Acetonitrile-dependent oxyphosphorylation: A mild one-pot synthesis of β-ketophosphonates from alkenyl acids or alkenes

Article abstract of DOI:10.1016/j.tet.2017.03.026

An efficient one-pot synthesis of β-ketophosphonates has been developed, via the reaction of α,β-alkenyl carboxylic acids or alkenes with H-phosphonates and air oxygen, catalyzed by CuSO₄·5H₂O in CH₃CN. CH₃CN plays a decisive role, probably by forming an active oxygen complex [(MeCN)_nCu^II-O-O·].

Full text of DOI:10.1016/j.tet.2017.03.026

Accepted Manuscript
Acetonitrile-dependent oxyphosphorylation: A mild one-pot synthesis of β-
ketophosphonates from alkenyl acids or alkenes
Xi Chen, Xiaolan Chen, Xu Li, Chen Qu, Lingbo Qu, Wenzhu Bi, Kai Sun, Yufen Zhao
PII:
S0040-4020(17)30263-6
10.1016/j.tet.2017.03.026
TET 28532
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 11 January 2017
Revised Date: 10 March 2017
Accepted Date: 10 March 2017
Please cite this article as: Chen X, Chen X, Li X, Qu C, Qu L, Bi W, Sun K, Zhao Y, Acetonitrile-
dependent oxyphosphorylation: A mild one-pot synthesis of β-ketophosphonates from alkenyl acids or
alkenes, Tetrahedron (2017), doi: 10.1016/j.tet.2017.03.026.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Leave this area blank for abstract info.
Acetonitrile-dependent oxyphosphorylation:
a mild one-pot synthesis of
β-ketophosphonates from alkenyl acids or
alkenes
Xi Chen a, Xiaolan Chen a, *, Xu Li b, Chen Qu c, Lingbo Qu d, Wenzhu Bi a, Kai Sun a, Yufen Zhao a, e
aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450052, China. E-mail: chenxl@zzu.edu.cn.
bInstitute of Chemistry Co. Ltd. Henan Academy of Sciences, Zhengzhou, 450002, China
cDepartment of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, United States
dLuoyang Institute of Science and Technology, Luoyang, 471023, China
eDepartment of Chemistry, Xiamen University, Xiamen, 361005, China

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Acetonitrile-dependent oxyphosphorylation: a mild one-pot synthesis of β-
ketophosphonates from alkenyl acids or alkenes
Xi Chen a, Xiaolan Chen a, *, Xu Li b, Chen Qu c, Lingbo Qu d, Wenzhu Bi a, Kai Sun a, Yufen Zhao a, e
aCollege of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450052, China. E-mail: chenxl@zzu.edu.cn.
bInstitute of Chemistry Co. Ltd. Henan Academy of Sciences, Zhengzhou, 450002, China
cDepartment of Chemical and Biomolecular Engineering, University of Notre Dame, Notre Dame, Indiana 46556, United States
dLuoyang Institute of Science and Technology, Luoyang, 471023, China
eDepartment of Chemistry, Xiamen University, Xiamen, 361005, China
ARTICLE INFO
ABSTRACT
Article history:
Received
An efficient one-pot synthesis of β-ketophosphonates has been developed, via the reaction of
α,β-alkenyl carboxylic acids or alkenes with H-phosphonates and air oxygen, catalyzed by
Received in revised form
Accepted
CuSO4
·
5H2O in CH3CN. CH3CN plays a decisive role, probably by forming an active oxygen
].
complex [(MeCN)nCuII-O-O
·
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Oxyphosphorylation
Acetonitrile-dependent
β-Ketophosphonates
Alkenyl acids
Alkenes
1. Introduction
developed methods suffer from inaccessible materials, and
moreover, for some reactions, expensive catalysts, or harsh basic
or acidic reaction conditions are required. Thus, more benign,
efficient and atom-economic synthetic strategies have been
pursued aggressively over the past few years.
Active-oxygen species generated on a copper complex has
long been a hot research not only in chemistry but also in
physiology and biology, since it has close relevance to oxidation
reactions in biological as well as synthetic and catalytic
processes.1 A great deal of efforts has thus made in recent years
to develop specific copper ligands, enabling stabilizing such
reactive active-oxygen complex in synthetic studies.2 Even
though it is well known that acetonitrile is an excellent ligand for
copper (II) ion, it is pity that oxidation reactions participated by
copper (II)-acetonitrile complex have been reported rarely.3 It
remains challenging to develop efficient aerobic oxidation
systems participated by copper (II)-acetonitrile complex.
In 2011, Ji’s group opened up a new route to access β-
ketophosphonates by reacting easily available alkenes with
dioxygen and H-phosphonates in the presence of Cu-Fe
cocatalysts (Scheme 1, path d).11 In 2015, our group created an
elegant synthesis of β-ketophosphonates from alkynes and
dialkyl H-phosphonates in the presence of AgNO3/CuSO4 and
K2S2O8 (Scheme 1, path e).12 The other synthetic methods
concerning direct oxyphosphorylation of alkynes with H-
phosphonates were subsequently reported by He’s group and
Song’s group, respectively.13 Over the past few years, the use of
both α,β-alkynyl carboxylic acids and α,β-alkenyl carboxylic
acids, synthetically as terminal alkyne and alkene equivalents,
began to be reported in the literature.14 Direct use of α,β-alkynyl
carboxylic acids and α,β-alkenyl carboxylic acids has some
advantages, such as no unpleasant smell, easy handling and
storage due they are solids.14a It is worth mentioning here that,
α,β-alkenyl carboxylic acids are generally more cheaper than
corresponding α,β-alkynyl carboxylic acids. Thus, exploration of
new synthetic methods for β-ketophosphonates with α,β-alkenyl
carboxylic acids would be preferentially encouraged. Song’s
group very recently put forward synthetic strategies to reach β-
ketophosphonates, in which CuOTf/FeCl3-cocatalysts were used
to activate the decarboxylation-oxyphosphorylation reaction of
β-Ketophosphonates are versatile intermediates for various
synthetically useful transformations,4 especially for the
construction of alkenes through the well known Horner-
Wadsworth-Emmons (HWE) reaction.5 β-Ketophosphonates also
exhibit interesting bioactivities and prominent metal-complexing
abilities.6 They have been successfully applied as extractants for
transition elements, lanthanides, actinoid and alkali metals etc.7
Great efforts have been made during the past several decades to
synthesize β-ketophosphonate scaffolds. Earlier synthetic
methods mainly include Arbuzov reaction (Scheme 1, path a),8
acylation of alkylphosphonates under strong basic or acidic
reaction conditions (Scheme 1, path b),9 and hydration of
alkynylphosphonates catalyzed by palladium (II) and gold (I)
catalysts (Scheme 1, path c).10 However, nearly all those earlier

2
Tetrahedron
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Table 1. Optimization of the reaction parametersa,b
Scheme 1. Comparison of previous methods with this work
alkenyl or alkynyl carboxylic acids with H-phosphonates
(Scheme 1, path f).13a Herein, we disclose a simpler synthetic
strategy, by which a variety of β-ketophosphonates were
synthesized efficiently by the reaction of α,β-alkenyl carboxylic
acids or alkenes with H-phosphonates and air oxygen, catalyzed
by CuSO4·5H2O in CH3CN under open air conditions. In a sharp
contrast to Song’s method, the most prominent advantage of our
reaction is using common and inexpensive CuSO4·5H2O, instead
of using much more expensive CuOTf as a catalyst. The
advantages also include a base-free condition and a wide reaction
scope. The scope of the reaction encompasses both alkenyl
carboxylic acids and alkenes, being suitable for transformation of
not only alkenyl carboxylic acids but also alkenes into the
corresponding β-ketophosphonates.
