Efficient synthesis of α-substituted-α-arylmethyl phosphonates using trichloroacetimidate C–C coupling method

Article abstract of DOI:10.1016/j.tet.2018.02.033

A simple convenient protocol for the synthesis of diethyl α,α-diaryl methylphosphonate derivatives 5a-f, 6b-f, 7a-f and 8a-f, diethyl α-alkenyl α-aryl methylphosphonates 9a-d and 10a-d and α-(oxoalkyl) α-aryl methylphosphonate 11a-d and 12a-d is described. Trichloroacetimidates 3a-d were treated with activated arenes, styrene, allyltrimethylsilane or silylenol ethers C-nucleophiles in the presence TMSOTf to afford the desired products in good yields and short reaction time.

Full text of DOI:10.1016/j.tet.2018.02.033

Accepted Manuscript
Efficient synthesis of α-substituted-α-arylmethyl phosphonates using
trichloroacetimidate C-C coupling method
Walid Fathalla, Pavel Pazdera, Samir El-Rayes, Ibrahim.A.I. Ali
PII:
S0040-4020(18)30167-4
10.1016/j.tet.2018.02.033
TET 29304
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 29 December 2017
Revised Date: 12 February 2018
Accepted Date: 14 February 2018
Please cite this article as: Fathalla W, Pazdera P, El-Rayes S, Ali IAI, Efficient synthesis of α-
substituted-α-arylmethyl phosphonates using trichloroacetimidate C-C coupling method, Tetrahedron
(2018), doi: 10.1016/j.tet.2018.02.033.
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ACCEPTED MANUSCRIPT
Efficient
Synthesis
of
α-substituted-α-arylmethyl
phosphonates Using Trichloroacetimidate C-C Coupling
Method
Walid Fathalla*, Pavel Pazdera Samir El-Rayes and Ibrahim. A. I. Ali
OR1
OR1
R2
O
R2
O
acceptor
C-nucleophiles
NH
Cl3C
O
P
O
acceptor
C-nucleophiles
TMSOTf, CH2Cl2,
25 oC, 4h.
P
O
O
O
3a-d
5-8(a-f)
9-12(a-d)
40 compounds

ACCEPTED MANUSCRIPT
Efficient Synthesis of α-substituted-α-arylmethyl
phosphonates Using Trichloroacetimidate C-C Coupling
Method
Walid Fathallaa*, Pavel Pazderab Samir El-Rayesc and Ibrahim. A. I. Alic
aDepartment of Physics and Math., Faculty of Engineering, Port-Said University,
Port-Said, Egypt.
b Centre for Syntheses at Sustainable Conditions and Their Management, Faculty of
Science, Masaryk University, Brno, Czech Republic.
cDepartment of Chemistry, Faculty of Science, Suez Canal University, Ismailia,
Egypt.
Abstract
A
simple convenient protocol for the synthesis of diethyl α,α-diaryl
methylphosphonate derivatives 5a-f, 6b-f, 7a-f and 8a-f, diethyl α-alkenyl α-aryl
methylphosphonates 9a-d and 10a-d and α-(oxoalkyl) α-aryl methylphosphonate
11a-d and 12a-d is described. Trichloroacetimidates 3a-d were treated with activated
arenes, styrene, allyltrimethylsilane or silylenol ethers C-nucleophiles in the presence
TMSOTf to afford the desired products in good yields and short reaction time
Keywords: α-hydroxyphosphonates; trichloroacetimidate coupling method; C-
nucleophile acceptors.
1

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INTRODUCTION
Phosphonic acid and phosphonates are very important class of organic compounds
owing to their wide variety of applications in all fields; industrial, agricultural,
milatary and medicinal.1-3 Particularly α-functionalized phosphonic acids (containing
P-C bond) are valuable intermediates for the preparation of medicinal compounds and
synthetic intermediates.4-8 α-Alkyl Phosphonates could be prepared by the reaction of
an aryl/alkyl halide with trialkyl phosphite via P-C bond formation as described by
Michaelis-Arbuzov reaction.9, 10 Also, arylphosphonates are prepared via aryl C–P
bond formation by the palladium-catalyzed cross-coupling of dialkylphosphite with
aromatic electrophiles.11,12 Great attention was focused on α-hydroxy phosphonates
since it enables a mild process for the preparation of α-substituted methyl
phosphonates13 with promising biological activities.14 α-Hydroxyphosphonates is
prepared according to the Abramov and Pudovik method15,16 by the reaction of
aldehydes with di and trialkyl phosphite in the presence of base.
Trichloroacetimidates have been used widely in organic synthesis for C-O or C-C
bond formations.17-21 This strategy involves the transformation of the substrate alcohol
into the corresponding trichloroacetimidate by the reaction with trichloroacetonitrile
in the presence of a base. A range of C-nucleophiles react with the
trichloroacetimidate intermediates in the presence of a Lewis acid to give the desired
products, Scheme 1.
excellent leaving group.
NH
acceptor
C-nucleophiles
activation
CCl3CN
OH
O
CCl3
O
Lewis acid
O
P
O
P
O
O
P
O
O
acceptor
O
H3CO
O
H3CO
C-nucleophiles
H3CO
Scheme 1. The strategy of trichloroacetimidate coupling method.
2

