6 Hz, 1H), 3.74 (d, J = 10.8 Hz, 6H), 2.36 (s, 3H); C NMR
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(100 MHz, CDCl3) δ 138.3, 138.2 (d, J = 174.5 Hz), 133.4 (d, J = 11.7 Hz), 131.7 (d, J = 8.1 Hz), 129.2,
127.2 (d, J = 5.8 Hz), 52.6 (d, J = 5.6 Hz), 21.1.
Dimethyl (1-(4-Methoxyphenyl)vinyl)phosphonate (9c). Colorless oil. yield 72% (35 mg). Rf = 0.30
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.46-7.48 (m, 2H), 6.88-6.90 (m, 2H),
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6.26 (dd, J = 22.0, 1.6 Hz, 1H), 6.14 (dd, J = 46.4, 1.6 Hz, 1H), 3.82, 3.75 (d, J = 11.2 Hz, 6H); C
NMR (100 MHz, CDCl3) δ 159.7, 137.6 (d, J = 173.5 Hz), 130.8 (d, J = 8.2 Hz), 128.6 (d, J = 12.8 Hz),
128.5 (d, J = 6.0 Hz), 113.9, 55.2, 52.6 (d, J = 5.7 Hz); IR (film) 1512, 1252, 1183, 1031, 839, 800, 732
cm-1; EI-MS (m/z, relative intensity): 242 (88), 227 (100), 195 (7), 183 (20), 167 (18); HRMS (ESI)
calcd for C11H16O4P [(M+H)+] 243.0781, found: 243.0780.
Dimethyl (1-([1,1'-Biphenyl]-4-yl)vinyl)phosphonate (9d). Colorless oil. yield 87% (51 mg). Rf = 0.30
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.59-7.61 (m, 6H), 7.43-7.46 (m, 2H),
7.31-7.36 (m, 1H), 6.37 (dd, J = 22.0, 1.2 Hz, 1H), 6.26 (dd, J = 46.0, 1.2 Hz, 1H), 3.78 (d, J = 11.2 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ 141.2, 140.3, 138.0 (d, J = 173.7 Hz), 135.2 (d, J = 11.8 Hz), 132.2
(d, J = 7.9 Hz), 128.8, 127.7 (d, J = 5.8 Hz), 127.5, 127.2, 127.0, 52.7 (d, J = 5.6 Hz); IR (film) 1238,
1028,, 858, 830, 774, 743 cm-1; EI-MS (m/z, relative intensity): 288 (97), 258 (10), 191 (30), 178 (100),
167 (10), 152 (19); HRMS (ESI) calcd for C16H18O3P [(M+H)+] 289.0988, found: 289.0988.
Dimethyl (1-(4-(Trimethylsilyl)phenyl)vinyl)phosphonate (9e). Colorless oil. yield 81% (46 mg). Rf =
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0.35 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.48-7.53 (m, 4H), 6.36 (dd, J =
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22.4, 1.6 Hz, 1H), 6.22 (dd, J = 46.0, 1.6 Hz, 1H), 3.75 (d, J = 11.2 Hz, 6H), 0.27 (s, 9H); C NMR
(100 MHz, CDCl3) δ 140.8, 138.5 (d, J = 173.6 Hz), 136.6 (d, J = 11.5 Hz), 133.5, 132.6 (d, J = 7.9 Hz),
126.5 (d, J = 5.7 Hz), 52.6 (d, J = 5.6 Hz), -1.3; IR (film) 1250, 1054, 1029, 910, 856, 835, 732 cm-1;
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EI-MS (m/z, relative intensity): 284 (15), 269 (100), 159 (9); HRMS (ESI) calcd for C13H22O3PSi
[(M+H)+] 285.1070, found: 285.1069.