a Reaction conditions: 0.2 mmol of 1a, and 4 mL of solvent in a 25
mL round bottom flask for 6 h. b Isolated yields. NR = no reaction
ND = no detected
Table 2. Scope of the oxyphosphorylation of alkenyl acidsa,
b
2. Results and discussion
We initiated the important study, starting with establishing
optimal experimental conditions using the model reaction of
cinnamic acid (1a) with diethyl phosphite (2a) under open-air
conditions, as summarized in Table 1. The solvent system
employed sometimes notably affect the reaction efficiency. The
effect of solvents on the model reaction was first investigated by
reacting 1a with 2 equiv. of 2a in various solvent in the presence
of CuSO4·5H2O (10 mol %) at 60 °C for 6 h (Table 1. entries 1-
8). Astonishingly, conducting the reaction in any solvents like
THF, DCE, DMF, 1,4-dioxane, EtOH, EtOAc and DMSO, did
not bring about any product of 3a (entries 1-7), but in only
CH3CN, the reaction proceeded smoothly, affording 3a in 74%
yield (entry 8). This abnormal solvent effect phenomenon
puzzled us and encouraged us to explore the deep reason behind
the result shortly afterwards. The effects of some common metal
salt catalysts on the reaction were then investigated, as
summarized in entries 8-16. CuCl, CoCl2·6H2O and NiCl2·6H2O
exhibited no any catalytic activity for the model reaction (entries
12, 14 and 15). Cu(OAc)2·H2O and FeCl3·6H2O afforded only
trace product of 3a, which was detected by 31P NMR (entries 11,
13). Comparatively, Cu(NO3)2·3H2O and Ag2CO3 gave about
48% and 39% yields of product, respectively (entries 10, 16).
Anhydrous cupric sulfate CuSO4 (entry 9) gave a little low yield
of 3a (74%) than that of CuSO4·5H2O (entry 8). Thus,
CuSO4·5H2O, the cheapescopper salt, was still the best one
among metal salt catalysts tested (entry 8).The investigation on
the amount of CuSO4·5H2O (entries 8, 17-18) indicated that 10
mol% was still the most appropriate amount of the catalysts.
Then the influence of temperature on the model reaction was
investigated (entries 8, 19-21). It can be seen that the 60 °C is the
most appropriate temperature, among the tested temperature
a Reaction conditions: 0.2 mmol of 1, 0.4 mmol of 2, CuSO4
·5H2O
(10 mol%) and 4 mL of CH3CN in a 25 mL round bottom flask at
60 °C for 6 h. b Isolated yields.
regions 40-70 °C. At last, the ideal amount of diethyl phosphite
was explored (entries 8, 22-24). The result indicates that 2.0
equiv. is the best choice. Therefore, the best yield of 3a was
obtained by employing 10 mol% CuSO4·5H2O and 2.0
equivalents of diethyl phosphite in CH3CN at 60 °C for 6 h (entry
23).

were all compatible well for the oxyphosphorylation reaction. To
With the optimized conditions in hand, we AbeCgaCn EtoPexTaEmiDne MANUSCRIPT
the generality and the substrate scope of this synthetic strategy,
as demonstrated in Table 2. As it can be seen, a series of dialkyl
H-phosphonates, including diethyl phosphite, diisopropyl,
diisobutyl, dibenzyl, and diphenyl phosphates, reacted well with
cinnamic acid itself, affording the corresponding β-
ketophosphonates 3a-e in good to excellent yields (Table 2).
Much to our delight, diphenylphosphine oxide and ethyl
our delight, 1H-indene and (Z)-1-methoxy-4-(prop-1-en-1-
yl)benzene, two internal alkenes, reacted smoothly with diethyl
phosphite, affording the corresponding β-ketophosphonates 3af
and 3ag in moderate yields.
Next, we carried out three more experiments to explore the
related reaction mechanism (Scheme 2). When TEMPO (2,2,6,6-
tetramethyl-l-piperidinyloxy), a widely used radical scavenger,
was added into the reaction mixture, the reaction was found to be
completely restrained, suggesting that radical processes might be
involved (Scheme 2a). When the reaction was carried out under a
nitrogen atmosphere, no desire product was obtained, indicating
that the presence of oxygen is indispensable (Scheme 2b). Then
an isotope labeling study was conducted. In the presence of
H218O, no corresponding isotope-labeled β-ketophosphonate was
detected by high-resolution ESI-MS (Scheme 2c), implying that
carbonyl oxygen in the product should originally be from oxygen
in air.
phenylphosphinate,
two
other
kinds
of
important
organophosphorous reagents, were found to be well compatible
for the decarboxylation-oxyphosphorylation reaction, leading to
the desired products 3f and 3g in excellent yields, respectively.
Meanwhile, a large variety of substituted phenylacrylic acid,
bearing both electron-donating groups (Me, OCH3) and electron-
withdrawing groups (F, Br, NO2) on the phenyl ring, reacted
smoothly with various organophosphorus reagents, affording the
corresponding target products in good to excellent yields (3h-y).
It can be seen here that the electronic effects of the substituents
attached to phenyl rings had no noticeable influence on the
efficiency of decarboxylation-oxyphosphorylation reactions.
Furthermore, (E)-3-(furan-2-yl)acrylic acid, a heteroaromatic
alkenyl carboxylic acids, as well as (E)-2-methyl-3-phenylacrylic
acid, a α-substituted alkenyl carboxylic acids, reacted well with
dialkyl H-phosphonates, giving 3z, 3aa-b in good yields,
respectively.