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In continuation of our interest in the chemistry of phosphonate
trichloroacetimidates we targeted a number of diethyl α,α-diaryl methylphosphonate
derivatives 5a-f, 6b-f, 7a-f and 8a-f, diethyl α-alkenyl α-aryl methylphosphonates
9a-d and 10a-d and α-(oxoalkyl) α-aryl methylphosphonate 11a-d and 12a-d.
Results and discussion.
Nucleophilic addition of diethyl phosphite to benzaldehydes 1a-d in 1:1 molar ratio,
in the presence of triethylamine as a base gave the diethyl (hydroxy)arylmethyl
phosphonates 2a-d in good yields (Scheme 2). The corresponding
trichloroacetimidates 3a-d were synthesized by the addition of trichloroacetonitrile to
α-hydroxyphosphonates 2a-d in the presence of DBU, as shown in Scheme 2.
OR1
OR1
R2
O
R2
O
OR1
CCl3CN
DBU
R2
NH
NEt3
HPO(OC2H5)2
+
70 oC, 3 h.
CH2Cl2
25 oC, 2 h.
Cl3C
O
P
O
HO
P
O
O
O
H
O
1a-d
2a-d
3a-d
OR1
R2
1-3
a
b
OCH3
OCH3
H
CH3O
O
c
d
CH3O
CH3O
O
Scheme 2. Synthesis of diethyl (2,2,2-trichloro-1-iminoethoxy)arylmethyl
phosphonates 3a-d.
The reaction of trichloroacetimidates 3a-d with methoxy-substituted arenes 4a-f in the
presence of catalytic amount of TMSOTf at room temperature gave readily the
corresponding diethyl α,α-diaryl methylphosphonate derivatives 5a-f, 6b-f, 7a-f and
8a-f in 47-91% yield (Scheme 3, Table 1).
3

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R7
R6
R3
R4
OR1
OR1
R2
R2
O
R5
R5
4(a-f)
NH
R4
R3
O
P
TMSOTf, CH2Cl2,
25 oC, 4h.
Cl3C
O
P
O
O
R6
O
O
R7
3a-d
3a-d,
5a-f, 6b-f and 7-8a-f
OR1
R2
compounds 4a-f, 5a-f, 6b-f and 7-8a-f
R3-7 groups are presented in table 1
5a-f, 6b-f and 7-8a-f
a
b
OCH3
OCH3
H
a: R3= CH3O, R4-7=H
b: R3-4= CH3O, R5-7=H
c: R3, 5= CH3O, R4, 6-7=H
d: R5, 7= CH3O, R3,4, 6=H
e: R3-5= CH3O, R6-7=H
f: R3,5,6= CH3O, R4,7=H
3a
3b
3c
5a-f
CH3O
5b, 6b-f
7a-f
O
CH3O
CH3O
c
d
3d
8a-f
O
Scheme 3. Synthesis of diethyl α,α-diaryl methylphosphonate derivatives 5a-f, 6b-f,
7a-f and 8a-f.
The structures of the isolated products were confirmed by isolation of the same
product using different reaction pathways i.e: from two different substrates. Thus,
diethyl (3,4-dimethoxyphenyl)(4-methoxyphenyl)methylphosphonate (5b) was
prepared either by the reaction of diethyl (2,2,2-trichloro-1-iminoethoxy)(4-
methoxyphenyl) methylphosphonate (3a) with 1,2-dimethoxybenzene (4b) in the
presence of TMSOTf to afford 5b in 84 % yield or by the reaction of diethyl (2,2,2-
trichloro-1-iminoethoxy)(3,4-dimethoxyphenyl)methylphosphonate (3b) with anisole
(4a) in the presence of TMSOTf to afford 5b in 87 % yield.
4

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Table 1. Structures of diethyl α,α-diaryl methylphosphonate derivatives 5a-f, 6b-f,
7a-f and 8a-f.
Yields
(isolated)
Yields
(isolated)
No.
Structure
No.
Structure
OR1
OR1
R2
O
R2
78%
-
69%
95%
81%
90%
86%
71%
5a
6a
7a
8a
5d
6d
7d
8d
O
O
O
P
O
P
O
O
O
O
OR1
OR1
R2
O
R2
O
84%a, 87%b
91%
63%
76%
89%
86%
5b
6b
7b
8b
5e
6e
7e
8e
O
O
O
O
76%
87%
P
O
P
O
O
O
OR1
OR1
R2
O
R2
72%
84%
71%
78%
59%
86%
63%
47%
5c
6c
7c
8c
5f
6f
7f
8f
O
O
O
P
O
P
O
O
O
O
O
O
Compound 5b is formed from two reaction pathways:
a: isolated yield by the reaction of 1,2-dimethoxy benzene (4b) with diethyl (2,2,2-trichloro-1-
iminoethoxy)(4-methoxyphenyl)methyl phosphonate (3a) (R1=CH3, R2= H).
b: isolated yield by the reaction of anisole (4a) with diethyl (2,2,2-trichloro-1-iminoethoxy)(3,4-
dimethoxyphenyl)methyl phosphonate (3b).
The structure assignment of derivatives 5a-f, 6b-f, 7a-f and 8a-f was based on 1H, 13C
and 31P NMR spectral and physicochemical analysis. The 31P-NMR spectra were used
as an indicator for the purity of the isolated compounds showing a single peak
resonance. For example, the 31P-NMR spectrum of 5a showed a signal at δ= 27.3 ppm
1
which is characteristic of a phosphonate group. The H NMR spectrum of diethyl
5