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Methyl 4-(1-(Dimethoxyphosphoryl)vinyl)benzoate (9f). Colorless oil. yield 83% (45 mg). Rf = 0.25
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 8.02-8.04 (m, 2H), 7.57-7.60 (m, 2H),
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6.43 (dd, J = 22.0, 1.2 Hz, 1H), 6.19 (dd, J = 45.6, 1.2 Hz, 1H), 3.93 (s, 3H), 3.76 (d, J = 11.2 Hz, 6H);
13C NMR (100 MHz, CDCl3) δ 166.6, 140.9 (d, J = 11.7 Hz), 138.1 (d, J = 175.6 Hz), 133.6 (d, J = 7.4
Hz), 129.9, 129.7, 127.4 (d, J = 5.7 Hz), 52.8 (d, J = 5.8 Hz), 52.1; IR (film) 1724, 1283, 1237, 1116,
1028, 830, 732 cm-1; EI-MS (m/z, relative intensity): 270 (100), 239 (45), 210 (28), 102 (45), 93 (48);
HRMS (ESI) calcd for C12H16O5P [(M+H)+] 271.0730, found: 271.0730.
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Dimethyl (1-(4-Fluorophenyl)vinyl)phosphonate (9g). Colorless oil. yield 89% (47 mg). Rf = 0.30
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.48-7.52 (m, 2H), 7.03-7.07 (m, 2H),
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6.32 (dd, J = 22.0, 1.2 Hz, 1H), 6.16 (dd, J = 46.0, 1.2 Hz, 1H), 3.76 (d, J = 10.8 Hz, 6H); C NMR
(100 MHz, CDCl3) δ 162.8 (JC-F = 247.7 Hz), 137.6 (d, JC-P = 175.3 Hz), 132.4 (dd, JC-F = 3.2 Hz, JC-P
=
11.9 Hz), 132.1 (d, JC-P = 8.2 Hz), 129.2 (dd, JC-F = 8.1 Hz, JC-P = 5.8 Hz), 115.4 (JC-F = 21.4 Hz), 52.7
(d, JC-P = 5.8 Hz); IR (film) 1509, 1237, 1029, 844, 832, 812, 731 cm-1; EI-MS (m/z, relative intensity):
230 (96), 135 (60), 121 (100), 110 (30), 101 (80); HRMS (ESI) calcd for C10H13FO3P [(M+H)+]
231.0581, found: 231.0581.
Dimethyl (1-(Naphthalen-1-yl)vinyl)phosphonate (9h). Colorless oil. yield 86% (45 mg). Rf = 0.30
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.98-8.00 (m, 1H), 7.81-7.87 (m, 2H),
7.40-7.50 (m, 4H), 6.70 (dd, J = 22.8, 2.0 Hz, 1H), 6.06 (dd, J = 47.6, 2.0 Hz, 1H), 3.68 (d, J = 11.2 Hz,
6H); 13C NMR (100 MHz, CDCl3) δ 137.8 (d, J = 176.2 Hz), 135.4 (d, J = 8.0 Hz), 134.2 (d, J = 9.4 Hz),
133.7, 131.4 (d, J = 5.1 Hz), 128.3 (d, J = 2.5 Hz), 128.2, 126.3 (d, J = 4.8 Hz), 126.2, 125.9, 125.4,
124.9 (d, J = 2.2 Hz), 52.9 (d, J = 6.0 Hz); IR (film) 1253, 1236, 1055, 1030, 833, 813, 780, 734 cm-1;
EI-MS (m/z, relative intensity): 262 (12), 229 (5), 152 (100); HRMS (ESI) calcd for C14H16O3P [(M+H)+]
263.0832, found: 263.0832.
Dimethyl (1-(Anthracen-9-yl)vinyl)phosphonate (9i). Colorless oil. yield 83% (52 mg). Rf = 0.30
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(petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 8.43-8.44 (m, 1H), 8.08-8.11 (m, 2H),
7.97-7.99 (m, 2H), 7.44-7.50 (m, 2H), 6.94 (dd, J = 22.4, 2.0 Hz, 1H), 6.09 (dd, J = 48.0, 2.0 Hz, 1H),
3.57 (d, J = 10.8 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 137.8 (d, J = 178.2 Hz), 136.3 (d, J = 7.5 Hz),
131.2 (d, J = 2.4 Hz), 130.7 (d, J = 7.3 Hz), 129.8 (d, J = 4.8 Hz), 128.3 , 127.5 (d, J = 3.6 Hz), 126.3 (d,
J = 2.0 Hz), 125.6, 125.2, 52.9 (d, J = 6.5 Hz); IR (film) 1252, 1057, 1032, 831, 785, 741 cm-1; HRMS
(ESI) calcd for C18H18O3P [(M+H)+] 313.0988, found: 313.0987.