The methodology covered much more wide range of reactants
than we expected. Alkenes, commonly employed as readily
available building blocks for a wide variety of reactions, to our
surprise, were well compatible for the oxyphosphorylation
reaction as well. Styrene was initially selected to submit to the
reaction conditions. Further optimization of reaction condition
indicated that the corresponding β-ketophosphonates could be
obtained in excellent yield using relatively less amount of H-
phosphonate within much reduced time (for details see
Supplementary Material Table S1). Subsequently, a large variety
of alkenes and H-phosphonates were employed to explore the
scope of the reaction (Table 3). All the organophosphorus
reagents mentioned above, as well as a large variety of alkenes
Scheme 2. Additional studies for mechanism. Reaction
conditions: X = COOH, 0.2 mmol of 1a, 0.4 mmol of 2a,
CuSO4·5H2O (10 mol%), and 4 mL of CH3CN at 60 °C for 6
h. X = H, 0.2 mmol of 4a, 0.3mmol of 2a, CuSO4·5H2O (10
mol%), and 4 mL of in CH3CN at 60 °C for 3 h. (a) TEMPO
(4 equiv.) under air (b) nitrogen ball (c) H218O (1 equiv.)
Table 3. Scope of the oxyphosphorylation of alkenesa,b
Scheme 3. Proposed reaction mechanism
A plausible mechanism for the decarboxylation-oxyphos-
phorylation reaction is thus proposed accordingly as indicated in
Scheme 3. It is well known that copper(II) ion easily forms
acetonitrile-soluble complex [Cu(MeCN)n]2+.15 In this case,
complex [Cu(MeCN)n]2+ 5 is an indispensable initiator for the
subsequent cascade of the decarboxylation-oxyphosphorylation
reaction. As reported by many literatures, copper-active-oxygen
proteins play essential roles in oxygen transport in biological
systems, being one of the hot researches of biochemistry.16
Copper-active-oxygen complexes are also key intermediates
a Reaction conditions: 0.2 mmol of 4, 0.3mmol of 2, CuSO4
·5H2O
(10 mol%) and 4 mL of CH3CN in a 25 mL round bottom flask at
involved in
a variety of Cu-catalyzed-aerobic oxidation
60 °C for 3 h. b Isolated yields.
reactions.17 It is well known that molecular oxygen is a diradical

4
Tetrahedron
ACCEPTED MANUSCRIPT
in the ground state with one unpaired electron on each oxygen.
Then, CH3CN was evaporated, and the reaction mixture was
Here O2 in air reacts further with copper(II)-acetonitrile complex
5, giving copper-active-oxygen complex 6, which then quickly
attacks dialkyl H-phosphonate 2, forming hydroperoxide
complex 7 as well as phosphonyl radical 8. The resulting radical
8 regioselectively adds to α,β-alkenyl carboxylic acid 1, leading
to the formation of radical 9. Radical 9 continuously reacts with
hydroperoxide complex 7 to produce hydroperoxide intermediate
10, and meanwhile, complex [Cu(MeCN)n]2+ 5 is regenerated.
Afterwards, intermediate 10 dehydrates to produce compound 11.
Subsequently, an energetically favorable decarboxylation of
compound 11 is followed, leading to the formation of target β-
ketophosphonate 3. A similar mechanism concerning using
alkenes as reactants to synthesize the related β-ketophosphonates
can be found in Supplementary Material Scheme S2 in details.
quenched with water, followed by extraction with ethyl acetate.
The combined organic layers were washed with brine and dried
over anhydrous Na2SO4. After filtration, the solvent was
evaporated in vacuo. The crude product was purified by silica gel
chromatography (petroleum ether: ethyl acetate =1:1) to give the
desired product.
4.3. Characterization data for products
Diethyl (2-oxo-2-phenylethyl)phosphonate (3a) 11
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.89 (d, 2H, J =
1
7.6 Hz), 7.46 (t, 1H, J = 7.2 Hz), 7.35 (t, 2H, J = 7.6 Hz), 4.05-
3.98 (m, 4H), 3.56 (d, 2H, J = 22.8 Hz), 1.15 (t, 6H, J = 7.2 Hz);
13C NMR (CDCl3, 100 MHz); δ: 191.85 (d, JP-C = 6.5 Hz), 136.42
( JP-C = 1.9 Hz), 133.59, 128.92, 128.52, 62.59 (d, JP-C = 6.4 Hz),
38.78 (d, JP-C 129.3 Hz), 16.12 (d, JP-C = 6.4 Hz); 31P NMR
(CDCl3, 162 MHz) δ: 17.76; HRMS: calcd for C12H17O4P
[M+H]+ 257.0937, found 257.0941.
3. Conclusion
In conclusion, a relatively simple synthetic strategy has been
developed, by which a large variety of β-ketophosphonates were
synthesized smoothly by the reaction of α,β-alkenyl carboxylic
acids or alkenes with H-phosphonates, catalyzed by CuSO4·5H2O
in CH3CN under open air conditions. Molecular oxygen (O2) is
prerequisite for achieving the meaningful synthesis of β-
ketophosphonates. Oxygen (O2) in air is initially trapped by
[Cu(MeCN)n]2+ to form active oxygen complex [(MeCN)nCuII-O-
Diisopropyl (2-oxo-2-phenylethyl)phosphonate (3b) 11
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.98 (d, 2H, J =
7.2 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.39 (t, 2H, J = 8.0 Hz), 4.74-
4.66 (m, 2H), 3.57 (d, 2H, J = 22.8 Hz), 1.24 (dd, 12H, J = 3.2
Hz, 6.4 Hz); 13C NMR (CDCl3, 100 MHz); δ: 192.06 (d, JP-C = 6.6
Hz), 136.66, 133.48, 129.11, 128.47, 71.50 (d, JP-C = 6.6 Hz),
39.68 (d, JP-C = 129.6 Hz), 23.82 (dd, JP-C = 5.2 Hz, 21.3Hz); 31P
NMR (CDCl3, 162 MHz) δ: 17.84; HRMS: calcd for C14H21O4P
[M+Na]+ 307.1070, found 307.1068
O·], by which
a
highly efficient and mild cascade
decarboxylation-oxyphosphorylation reaction is thus triggered.
The prominent advantages of our reaction include using
inexpensive CuSO4·5H2O as a catalyst, base or acid free and
open air conditions as well as a wide reaction scope. The scope
of the reaction encompasses alkenyl carboxylic acids, alkenes, as
well as a series of organophosphorous reagents, including
diphenylphosphine oxide, dialkyl H-phosphonates and ethyl
phenylphosphinate. To our knowledge, it is the first example to
show how active oxygen complex [(MeCN)nCuII-O-O·] is
involved in the environmentally benign synthetic process of
synthesizing a variety of biologically and chemically significant
β-ketophosphonates. The investigation concerning using
[(MeCN)nCuII-O-O·] as reaction initiator for other related
synthetic approaches is currently underway.