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bis(4-methoxyphenyl)methylphosphonate 5a gave signals at δ= 1.12-1.17, 3.86-4.06,
3.78 and 3.80 ppm, associated with two CH3CH2O groups and two OCH3 groups
respectively. The 1H NMR spectrum of 5a also shows a doublet at δ = 4.31 ppm with
2
coupling constant 24.0 Hz typically associated with JH-P coupling. This signal is
common for all diethyl α,α-diaryl methylphosphonate derivatives 5a-f, 6b-f, 7a-f and
8a-f and was used to confirm the C–P linkage. The 13C NMR spectrum of 5a
displayed five doublets at δ= 16.3, 16.4, 49.5, 62.3 and 62.6 ppm with C-P coupling
constants 5.2, 5,2, 138.9, 6.8 and 6.8 Hz associated with two CH3, CH-P and two CH2
groups, respectively.
This method has the advantage of regioselective alkylation of a variety of π-
electron rich benzene derivatives with α-aryl methyl phosphonate residue via C-C
bond formation at room temperature in high yields.
Our next target, was the functionalization of α-arylmethyl phosphonates with
alkene C-nucleophiles. Thus, trichloroacetimidates 3a-d were reacted separately with
allyltrimethylsilane and styrene in the presence of TMSOTf in CH2Cl2 to provide the
diethyl α-alkenyl-α-aryl methylphosphonates 9a-d and 10a-d, respectively (Scheme
4).
6

ACCEPTED MANUSCRIPT
OR1
R2
OR1
OR1
R2
O
R2
O
Si(CH3)3
NH
O
TMSOTf, CH2Cl2,
25 oC, 4 h.
TMSOTf, CH2Cl2,
25 oC, 4 h.
Cl3C
O
P
P
O
P
O
O
O
O
O
10a-d
3a-d
9a-d
a: 72%
b: 75%
c: 61%
d: 67%
a: 78%
b: 88%
c: 76%
d: 62%
OR1
R2
3a-d, 9-10
a
b
OCH3
OCH3
H
CH3O
O
c
d
CH3O
CH3O
O
Scheme 4. Synthesis of diethyl alkenyl α-aryl methylphosphonates 9a-d and 10a-d.
Incorporating a ketone functional group at the β-position with respect to the α-
arylmethyl phosphonate was successfully achieved by the reaction of
trichloroacetimidate 3a-d with 1-trimethylsiloxycyclohexene or 1-phenyl-1-
trimethylsiloxyethylene in CH2Cl2 and in the presence of TMSOTf, which afforded α-
(oxoalkyl) α-aryl methylphosphonates 11a-d and 12a-d, respectively (Scheme 5).
OSi(CH3)3
OR1
OR1
OSi(CH3)3
OR1
R2
O
R2
O
R2
O
NH
O
O
TMSOTf, CH2Cl2,
25 oC, 4 h.
TMSOTf, CH2Cl2,
25 oC, 4 h.
Cl3C
O
P
O
P
O
P
O
O
O
O
3a-d
OR1
11a-d
12a-d
R2
3a-d, 11-12
a: 56%
b: 74%
c: 53%
d: 62%
a: 82%
b: 75%
c: 88%
d: 66%
a
b
OCH3
OCH3
H
CH3O
O
c
d
CH3O
CH3O
O
Scheme 5. Synthesis of α-(oxoalkyl) α-aryl methylphosphonate 11a-d and 12a-d.
CONCLUSION
7

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In conclusion, an efficient method for the synthesis of various phosphonate
derivatives using a trichloroacetimidate coupling method was introduced.
Trichloroacetimidates 3a-d reacted with a range C-nucleophiles in the presence of
TMSOTf to afford the desired products via C-C bond formation.
Experimental
Solvents were purified and dried by standard procedures. The boiling point range of
o
the petroleum ether used was 40-60 C. Thin layer chromatography (TLC): silica gel
60 F254 plastic plates (E. Merck, layer thickness 0.2 mm) detected by UV absorption.
Elemental analyses were performed on a Flash EA-1112 instrument at the
Microanalytical laboratory, Faculty of Science, Suez Canal University, Ismailia,
Egypt. Melting points were determined on a Buchi 510 melting-point apparatus and
1
31
the values are uncorrected. The H, 13C and P NMR spectra were recorded at 300
MHz, 75.5 MHz and 194.4 MHz, respectively (Bruker AC 300 and 500) in CDCl3
with tetramethylsilane as an internal standard. The NMR analysis were performed at
Organic Chemistry Department Masaryk University, Brno, Czech Republic. 3,4-
Dimethoxybenzaldehyde 1b 3-methoxy-4-(prop-2-ynyloxy)benzaldehyde 1c and 3-
methoxy-4-(allyloxy)benz-aldehyde 1d were prepared by alkylation of vanillin with
dimethyl sulfate, allyl bromide and propargyl bromide in the presence of K2CO3 in
acetone as described in the literature.22-23 C-arene nucleophiles 4(b-f) were prepared
from the reaction of the corresponding phenols with dimethyl sulfate in the presence
of K2CO3 in acetone as described in the literature.22
Diethyl α-hydroxy-α-aryl methylphosphonate 2a-d.23
To a mixture of diethyl phosphonate (20.7 g, 150 mmol) and triethylamine (1.09 g,
11 mmol) was added aldehydes 1a-d (150 mmol) portionwise during a period of 1 h
at 50 °C-70 °C. The reaction mixture was subsequently stirred at 70 °C for 2 h. After
8