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Dimethyl (1-(Thiophen-2-yl)vinyl)phosphonate (9j). Colorless oil. yield 76% (33 mg). Rf = 0.30
(petroleum ether:EtOAc = 2:3); 1H NMR (400 MHz, CDCl3) δ 7.34 (dt, J = 4.0, 1.2 Hz, 1H), 7.26 (dt, J
= 5.2, 1.2 Hz, 1H), 7.01 (dd, J = 4.8, 3.6 Hz, 1H), 6.28 (d, J = 44.4 Hz, 1H), 6.20 (d, J = 21.2 Hz, 1H),
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3.78 (d, J = 11.2 Hz, 6H); C NMR (100 MHz, CDCl3) δ 138.6 (d, J = 16.8 Hz), 131.3 (d, J = 176.4
Hz), 129.7 (d, J = 7.1 Hz), 127.8, 127.4 (d, J = 3.3 Hz), 125.8, 52.8 (d, J = 5.4 Hz); IR (film) 1271, 1232,
1027, 854, 833, 732 cm-1; EI-MS (m/z, relative intensity): 218 (41), 188 (46), 123 (15), 109 (100), 65
(28); HRMS (ESI) calcd for C8H12O3PS [(M+H)+] 219.0239, found: 219.0239.
Dimethyl (E)-(1-Phenylprop-1-en-1-yl)phosphonate (9k).17 Colorless oil. yield 64% (29 mg). Rf =
1
0.35 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.29-7.39 (m, 3H), 7.19-7.22 (m,
2H), 6.34 (dq, J = 22.8, 2.8 Hz, 1H), 3.69 (d, J = 10.8 Hz, 6H), 1.74 (dd, J = 6.8, 3.6 Hz, 3H); 13C NMR
(100 MHz, CDCl3) δ 144.8 (d, J = 10.2 Hz), 134.5 (d, J = 10.1 Hz), 131.4 (d, J = 180.4 Hz), 129.1 (d, J
= 5.0 Hz), 128.3, 127.5 (d, J = 2.1 Hz), 52.5 (d, J = 5.9 Hz), 15.6 (d, J = 18.8 Hz).
Dimethyl (2-Methyl-1-phenylprop-1-en-1-yl)phosphonate (9l). Colorless oil. yield 50% (24 mg). Rf =
1
0.35 (petroleum ether:EtOAc = 2:3); H NMR (400 MHz, CDCl3) δ 7.25-7.35 (m, 3H), 7.11-7.13 (m,
2H), 3.60 (d, J = 10.8 Hz, 6H), 2.31 (d, J = 3.2 Hz, 3H), 1.65 (d, J = 2.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ 154.8 (d, J = 11.7 Hz), 138.6 (d, J = 10.5 Hz), 129.5 (d, J = 4.4 Hz), 128.2, 126.9 (d, J = 2.2
Hz), 126.0 (d, J = 181.4 Hz), 52.1 (d, J = 5.9 Hz), 24.2 (d, J = 18.3 Hz), 23.2 (d, J = 7.1 Hz); IR (film)
1235, 1057, 1031, 910, 823, 731, 703 cm-1; EI-MS (m/z, relative intensity): 239 (84), 225 (10), 149 (25),
129 (100), 115 (42); HRMS (ESI) calcd for C12H18O3P [(M+H)+] 241.0988, found:241.0987.
■ ASSOCIATED CONTENTS
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Supporting Information
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Copies of H and 13C spectra for all products are available free of charge via the Internet at
http://pubs.acs.org.
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■ AUTHOR INFORMATION
Corresponding Author
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*E-mail: wangjb@pku.edu.cn
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This project was supported by the National Basic Research Program of China (973 Program,
2012CB821600) and the National Natural Science Foundation of China (Grant 21472004 and
21332002).
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