Diisobutyl (2-oxo-2-phenylethyl)phosphonate (3c)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.91 (d, 2H, J =
7.2 Hz), 7.47 (t, 1H, J = 7.2 Hz), 7.36 (t, 2H, 8.0 Hz), 3.78-3.68
(m, 4H), 3.56 (d, 2H, J = 22.8 Hz), 1.83-1.73 (m, 2H), 0.77 (d,
6.8 Hz); 13C NMR (CDCl3, 100 MHz); δ: 191.70 (d, JP-C = 6.9
Hz), 136.48 (d, JP-C = 1.4 Hz), 133.54, 128.96, 128.51, 72.31 (d,
JP-C = 6.8 Hz), 38.04 (d, JP-C = 129.0 Hz), 29.03 (d, JP-C = 6.6
Hz), 18.50 (d, JP-C = 1.3 Hz); 31P NMR (CDCl3, 162 MHz) δ:
19.85; HRMS: calcd for C16H25O4P [M+H]+ 313.1563, found
313.1572
Dibenzyl (2-oxo-2-phenylethyl)phosphonate (3d) 13c
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.93 (d, 2H, J =
7.6 Hz), 7.54 (t, 1H, J = 7.2 Hz), 7.40 (t, 2H, J = 7.6 Hz), 7.34-
7.28 (m, 10H), 5.09-4.98 (m, 4H), 3.68 (d, 2H, J = 22.4); 13C
NMR (CDCl3, 100 MHz); δ: 191.71 (d, JP-C = 6.5 Hz), 136.44 (d,
JP-C = 2.4 Hz), 135.90 (d, JP-C = 5.2 Hz), 133.72, 129.04, 128.66,
4. Experimental Section
4.1. General information
All commercial reagents and solvents were used without
further purification. 1H, 13C, and 31P NMR spectra were recorded
with a Bruker Avance 400 MHz spectrometer. All NMR spectra
were recorded in CDCl3 at room temperature (20 ± 3 °C). 1H and
13C chemical shifts are quoted in parts per million downfield
from tetramethylsilane (TMS). 31P chemical shifts are quoted in
parts per million relative to 85% H3PO4 as an external standard.
High resolution mass spectra (HR MS) were obtained with a
Waters Micromass Q-Tof Micro instrument using the ESI
technique.
128.59, 128.51, 128.06, 68.08 (d, JP-C = 6.5 Hz), 38.68 (d, JP-C
=
130.8); 31P NMR (CDCl3, 162 MHz) δ: 21.35; HRMS: calcd for
C22H21O4P [M+H]+ 381.1250, found 381.1256
Diphenyl (2-oxo-2-phenylethyl)phosphonate (3e)6a
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.04 (d, 2H, J =
7.2 Hz), 7.61 (t, 1H, J = 7.2 Hz), 7.50 (t, 2H, 7.6 Hz), 7.32-7.18
(m, 4H), 7.17-7.15 (m, 6H), 3.94 (d, 2H, 22.8 Hz); 13C NMR
(CDCl3, 100 MHz); δ: 190.78 (d, JP-C = 6.9 Hz), 150.03 (d, JP-C
=
8.9 Hz), 136.42, 133.97, 129.82, 129.08, 128.79, 125.49, 120.60
(d, JP-C = 4.4 Hz), 37.86 (d, 132.7 Hz); 31P NMR (CDCl3, 162
MHz) δ: 13.14; HRMS: calcd for C20H17O4P [M+H]+ 353.0937,
found 353.0941
4.2. General Procedure for the Synthesis of β-ketophos-
phonates
2-(diphenylphosphoryl)-1-phenylethan-1-one (3f) 13c
Starting from the alkenyl acids: alkenyl acids 1 (0.2 mmol),
H-phosphonates 2 (0.4 mmol), and CuSO4·5H2O (10 mol%) were
dissolved in 4 mL CH3CN at round-bottomed flask and stirred at
60 °C for 6 h in an air atmosphere.
White solid, 1H NMR (CDCl3, 400 MHz,) δ: 7.95 (d, 2H, J =
7.6 Hz), 7.81-7.76(m, 4H), 7.49-7.35 (m, 9H), 4.13 (d, 2H, J =
15.2 Hz); 13C NMR (CDCl3, 100 MHz); δ: 192.86 (d, JP-C =5.6
Hz), 136.95, 133.61, 132.27 (d, JP-C = 5.2 Hz), 132.18, 131.20 (d,
JP-C = 4.8 Hz), 129.23, 128.70, 128.55 (d, JP-C = 4.5 Hz), 43.13
(d, JP-C = 58.0 Hz); 31P NMR (CDCl3, 162 MHz) δ: 26.96;
HRMS: calcd for C20H17O2P [M+H]+ 321.1039, found 321.1040.
Starting from the alkenes: alkenes 4 (0.2 mmol), H-
phosphonates 2 (0.3 mmol), and CuSO4·5H2O (10 mol%) were
dissolved in 4 mL CH3CN at round-bottomed flask and stirred at
60 °C for 3 h in an air atmosphere.

Ethyl (2-oxo-2-phenylethyl)(phenyl)phosphonate (3g) 11
23.82 (dd, JP-C = 3.8 Hz, 21.2 Hz), 21.23; 31P NMR (CDCl3, 162
MHz) δ: 18.25; HRMS: calcd for C15H23O4P [M+H]+ 299.1407,
found 299.1401.
ACCEPTED MANUSCRIPT
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.94 (dd, 2H, J =
0.8, 8.0 Hz), 7.79-7.73 (m, 2H), 7.55-7.50 (m, 2H), 7.45-7.39 (m,
4H), 4.15-3.87 (m, 2H), 3.78 (dd, 2H, JP-H = 4.8Hz, 18.8Hz), 1.23
(t, 3H, J = 6.8 Hz); 13C NMR (CDCl3, 100 MHz); δ: 192.12 (d, JP-
C = 5.5 Hz), 136.86, 133.54, 132.73 (d, JP-C = 2.8 Hz), 131.87 (d,
JP-C = 10.2 Hz), 130.65 (d, JP-C = 132.0 Hz), 129.49, 128.90 (d, JP-
C = 13.2 Hz) 128.56, 61.50 (d, JP-C = 6.3 Hz), 43.05 (d, JP-C = 85.8
Hz), 16.33 (d, JP-C = 6.5 Hz); 31P NMR (CDCl3, 162 MHz) δ:
33.69; HRMS: calcd for C16H17O3P [M+Na]+ 311.0808, found
311.0810
Diisobutyl (2-oxo-2-(o-tolyl)ethyl)phosphonate (3n)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.72 (d, 1H, J =
7.6 Hz), 7.35 (t, 1H, J = 6.8 Hz), 7.26-7.20 (m, 2H), 3.78 (t, 4H,
J = 6.8 Hz), 3.59 (d, 2H, J = 22.8 Hz), 2.48 (3H), 1.86-1.80 (m,
2H), 0.84 (d, 12H, J = 6.4 Hz); 13C NMR (CDCl3, 100 MHz); δ:
194.90 (d, JP-C = 6.7 Hz), 138.99, 137.20, 131.95 (d, JP-C = 8.0
Hz), 129.65, 125.69, 72.33 (d, JP-C = 6.7 Hz), 41.26 (d, JP-C
=128.4 Hz), 29.10 (d, JP-C = 6.6 Hz), 21.33, 18.58 (d, JP-C = 1.2
Hz); 31P NMR (CDCl3, 162 MHz) δ: 18.51; HRMS: calcd for
C17H27O4P [M+H]+ 327.1720, found 327.1724.