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cooling it was left over night to give white crystals, which were filtered and washed
filter and wash with cold toluene and then recrystallized from toluene to give pure
products.
Diethyl hydroxy(4-methoxyphenyl)methyl phosphonate (2a). 34.4 g, Yield 84%,
1
white crystals. mp 90-91 °C. H-NMR spectrum, (300 MHz, CDCl3), δ, ppm (J, Hz):
1.19-1.29 (m, 6 H, 2 CH3), 3.80 (s, 3 H, OCH3), 3.89-4.10 (m, 4 H, 2 CH2), 4.33 (bs,
1 H, OH), 4.95 (d, JHP = 9.0 Hz, 1 H, CHP), 6.87 (d, J = 9.0 Hz, 2 H, H-Ar), 7.39-
13
7.43 (m, 2 H, H-Ar). C-NMR (75.0 MHz, CDCl3), δ, ppm: 16.3 (d, JCP = 4.0 Hz,
CH3), 16.4 (d, JCP = 4.0 Hz, CH3), 55.2 (OCH3), 62.9 (d, JCP = 7.6 Hz, CH2OP), 63.2
(d, JCP = 7.6 Hz, CH2OP), 70.3 (d, JCP = 161.6 Hz, CHP), 113.0, 113.7, 128.4, 128.5,
31
128.8, 159.5 (C-Ar). P-NMR (194.4 MHz, CDCl3), δ, ppm: 21.7 (P). Found, %: C,
52.39; H, 6.81. For C12H19O5P (274.1). Calculated, %: C, 52.55; H, 6.98.
Diethyl hydroxy(3,4-dimethoxyphenyl)methyl phosphonate (2b). 40.6 g, Yield
1
89% white crystals. mp 101-103 °C. H-NMR spectrum, (300 MHz, CDCl3), δ, ppm
(J, Hz): 1.16-1.26 (m, 6 H, 2 CH3), 3.83 (s, 3 H, OCH3), 3.88 (s, 3 H, OCH3), 3.92-
4.07 (m, 4 H, 2 CH2), 4.62 (bs, 1H, OH), 4.89 (d, JHP = 9.0 Hz, 1 H, CHP), 6.81 (d, J
= 9.0 Hz, 1 H, H-Ar), 6.95-7.07 (m, 1 H, H-Ar), 7.08 (s, 1 H, H-Ar). 13C-NMR (75.0
MHz, CDCl3), δ, ppm: 16.3 (d, JCP = 4.0 Hz, CH3), 16.4 (d, JCP = 4.0 Hz, CH3), 55.8
(OCH3), 55.9 (OCH3), 62.9 (d, JCP = 7.6 Hz, CH2OP), 63.2 (d, JCP = 7.6 Hz, CH2OP),
70.4 (d, JCP = 161.6 Hz, CHP), 110.5, 110.8, 110.9, 129.3, 148.7, 148.8 (C-Ar). 31P-
NMR (194.4 MHz, CDCl3), δ, ppm: 21.7 (P). Found, %: C, 51.12; H, 6.89. For
C13H21O6P (304.1). Calculated, %: C, 51.31; H, 6.96.
Diethyl hydroxy(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)methyl phosphonate
(2c). 36.9 g, Yield 75%, white crystals. mp. 87-88 °C. 1H-NMR spectrum, (300 MHz,
9

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CDCl3), δ, ppm (J, Hz): 1.19-1.37 (m, 6 H, 2 CH3), 2.50 (t, J= 3.0 Hz, 1 H, CH), 3.86
(s, 3 H, OCH3), 3.92-4.17 (m, 4 H, 2 CH2), 4.39 (bs, 1 H, OH), 4.74 (d, J = 3.0 Hz, 2
H, OCH2), 4.93 (d, JHP = 9.0 Hz, 1 H, CHP), 6.99-7.12 (m, 3 H, H-Ar). 13C-NMR
(75.0 MHz, CDCl3), δ, ppm: 16.3 (d, JCP = 4.0 Hz, CH3), 16.4 (d, JCP = 4.0 Hz, CH3),
55.9 (OCH3), 56.8 (OCH2), 63.0 (d, JCP = 7.6 Hz, CH2OP), 63.2 (d, JCP = 7.6 Hz,
CH2OP), 70.5 (d, JCP = 160.8 Hz, CHP), 75.8 (C≡CH), 78.5 (C≡CH), 110.9, 114.0,
31
119.5, 130.7, 146.6, 149.6 (C-Ar). P-NMR (194.4 MHz, CDCl3), δ, ppm: 21.5 (P).
Found, %: C, 54.68; H, 6.43. For C15H21O6P (328.1). Calculated, %: C, 54.88; H,
6.45.
Diethyl (4-(allyloxy)-3-methoxyphenyl)(hydroxy)methyl phosphonate (2d). 41.0
g, Yield 83%, white crystals. mp 108-109 °C. 1H-NMR (300.0 MHz, CDCl3) δ= 1.20-
1.30 (m, 6 H, 2 CH3), 3.88 (s, 3 H, OCH3), 3.91-4.11 (m, 4 H, 2 CH2), 4.61 (d, J= 3.0
Hz, 2 H, OCH2), 4.94 (d, JHP = 9.0 Hz, 1 H, CHP), 5.28 (d, J= 18 Hz, 1 H,
OCH2CH=CH2), 5.39 (d, J= 18 Hz, 1 H, OCH2CH=CH2), 6.02-6.13 (m, 1 H, CH),
6.84-7.28 (m, 3 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 4.0 Hz,
CH3), 16.4 (d, JCP = 4.0 Hz, CH3), 55.9 (OCH3), 63.0 (d, JCP = 5.3 Hz, CH2OP), 63.2
(d, JCP = 5.3 Hz, CH2OP), 69.9 (OCH2CH=CH2), 70.5 (d, JCP = 160.8 Hz, CHP),
110.8, 113.6 (C-Ar), 117.9 (OCH2CH=CH2), 119.5, 129.5 (C-Ar), 133.3
(OCH2CH=CH2), 147.9, 149.3 (CAr); 31P-NMR (194.4 MHz, CDCl3) δ= 21.6 (P).
Found, %: C, 54.23; H, 6.80. For C15H23O6P (330.3). Calculated, %: C, 54.54; H,
7.02.
Preparation of diethyl (2,2,2-trichloro-1-iminoethoxy)arylmethyl phosphonates
3a-d.
10