Diethyl (2-oxo-2-(p-tolyl)ethyl)phosphonate (3h) 13c
yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.90 (d, 2H, J = 8.0
Hz), 6.25 (d, 2H, J = 8.0 Hz), 4.16-4.09 (m, 4H), 3.60 (d, 2H,
22.8 Hz), 2.40 (3H), 1.27 (t, 6H, J = 7.2 Hz); 13C NMR (CDCl3,
100 MHz); δ: 191.47 (d, JP-C = 6.5 Hz), 144.68, 134.08, 129.30,
129.25, 62.68 (d, JP-C = 6.5 Hz), 38.48 (d, JP-C = 129.4 Hz),
21.69, 16.24 (d, JP-C = 6.2 Hz); 31P NMR (CDCl3, 162 MHz) δ:
21.25; HRMS: calcd for C13H19O4P [M+H]+ 271.1094, found
271.1096.
Diisopropyl (2-oxo-2-(p-tolyl)ethyl)phosphonate (3i) 11
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.90 (d, 2H, J =8.0
Hz), 7.24 (d, 2H, J = 7.6 Hz), 4.77-4.66 (m, 6H), 3.57 (d, 2H, J =
22.8 Hz), 2.39 (3H), 1.27 (dd, 12H, J = 4.0 Hz, 6.4Hz); 13C NMR
(CDCl3, 100 MHz); δ: 191.61 (d, JP-C = 6.6 Hz), 144.46, 134.22,
129.29, 129.19, 71.61 (d, JP-C = 6.7 Hz), 39.62 (d, JP-C = 130.0
Hz), 23.84 (dd, JP-C = 5.2 Hz, 21.7 Hz), 21.67; 31P NMR (CDCl3,
162 MHz) δ: 22.84; HRMS: calcd for C15H23O4P [M+Na]+
321.1226, found 321.1228.
Diethyl (2-(4-methoxyphenyl)-2-oxoethyl)phosphonate (3o)10b
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.97 (d, 2H, J =
8.8 Hz), 6.92 (d, 2H, J = 8.8 Hz), 4.16-4.08 (m, 4H), 3.85 (s, 3H),
3.58 (d, 2H, J = 22.8 Hz), 1.27 (t, 6H, J = 7.2 Hz); 13C NMR
(CDCl3, 100 MHz); δ: 190.23 (d, JP-C = 6.1 Hz), 164.02, 131.51,
129. 60 (d, JP-C = 2.0 Hz), 113.78, 62.70 (d, JP-C = 7.5Hz), 55.52,
38.20 (d, JP-C = 129.3Hz), 16.24 (d, JP-C = 6.3 Hz); 31P NMR
(CDCl3, 162 MHz) δ: 20.70; HRMS: calcd for C13H19O5P
[M+Na]+ 309.0862, found 309.0861.
Diisobutyl
(3p)
(2-(4-methoxyphenyl)-2-oxoethyl)phosphonate
1
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.96 (d, 2H, J =
8.8 Hz), 6.89 (d, 2H, J = 8.8 Hz), 3.83 (s, 3H), 3.82-3.72 (m, 4H),
3.56 (d, 2H, J = 22.8 Hz), 1.90-1.80 (m, 2H), 0.84 (d, 12H, J =
6.8 Hz); 13C NMR (CDCl3, 100 MHz); δ: 190.13 (d, JP-C = 6.6
Hz), 163.95, 131.49, 129.63, 113.74, 72.37 (d, JP-C = 7.8 Hz),
55.49, 37.76 (d, JP-C = 129.0 Hz), 29.13 (d, JP-C = 6.5 Hz), 18.58
(d, JP-C = 1.1 Hz); 31P NMR (CDCl3, 162 MHz) δ: 20.6; HRMS:
calcd for C17H27O5P [M+H]+ 343.1669, found 343.1674.
Dibenzyl (2-oxo-2-(p-tolyl)ethyl)phosphonate (3j)
Yellow oil, 1H NMR (CDCl3, 400 MHz) δ: 7.83 (d, 2H, J = 7.6
Hz), 7.27 (10H), 7.28 (d, 2H, J = 7.6 Hz), 5.08-4.97 (m, 4H),
3.61 (d, 2H, J = 22.4 Hz), 2.36 (3H); 13C NMR (CDCl3, 100
MHz); δ: 191.27 (d, JP-C = 6.4), 144.66, 135.98 (d, JP-C = 6.2 Hz),
134.03 (d, JP-C = 2.5 Hz), 129.34, 129.20, 128.56, 128.45, 128.04,
67.97 (d, 6.2 Hz), 38.65 (d, JP-C = 130.5Hz), 21.71; 31P NMR
(CDCl3, 162 MHz) δ: 21.52; HRMS: calcd for C23H23O4P
[M+H]+ 395.1407, found395.1412
Diethyl (2-(4-fluorophenyl)-2-oxoethyl)phosphonate (3q) 10b
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.03-8.00 (dd, 2H,
J = 5.6 Hz, 8.8 Hz), 7.10 (t, 2H, J = 8.4 Hz), 4.12-4.05 (m, 4H),
3.56 (d, 2H, J = 22.8 Hz), 1.24(t, 6H, J = 7.2 Hz); 13C NMR
(CDCl3, 100 MHz); δ: 190.28 (d, JP-C = 6.5 Hz), 166.15 (d, JF-C
254.5 Hz), 132.93, 131.80 (d, JF-C = 9.4 Hz), 115.75 (d, JF-C
=
=
2-(diphenylphosphoryl)-1-(p-tolyl)ethan-1-one (3k)12
White solid, 1H NMR (CDCl3, 400 MHz) δ: 7.82-7.78 (m, 6H),
7.42 (t, 2H, J = 7.2 Hz), 7.34-7.29 (m, 4H), 7.09 (d, 2H, J = 8.0
Hz), 4.30 (d, 2H, J = 15.2 Hz), 2.29 (s, 3H); 13C NMR (CDCl3,
100 MHz); δ: 193.36, 144.76, 134.43, 132.24 (d, JP-C = 2.2 Hz),
131.24 (d, JP-C = 10.4 Hz), 131.54, 131.44, 129.52, 129.33,
128.64 (d, JP-C = 12.4 Hz), 42.59 (d, JP-C = 60.1 Hz), 21.75; 31P
NMR (CDCl3, 162 MHz) δ: 28.35; HRMS: calcd for C21H19O2P
[M+H]+ 335.1195, found 335.1198.
21.8 Hz), 62.75 (d, JP-C = 6.5 Hz), 38.64 (d, JP-C = 128.8 Hz),
16.19 (d, JP-C = 6.3 Hz); 31P NMR (CDCl3, 162 MHz) δ: 19.69;
HRMS: calcd for C12H16FO4P [M+H]+ 275.0843, found
275.0846.
Diisopropyl (2-(4-fluorophenyl)-2-oxoethyl) phosphonate (3r)
11
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.04 (dd, 2H, J =
5.6 Hz, 8.4 Hz), 7.12 (t, 2H, J = 8.8 Hz), 4.76-4.65 (m, 2H), 3.55
(d, 2H, 5-H, J = 23.2 Hz), 1.26 (dd, 12H, J = 1.2 Hz, 6.0 Hz); 13
C
Diethyl (2-oxo-2-(o-tolyl)ethyl)phosphonate (3l) 13c
NMR (CDCl3, 100 MHz); δ: 190.44 (d, JP-C = 6.5 Hz), 166.01 (d,
JF-C = 254.3 Hz), 133.10, 131.92 (d, JF-C = 9.5 Hz), 115.60 (d, JF-C
= 21.8 Hz), 71.65 (d, JP-C = 6.7 Hz), 39.78 (d, JP-C = 129.1 Hz),
23.83 (dd, JP-C = 3.8 Hz, 17.6 Hz); 31P NMR (CDCl3, 162 MHz)
δ: 17.41; HRMS: calcd for C14H20FO4P [M+Na]+ 325.0975,
found 325.0979.
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.75 (d, 1H, J =
8.0 Hz , 7.39 (t, 1H, J = 6.2 Hz), 7.31-7.25 (m, 2H), 4.16-4.08
(m, 4H), 3.60 (d, 2H, J = 22.4 Hz), 2.52 (3H), 1.27 (t, 6H, J = 5.8
Hz); 13C NMR (CDCl3, 100 MHz); δ: 195.03 (d, JP-C = 6.5 Hz),
138.96, 137.21, 131.96 (d, JP-C = 4.2 Hz), 129.60, 125.69, 62.59
(d, JP-C = 6.4 Hz), 41.00 (d, JP-C =126.9 Hz), 21.30, 16.19 (d, JP-C
= 6.2 Hz); 31P NMR (CDCl3, 162 MHz) δ: 20.32; HRMS: calcd
for C13H19O4P [M+H]+ 271.1094, found 271.1097.
Diisobutyl (2-(4-fluorophenyl)-2-oxoethyl)phosphonate (3s)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.00 (dd, 2H, J =
5.2 Hz, 8.8 Hz), 7.08 (t, 2H, J = 8.8 Hz), 3.82-3.73 (m, 4H), 3.56
(d, 2H, J = 23.2 Hz), 1.87-1.77 (m, 2H), 0.82 (d, 12H, J = 6.8
Hz); 13C NMR (CDCl3, 100 MHz); δ: 190.16 (d, JP-C = 6.6 Hz),
165.52 (d, JF-C = 254.4 Hz), 132.94, 131.80 (d, JF-C = 9.4 Hz),
115.68 (d, JF-C = 21.8 Hz), 72.42 (d, JP-C = 9.6 Hz), 38.17 (d, JP-C
= 128.6 Hz), 29.08 (d, JP-C = 6.5 Hz), 18.51; 31P NMR (CDCl3,
162 MHz) δ: 18.64; HRMS: calcd for C16H24O4P [M+H]+
331.1469, found 331.1475.
Diisopropyl (2-oxo-2-(o-tolyl)ethyl)phosphonate (3m) 11
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.72 (d, 1H, J =
7.6 Hz), 7.37 (t, 1H, J = 7.2 Hz), 7.28-7.22 (m, 2H), 4.75-4.67
(m, 2H), 3.56 (d, 2H, J = 22.8 Hz), 2.50 (3H), 1.25 (dd, 12H, J =
6.4 Hz, 8.4 Hz); 13C NMR (CDCl3, 100 MHz); δ: 195.34 (d, JP-C
=
6.7 Hz), 138.77, 137.56, 131.77 (d, JP-C = 5.3 Hz), 129.62,
125.57, 71.45 (d, JP-C = 6.6 Hz), 42.89 (d, JP-C =129.2 Hz), 29.70,

6
Tetrahedron
ACCEPTED MANUSCRIPT
Diethyl (2-(4-bromophenyl)-2-oxoethyl)phosphonate (3t) 10b
Diisobutyl (2-(furan-2-yl)-2-oxoethyl)phosphonate (3aa)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.86 (d, 2H, J =
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.60 (d, 1H, J =
0.8 Hz), 7.27 (d, 1H, J = 8.4 Hz), 6.54 (d, 1H, J = 1.6 Hz, 3.6
Hz), 3.87-3.77 (m, 4H), 3.49 (d, 2H, J = 22.8 Hz), 1.92-1.82 (m,
2H), 0.86 (d, 12H, J = 6.8 Hz); 13C NMR (CDCl3, 100 MHz); δ:
179.95 (d, JP-C = 7.0 Hz), 152.33, 147.06, 118.81, 112.86, 72.41
(d, JP-C = 7.0 Hz), 37.89 (d, JP-C = 129.2 Hz), 29.11 (d, JP-C = 6.6
Hz), 18.56; 31P NMR (CDCl3, 162 MHz) δ: 18.38; HRMS: calcd
for C14H23O5P [M+H]+ 303.1356, found 303.1360.
1
8.4 Hz), 7.59 (d, 2H, J = 7.6 Hz), 4.15-4.08 (m, 4H), 3.58 (d, 2H,
J = 22.8 Hz), 1.27 (t, 6H, J = 8.8 Hz); 13C NMR (CDCl3, 100
MHz); δ: 190.92 (d, JP-C = 6.5 Hz), 135.20, 131.93, 130.58,
129.10 (d, JP-C = 4.5 Hz), 62.81 (d, JP-C = 6.5 Hz), 38.21 (d, JP-C
=
128.6 Hz), 16.24 (d, JP-C = 6.3 Hz); 31P NMR (CDCl3, 162 MHz)
δ: 19.30; HRMS: calcd for C12H16BrO4P [M+H]+ 335.0042,
found 335.0041.