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A stirred solution of diethyl hydroxy(aryl)methylphosphonate 2a-d (10.0 mmol) in
dry dichloromethane (30 mL) was treated with trichloroacetonitrile (2.9 mL, 20
mmol) and DBU (0.8 mL, 5.0 mmol). The reaction mixture was stirred at room
temperature for 2 h. The solvent was evaporated under reduced pressure and the
product was purified by column chromatography 5 % triethylamine in
dichloromethane, to give 3a-d as brownish oil.
Diethyl (2,2,2-trichloro-1-iminoethoxy)(4-methoxyphenyl)methyl phosphonate
1
(3a). 3.6 g, Yield 87%, brownish oil. H-NMR spectrum, (300 MHz, CDCl3), δ, ppm
(J, Hz): 1.20-1.27 (m, 6 H, 2 CH3), 3.76 (s, 3 H, OCH3), 3.97-4.16 (m, 4 H, 2 CH2),
6.20 (d, JHP = 15.0 Hz, 1 H, CHP), 6.86 (d, J = 9.0 Hz, 2 H, H-Ar), 7.44 (d, J = 6.0
Hz, 2 H, H-Ar), 8.51 (brs, 1 H, NH). 13C-NMR (75.0 MHz, CDCl3), δ, ppm: 16.3 (d,
JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 55.2 (OCH3), 63.3 (d, JCP = 6.0 Hz,
CH2OP), 63.5 (d, JCP = 6.0 Hz, CH2OP), 74.8 (d, JCP = 172.1 Hz, CHP), 90.9 (CCl3),
113.8, 113.9, 124.7, 124.7, 129.2, 129.3 (C-Ar), 161.1 (C=N). 31P-NMR (194.4 MHz,
CDCl3), δ, ppm: 16.5 (P). Found, %: C, 39.96; H, 4.42; N, 3.29. For C14H19Cl3NO5P
(417.0). Calculated, %: C, 40.17; H, 4.57; N, 3.35.
Diethyl (2,2,2-trichloro-1-iminoethoxy)(3,4-dimethoxyphenyl)methyl phosph-
onate (3b). 4.2 g, Yield 94%, brownish oil. 1H-NMR spectrum, (300 MHz, CDCl3), δ,
ppm (J, Hz): 1.25-1.32 (m, 6 H, 2 CH3), 3.89 (s, 6 H, 2 OCH3), 4.02-4.23 (m, 4 H, 2
CH2), 6.23 (d, JHP = 12.0 Hz, 1 H, CHP), 6.86 (d, J = 9.0 Hz, 1 H, H-Ar), 7.09 (d, J =
9.0 Hz, 2 H, H-Ar), 8.53 (brs, 1 H, NH). 13C-NMR (75.0 MHz, CDCl3), δ, ppm: 16.4
(d, JCP = 6.0 Hz, CH3), 16.5 (d, JCP = 6.0 Hz, CH3), 55.8 (OCH3), 63.3 (d, JCP = 6.0
Hz, CH2OP), 63.7 (d, JCP = 6.0 Hz, CH2OP), 74.9 (d, JCP = 172.1 Hz, CHP), 91.0
(CCl3), 110.8, 120.6, 120.7, 125.2, 148.9, 149.5 (C-Ar), 161.2 (C=N). 31P-NMR
11

ACCEPTED MANUSCRIPT
(194.4 MHz, CDCl3), δ, ppm: 16.5 (P). Found, %: 40.02; H, 4.67; N, 3.05. For
C15H21Cl3NO6P (447.0). Calculated, %: C, 40.15; H, 4.72; N, 3.12.
Diethyl (2,2,2-trichloro-1-iminoethoxy)(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)
1
methyl phosphonate (3c). 3.8 g, Yield 80%, brownish oil. H-NMR spectrum, (300
MHz, CDCl3), δ, ppm (J, Hz): 1.22 (m, 6 H, 2 CH3), 2.50 (s, 1 H, CH), 3.85 (s, 3 H,
OCH3), 3.99-4.16 (m, 4 H, CH, 2 CH2), 4.73 (d, J= 3.0 Hz, 2 H, OCH2), 6.20 (d, JHP
= 12.0 Hz, 1 H, CHP), 6.99-7.28 (m, 3 H, H-Ar), 8.53 (brs, 1 H, NH). 13C-NMR (75.0
MHz, CDCl3), δ, ppm: 16.4 (d, JCP = 6.0 Hz, CH3), 16.5 (d, JCP = 6.0 Hz, CH3), 55.9
(OCH3), 56.7 (OCH2), 63.3 (d, JCP = 6.8 Hz, CH2OP), 63.6 (d, JCP = 6.8 Hz, CH2OP),
74.1 (d, JCP = 171.4 Hz, CHP), 75.9 (C≡CH), 78.4 (C≡CH), 90.9 (CCl3), 111.2, 113.9,
31
120.3, 126.6, 147.3, 149.6 (C-Ar), 161.1 (C=N). P- NMR (194.4 MHz, CDCl3), δ,
ppm: 16.3 (P). Found, %: C, 43.11; H, 4.36; N, 2.82. For C17H21Cl3NO6P (471.0).
Calculated, %: C, 43.20; H, 4.48; N, 2.96.
Diethyl
(2,2,2-trichloro-1-iminoethoxy)(4-(allyloxy)-3-methoxyphenyl)methyl
phosphonate (3d). 4.1 g, Yield 93%, brownish oil. 1H-NMR (300.0 MHz, CDCl3) δ=
1.05-1.12 (m, 6 H, 2 CH3), 3.67 (s, 3 H, OCH3), 3.82-4.00 (m, 4 H, 2 CH2), 4.38 (d,
J= 6.0 Hz, 2 H, OCH2), 5.07 (d, J= 12 Hz, 1 H, OCH2CH=CH2), 5.20 (d, J= 18 Hz, 1
H, OCH2CH=CH2), 5.80-5.91 (m, 1 H, CH), 6.08 (d, JHP = 15.0 Hz, 1 H, CHP), 6.69
13
(d, J= 7.0 Hz, 1 H, H-Ar), 6.87-6.95 (m, 2 H, H-Ar), 8.49 (s, 1H, NH). C- NMR
(75.0 MHz, CDCl3) δ= 16.4 (d, JCP = 6.0 Hz, CH3), 16.5 (d, JCP = 6.0 Hz, CH3), 55.7
(OCH3), 63.2 (d, JCP = 7.6 Hz, CH2OP), 63.4 (d, JCP = 7.6 Hz, CH2OP), 69.6
(OCH2CH=CH2), 74.6 (d, JCP = 171.4 Hz, CHP), 90.8 (CCl3), 111.2, 112.9 (C-Ar),
117.7 (OCH2CH=CH2), 120.5, 125.4, 133.1 (OCH2CH=CH2), 148.3, 149.2 (C-Ar),
12

ACCEPTED MANUSCRIPT
31
160.7 (C=NH). P-NMR (194.4 MHz, CDCl3) δ= 16.3 (P). Found, %: C, 42.84; H,
4.68. For C17H23Cl3NO6P (474.7). Calculated, %: C, 43.01; H, 4.88.
General procedure for the α,α-diaryl methyl phosphonate derivatives 5a-f, 6b-f,
7a-f and 8a-f. TMSOTf (0.03 mL, 0.14 mmol) was added to a solution of
trichloroacetimidate 3a-d (1.4 mmol) and C-nucleophiles (1.4 mmol) 4a-f in
dichloromethane (40 mL). The reaction mixture was stirred at room temperature for 4
h. The reaction mixture was neutralized with solid sodium bicarbonate, filtered and
concentrated under reduced pressure. The residue was purified by flash
chromatography1:2 pet.ether/ethylacetate to give the α,α-diaryl methylphosphonate
5a-f, 6b-f, 7a-f and 8a-f as a colourless oil.
Diethyl bis-(4-methoxyphenyl)methyl phosphonate (5a). From anisole (4a) and
1
trichloroacetimidate 3a, 0.65 g, Yield 78%, colorless oil. H-NMR (300.0 MHz,
CDCl3) δ= 1.12-1.17 (m, 6 H, 2 CH3), 3.78 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3),
3.86-4.06 (m, 4 H, 2 CH2), 4.31 (d, JHP = 24.0 Hz, 1 H, CHP), 6.84 (d, J = 9.0 Hz, 4
H, H-Ar), 7.43 (d, J = 9.0 Hz, 4 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d,
JCP = 5.2 Hz, CH3), 16.4 (d, JCP = 5.2 Hz, CH3), 49.5 (d, JCP = 138.9 Hz, CHP), 55.1
(OCH3), 55.2 (OCH3), 62.3 (d, JCP = 6.8 Hz, CH2OP), 62.6 (d, JCP = 6.8 Hz, CH2OP),
31
113.9, 114.7, 120.5, 129.1, 129.3, 130.3, 130.4, 158.6 (C-Ar). P-NMR (194.4MHz,
CDCl3) δ= 25.6 (P). Found, %: C, 62.58; H, 6.88. For C19H25O5P (364.4). Calculated,
%: C, 62.63; H, 6.92.
Diethyl (3,4-dimethoxyphenyl)(4-methoxyphenyl)methyl phosphonate (5b).
Method A. From 1,2-dimethoxy benzene (4b) and diethyl (2,2,2-trichloro-1-
iminoethoxy)(4-methoxyphenyl)methyl phosphonate (3a), 0.66 g, Yield 84%,
colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.13 (t, J = 12.0 Hz, 6 H, 2 CH3), 3.66
13