Diisopropyl (2-(4-bromophenyl)-2-oxoethyl)phosphonate (3u)
Diethyl (1-oxo-1-phenylpropan-2-yl)phosphonate (3ab) 12
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.99 (d, 2H, J =
11
1
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.82 (d, 2H, J =
8.4Hz), 7.54 (d, 2H, J = 8.8 Hz), 4.69-4.61 (m, 2H), 3.49 (d, 2H,
J = 23.3 Hz), 1.20 (dd, 12H, J = 2.4 Hz, 6.0 Hz); 13C NMR
(CDCl3, 100 MHz); δ: 191.16 (d, JP-C = 6.6 Hz), 135.42, 131.88,
130.78, 128.93, 71.67 (d, JP-C = 6.7 Hz), 39.96 (d, JP-C = 128.7
Hz), 23.96 (dd, JP-C = 5.2 Hz, 18.9 Hz); 31P NMR (CDCl3, 162
MHz) δ: 16.97; HRMS: calcd for C14H20BrO4P [M+Na]+
385.0175, found 385.0175.
7.2 Hz), 7.57 (t, 1H, J = 7.6 Hz), 7.47 (t, 2H, J = 7.6 Hz), 4.16-
4.03 (m, 5H), 1.54 (dd, 3H, J = 5.6 Hz, 18.0 Hz), 1.28 (t, 6H, J =
7.2 Hz); 13C NMR (CDCl3, 100 MHz); δ: 196.70 (d, JP-C = 5.0
Hz), 137.07, 133.54, 129.06, 128.70, 62.90 (dd, J = 6.8 Hz, JP-C
=
10.3 Hz), 41.50 (d, JP-C = 129.5 Hz), 16.47 (dd, JP-C = 6.0 Hz,
14.5 Hz), 12.43 (d, JP-C = 6.6 Hz); 31P NMR (CDCl3, 162 MHz)
δ: 22.31; HRMS: calcd for C13H19O4P [M+H]+ 271.1094, found
271.1094.
Diisobutyl (2-(4-bromophenyl)-2-oxoethyl)phosphonate (3v)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.77 (d, 2H, J =
7.2 Hz), 7.48 (d, 2H, J = 8.4 Hz), 3.75-3.67 (m, 4H), 3.50 (d, 2H,
J = 22.8 Hz), 1.81-1.71 (m, 2H), 0.76 (d, 12H, J = 6.8 Hz); 13C
NMR (CDCl3, 100 MHz); δ: 190.71 (d, JP-C = 6.7 Hz), 135.17,
Diethyl
(3ac) 13c
(2-(4-(tert-butyl)phenyl)-2-oxoethyl)phosphonate
1
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.87 (d, 2H, J =
8.4 Hz), 7.40 (d, 2H, J = 8.8 Hz), 4.08-4.01 (m, 4H), 3.53 (d, 2H,
J = 22.8 Hz), 1.25 (s, 9H), 1.92 (t, 6H, J = 7.2 Hz); 13C NMR
(CDCl3, 100 MHz); δ: 191.41 (d, JP-C = 6.5 Hz), 157.39, 133.93
(d, JP-C = 1.9 Hz), 129.00, 125.50, 62.53 (d, JP-C = 6.5 Hz), 38.30
(d, JP-C = 129.1 Hz), 35.09, 30.97, 16.18 (d, JP-C = 6.3 Hz); 31P
NMR (CDCl3, 162 MHz) δ: 19.77; HRMS: calcd for C16H25O4P
[M+H]+ 313.1563, found 313.1569.
131.80, 130.52, 128.85, 72.34 (d, JP-C = 7.1 Hz), 38.20 (d, JP-C
=
128.2 Hz), 29.03 (d, JP-C = 6.6 Hz), 18.51; 31P NMR (CDCl3, 162
MHz) δ: 19.25; HRMS: calcd for C16H24O4BrP [M+H]+
391.0668, found 391.0672.
Diethyl (2-(4-nitrophenyl)-2-oxoethyl)phosphonate (3w)18
1
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 8.31 (d, 2H, J =
Diisobutyl (2-(4-(tert-butyl)phenyl)-2-oxoethyl)phosphonate
8.8 Hz), 8.18 (d, 2H, J = 8.8 Hz), 4.18-4.11 (m, 4H), 3.67 (d, 2H,
J = 23.2 Hz), 1.28 (t, 6H, J = 7.2 Hz); 13C NMR (CDCl3, 100
MHz); δ: 190.63 (d, JP-C = 6.7 Hz), 150.57, 140.77, 130.15,
123.79, 63.09 (d, JP-C = 6.5 Hz), 39.27 (d, JP-C = 128.0 Hz), 16.24
(d, JP-C = 6.3 Hz); 31P NMR (CDCl3, 162 MHz) δ: 18.70; HRMS:
calcd for C12H16NO6P [M+H]+ 302.0788, found 302.0791.
(3ad)
1
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.89 (d, 2H, J =
8.8 Hz), 7.42 (d, 2H, J = 8.4 Hz), 3.82-3.73 (m, 4H), 3.57 (d, 2H,
J = 22.8 Hz), 1.87-1.77 (m, 2H), 1.28 (s, 9H), 0.81 (d, J = 6.8
Hz); 13C NMR (CDCl3, 100 MHz); δ: 191.37 (d, JP-C = 6.5 Hz),
157.37, 134.02, 129.03, 125.51, 72.30 (d, JP-C = 6.8 Hz), 37.95 (d,
JP-C = 6.8 Hz), 35.10, 31.00, 29.07 (d, JP-C = 6.6 Hz), 18.55 (d, JP-
C = 2.0 Hz); 31P NMR (CDCl3, 162 MHz) δ: 19.85; HRMS: calcd
for C20H33O4P [M+H]+ 369.2189, found 369.2194.
Diisopropyl (2-(4-nitrophenyl)-2-oxoethyl)phosphonate (3x)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.29 (d, 2H, J =
8.8 Hz), 8.18 (d, 2H, J = 8.4 Hz), 4.75-4.67 (m, 2H), 3. 61 (d,
2H, J = 22.8 Hz), 1.26 (d, 12H, 6.0 Hz); 13C NMR (CDCl3, 100
MHz); δ: 190.72 (d, JP-C = 6.9 Hz), 150.46, 140.95, 130.21,
123.68, 71.93 (d, JP-C = 6.8 Hz), 40.04 (d, JP-C = 128.0 Hz), 23.90
(dd, JP-C = 3.9 Hz, 13.9 Hz); 31P NMR (CDCl3, 162 MHz) δ:
16.44; HRMS: calcd for C14H20NO6P [M+H]+ 330.1101, found
330.1104.