ACCEPTED MANUSCRIPT
(s, 3 H, OCH3), 3.73 (s, 3 H, OCH3), 3.86 (s, 3 H, OCH3), 3.88-3.96 (m, 4 H, 2 CH2),
4.32 (d, JHP = 27.0 Hz, 1 H, CHP), 6.71-6.95 (m, 3 H, H-Ar), 6.98-7.05 (m, 2 H, H-
Ar), 7.35-7.39 (m, 2 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz,
CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 49.7 (d, JCP = 138.9 Hz, CHP), 55.0 (OCH3), 55.7
(OCH3), 55.8 (OCH3), 62.2 (d, JCP = 6.8 Hz, CH2OP), 62.7 (d, JCP = 6.8 Hz, CH2OP),
111.2, 112.7, 112.8, 113.9, 121.5, 121.6, 129.1, 129.7, 130.3, 148.1, 148.8, 158.6 (C-
Ar). 31P-NMR (194.4 MHz, CDCl3) δ= 25.5 (P). Found, %: C, 60.76; H, 6.79. For
C20H27O6P (394.4). Calculated, %: C, 60.91; H, 6.90.
Method B. From anisole (4a) and diethyl (2,2,2-trichloro-1-iminoethoxy)(3,4-
dimethoxyphenyl)methyl phosphonate (3b), 0.63 g, Yield 87%.
Diethyl (2,4-dimethoxyphenyl)(4-methoxyphenyl)methyl phosphonate (5c). From
1,3-dimethoxy benzene (4c) and trichloroacetimidate 3a, 077 g, Yield 72%, colorless
oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.09-1.15 (m, 6 H, 2 CH3), 3.71 (s, 3 H, OCH3),
3.73 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.84-4.04 (m, 4 H, 2 CH2), 4.97 (d, JHP
=
27.0 Hz, 1 H, CHP), 6.42-6.50 (m, 2 H, H-Ar), 6.79 (d, J = 9.0 Hz, 2 H, H-Ar), 7.41
13
(d, J = 9.0 Hz, 2 H, H-Ar), 7.77 (d, J = 9.0 Hz, 1 H, H-Ar). C-NMR (75.0 MHz,
CDCl3) δ= 16.2 (d, JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 40.2 (d, JCP
=
141.9 Hz, CHP), 55.1 (OCH3), 55.5 (OCH3), 55.6 (OCH3), 62.5 (d, JCP = 6.8 Hz,
CH2OP), 62.7 (d, JCP = 6.8 Hz, CH2OP), 98.7, 104.4, 106.1, 113.7, 118.0, 129.2,
130.3, 130.6, 157.5, 157.7, 158.5, 159.9 (C-Ar). 31P-NMR (194.4MHz, CDCl3) δ=
26.7 (P). Found, %: C, 60.78; H, 6.85. For C20H27O6P (394.4). Calculated, %: C,
60.91; H, 6.90.
Diethyl (2,5-dimethoxyphenyl)(4-methoxyphenyl)methyl phosphonate (5d). From
1,4-dimethoxy benzene (4d) and trichloroacetimidate 3a, 0.68 g, Yield 81%,
14

ACCEPTED MANUSCRIPT
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.10-1.16 (m, 6 H, 2 CH3), 3.74 (s, 3
H, OCH3), 3.78 (s, 6 H, 2 OCH3), 3.84-4.04 (m, 4 H, 2 CH2), 4.99 (d, JHP = 27.0 Hz, 1
H, CHP), 6.74-6.83 (m, 4 H, H-Ar), 7.44-7.56 (m, 3 H, H-Ar). 13C-NMR (75.0 MHz,
CDCl3) δ= 16.2 (d, JCP = 5.2 Hz, CH3), 16.3 (d, JCP = 5.2 Hz, CH3), 41.0 (d, JCP
=
141.2 Hz, CHP), 55.1 (OCH3), 55.7 (OCH3), 56.4 (OCH3), 61.9 (d, JCP = 6.8 Hz,
CH2OP), 62.6 (d, JCP = 6.8 Hz, CH2OP), 112.1, 113.0, 113.8, 116.0, 127.0, 129.0,
130.6, 130.7, 150.9, 151.0, 153.6, 158.5 (C-Ar). 31P-NMR (194.4MHz, CDCl3) δ=
26.2 (P). Found, %: C, 60.82; H, 6.84. For C20H27O6P (394.4). Calculated, %: C,
60.91; H, 6.90.
Diethyl (4-methoxyphenyl)(2,3,4-trimethoxyphenyl)methyl phosphonate (5e).
From 1,2,3-trimethoxy benzene (4e) and trichloroacetimidate 3a, 0.94 g, Yield 63%,
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.15-1.27 (m, 6 H, 2 CH3), 3.69 (s, 3
H, OCH3), 3.72 (s, 3 H, OCH3), 3.76 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3), 3.84-4.00
(m, 4 H, 2 CH2), 4.86 (d, JHP = 24.0 Hz, 1 H, CHP), 6.62 (d, J = 9.0 Hz, 1 H, H-Ar),
6.75-6.78 (m, 2 H, H-Ar), 7.38-7.41 (m, 2 H, H-Ar), 7.60 (d, J = 9.0 Hz, 1 H, H-Ar).
13C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 5.2 Hz, CH3), 16.6 (d, JCP = 5.2 Hz,
CH3), 41.2 (d, JCP = 141.2 Hz, CHP), 55.1 (OCH3), 55.8 (OCH3), 60.5 (OCH3), 61.0
(OCH3), 62.3 (d, JCP = 6.7 Hz, CH2OP), 62.4 (d, JCP = 6.7 Hz, CH2OP), 107.3, 113.8,
123.5, 124.2, 124.3, 129.3, 129.4, 130.4, 130.5, 142.1, 151.5, 152.8, 158.5 (C-Ar).
31P-NMR (194.4MHz, CDCl3) δ=26.2 (P). Found, %: C, 59.26; H, 6.75. For
C21H29O7P (424.4). Calculated, %: C, 59.43; H, 6.89.
Diethyl (4-methoxyphenyl)(2,4,6-trimethoxyphenyl)methyl phosphonate (5f).
From 1,3,5-trimethoxy benzene (4f) and trichloroacetimidate 3a, 1.01 g, Yield 59%,
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.12-1.27 (m, 6 H, 2 CH3), 3.73 (s, 3
H, OCH3), 3.78 (s, 9 H, 3 OCH3), 3.94-4.02 (m, 4 H, 2 CH2), 5.16 (d, JHP = 27.0 Hz, 1
15