Diethyl (2-oxo-3-phenoxypropyl)phosphonate (3ae) 12
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.31-7.27 (dd, 2H,
J = 0.8 Hz, 8.7 Hz), 7.00 (t, 1H, J = 7.2 Hz), 6.94 (dd, 2H, J = 0.8
Hz, J = 8.7 Hz), 4.71 (s, 2H), 4.20-4.12(m, 4H), 3.27 (d, 2H, J =
22.8 Hz), 1.32 (t, 6H, J = 6.8 Hz); 13C NMR (CDCl3, 100 MHz);
δ: 198.87 (d, JP-C = 6.6 Hz), 157.69, 129.86, 122.03, 114.75,
72.86, 63.03 (d, JP-C = 6.3 Hz), 38.70 (d, JP-C = 127.0 Hz), 16.47
(d, JP-C = 6.3 Hz); 31P NMR (CDCl3, 162 MHz) δ: 18.43; HRMS:
calcd for C15H23O5P [M+H]+ 287.1043, found 287.1043.
Diisobutyl (2-(4-nitrophenyl)-2-oxoethyl)phosphonate (3y)
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 8.31 (d, 2H, J =
8.8 Hz), 8.19 (d, 2H, J = 8.8 Hz), 3.88-3.79 (m, 4H), 3.68 (d, 2H,
J = 23.2 Hz), 1.93-18.3 (m, 2H), 0.87 (d, 12H, J = 6.8 Hz); 13C
NMR (CDCl3, 100 MHz); δ: 194.89 (d, JP-C = 6.6 Hz), 138.98,
Diethyl (1-oxo-2,3-dihydro-1H-inden-2-yl)phosphonate (3af)
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.74 (d, 1H, J =
1
137.21, 129.64, 125.69, 72.37 (d, JP-C = 7.0 Hz), 40.76 (d, JP-C
=
7.6 Hz), 7.58 (t, 1H, J = 7.2 Hz), 7.46 (d, 1H, J = 7.6 Hz), 7.36 (t,
1H, J = 7.6 Hz), 4.19-4.08 (m, 4H), 3.54-3.35 (m, 2H), 3.32-3.23
(m, 1H), 1.31 (t, 3H, J = 6.8 Hz), 1.21 (t, 3H, J = 7.2 Hz); 13C
NMR (CDCl3, 100 MHz); δ: 199.17 (d, JP-C = 4.8 Hz), 153.13 (d,
JP-C = 5.4 Hz), 136.43 (d, JP-C = 3.6 Hz), 135.07, 127.70, 126.41,
124.33, 63.00 (dd, JP-C = 6.7 Hz, 48.4 Hz), 46.03 (d, JP-C = 136.4
Hz), 28.61 (d, JP-C = 2.8 Hz), 16.30 (t, JP-C = 5.0 Hz); 31P NMR
(CDCl3, 162 MHz) δ: 22.68; HRMS: calcd for C13H17O4P
[M+H]+ 269.0937, found 269.0940.
128.4 Hz), 29.10 (d, JP-C = 6.6 Hz), 18.58; 31P NMR (CDCl3, 162
MHz) δ: 20.35; HRMS: calcd for C16H24NO6P [M+H]+ 358.1414,
found 358.1418.
Diethyl (2-(furan-2-yl)-2-oxoethyl)phosphonate (3z) 13c
Yellow oil, 1H NMR (CDCl3, 400 MHz,) δ: 7.56 (s, 1H), 7.23
(d, 1H, J = 3.2 Hz), 6.50 (q, 1H, J = 1.2 Hz, 3.6 Hz), 4.10-4.03
(m, 4H), 3.42 (d, 2H, J = 22.4 Hz), 1.21 (t, 6H, J = 6.8 Hz); 13C
NMR (CDCl3, 100 MHz); δ: 179.92 (d, JP-C = 6.9 Hz), 152.20,
147.16, 118.96, 112.74, 62.63 (d, JP-C = 6.4 Hz), 38.10 (d, JP-C
=
Diethyl (1-(4-methoxyphenyl)-1-oxopropan-2-yl)phosphonate
129.1 Hz), 16.18 (d, JP-C = 6.3 Hz); 31P NMR (CDCl3, 162 MHz)
δ: 19.50; HRMS: calcd for C10H15O5P [M+H]+ 247.0730, found
247.0736.
(3ag)
1
Yellow oil, H NMR (CDCl3, 400 MHz,) δ: 7.91 (d, 2H, J =
8.8 Hz), 6.86 (d, 2H, J = 8.8 Hz), 4.08-3.95 (m, 5H), 3.78 (s, 3H),

10. (a) Li, X. B.; Hu, G. B.; Luo, P.; Tang, G.; Gao, Y. X.; Xu, P. X.;
1.46-1.40 (dd, 3H, J = 6.8 Hz, 18.0 Hz), 1.20 (At, 3CHC, JE=P7T.2EHDz), MANUSCRIPT
1.13 (t, 3H, J = 7.2 Hz); 13C NMR (CDCl3, 100 MHz); δ: 194.64
(d, JP-C = 4.8 Hz), 163.73, 131.22, 129.63, 113.59, 62.55 (dd, JP-C
= 2.3 Hz, 6.7 Hz), 55.44, 40.71 (d, JP-C = 129.6 Hz), 16.26 (dd, JP-
C = 6.0 Hz, 18.9 Hz), 12.25 (d, JP-C = 5.4 Hz); 31P NMR (CDCl3,
162 MHz) δ: 23.93; HRMS: calcd for C14H21O5P [M+H]+
301.1199, found 301.1203.
Zhao, Y. F. Adv. Synth. Catal. 2012, 354, 2427-2432; (b) Xie, L.
Y.; Yuan, R.; Wang, R. J.; Peng, Z. H.; Xiang, J. N.; He, W. M.
Eur. J. Org. Chem. 2014, 2668-2671.
11. Wei, W.; Ji, J. X. Angew. Chem. Int. Ed. 2011, 50, 9097-9099.
12. Chen, X.; Li, X.; Chen, X. L.; Qu, L. B.; Chen, J. Y.; Sun, K.;
Liu, Z. D.; Bi, W. Z.; Xia, Y. Y.; Wu H. T.; Zhao, Y. F. Chem.
Commun. 2015, 51, 3846-3849
13. (a) Zhou, M. X.; Chen, M.; Zhou, Y.; Song, Q. L. Org. Lett. 2015,
17, 1786-1789; (b) Yi, N.; Wang, R. J.; Zou, H. X.; He, W. B.; Fu,
W. Q.; He, W. M. J. Org. Chem. 2015, 80, 5023-5029. (c) Zhou,
M.; Zhou, Y.; Song, Q. Chem. Eur. J. 2015, 21, 10654-10659; (d)
Zhang, G. Y.; Li, C. K.; Li, D. P.; Zeng, R. S.; Shoberu, A.; Zou,
J. P. Tetrahedron, 2016, 72, 2972-2978.
14. (a) Hu J.;, Zhao, N.; Yang, B.; Wang, G.; Guo, L. N.; Liang, Y.
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Acknowledgments
We acknowledge financial support from the Chinese National
Natural Science Foundation (No. 21072178 and No. 20472076),
and the 2016 Science and Technology Innovation Team in Henan
Province.
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