ACCEPTED MANUSCRIPT
H, CHP), 6.13 (s, 2 H, H-Ar), 6.76 (d, J = 9.0 Hz, 2 H, H-Ar), 7.41(d, J = 9.0 Hz, 2 H,
13
H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 4.5 Hz, CH3), 16.4 (d, JCP
=
4.5 Hz, CH3), 39.1 (d, JCP = 145.0 Hz, CHP), 55.1 (OCH3), 55.2 (OCH3), 55.6
(OCH3), 55.7 (OCH3), 62.0 (d, JCP = 7.6 Hz, CH2OP), 62.5 (d, JCP = 7.6 Hz, CH2OP),
91.1, 107.6, 113.3, 129.4, 130.6, 130.7, 158.1, 158.9, 160.5 (C-Ar). 31P-NMR
(194.4MHz, CDCl3) δ= 27.6 (P). Found, %: C, 59.32; H, 6.81. For C21H29O7P
(424.4). Calculated, %: C, 59.43; H, 6.89.
Diethyl bis(3,4-dimethoxyphenyl)methyl phosphonate (6b). From 1,2-dimethoxy
1
benzene (4b) and trichloroacetimidate 3b, 0.65 g, Yield 91%, colorless oil. H-NMR
(300.0 MHz, CDCl3) δ= 1.07 (t, J = 6.0 Hz, 6 H, 2 CH3), 3.76 (s, 3 H, OCH3), 3.80 (s,
3 H, OCH3), 3.88 (s, 3 H, OCH3), 3.90 (s, 3 H, OCH3), 3.93-3.96 (m, 4 H, 2 CH2),
4.25 (d, JHP = 24.0 Hz, 1 H, CHP), 6.73-6.76 (m, 2 H, H-Ar), 6.97-7.06 (m, 4 H, H-
13
Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 5.3 Hz, CH3), 16.4 (d, JCP = 5.3
Hz, CH3), 50.0 (d, JCP = 138.2 Hz, CHP), 55.7 (2 OCH3), 55.8 (2 OCH3), 62.2 (d, JCP
= 6.8 Hz, CH2OP), 62.6 (d, JCP = 6.8 Hz, CH2OP), 111.2, 112.7, 112.8, 121.5 121.6,
31
129.4, 129.5, 148.1, 148.8 (C-Ar). P-NMR (194.4MHz, CDCl3) δ=25.4 (P). Found,
%: C, 59.36; H, 6.77. For C21H29O7P (424.4). Calculated, %: C, 59.43; H, 6.89.
Diethyl (2,4-dimethoxyphenyl)(3,4-dimethoxyphenyl)methyl phosphonate (6c).
From 1,3-dimethoxy benzene (4c) and trichloroacetimidate 3b, 0.71 g, Yield 84%,
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.06-1.12 (m, 6H, 2 CH3), 3.72 (s, 3
H, OCH3), 3.77 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.85 (s, 3 H, OCH3), 3.88-3.98
(m, 4 H, 2 CH2), 4.91 (d, JHP = 27.0 Hz, 1 H, CHP), 6.39-6.48 (m, 2 H, H-Ar), 6.72
(d, J = 6.0 Hz, 1 H, H-Ar), 7.00-7.08 (m, 2 H, H-Ar), 7.77-7.88 (m, 1 H, H-Ar). 13C-
NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 7.6 Hz, CH3), 16.4 (d, JCP = 7.6 Hz, CH3),
40.6 (d, JCP = 141.2 Hz, CHP), 55.2 (OCH3), 55.6 (OCH3), 55.7 (OCH3), 55.8
16

ACCEPTED MANUSCRIPT
(OCH3), 62.3 (d, JCP = 6.8 Hz, CH2OP), 62.8 (d, JCP = 6.8 Hz, CH2OP), 98.7, 104.4,
111.1, 113.1, 118.1, 121.8, 129.9, 130.5, 147.8, 148.6, 157.5, 157.6 (C-Ar). 31P-NMR
(194.4MHz, CDCl3) δ= 26.5 (P). Found, %: C, 59.23; H, 6.78. For C21H29O7P (424.4).
Calculated, %: C, 59.43; H, 6.89.
Diethyl (2,5-dimethoxyphenyl)(3,4-dimethoxyphenyl)methyl phosphonate (6d).
1,4-dimethoxy benzene (4d) and trichloroacetimidate 3b, 0.66 g, Yield 90%, colorless
oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.11-1.17 (m, 6 H, 2 CH3), 3.74 (s, 3 H, OCH3),
3.76 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3), 3.91 (s, 3 H, OCH3), 3.96-4.06 (m, 4 H, 2
CH2), 5.04 (d, JHP = 24.0 Hz, 1 H, CHP), 6.75-6.82 (m, 3 H, H-Ar), 7.07-7.15 (m, 2
H, H-Ar), 7.55 (s, 1 H, C-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz,
CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 41.2 (d, JCP = 141.2 Hz, CHP), 16.2 (CH3), 16.3
(CH3), 55.5 (OCH3), 55.8 (OCH3), 55.7 (OCH3), 55.8 (OCH3), 62.3 (d, JCP = 6.8 Hz,
CH2OP), 62.7 (d, JCP = 6.8 Hz, CH2OP), 111.2, 112.1, 113.0, 113.2, 114.6, 115.9,
121.8, 126.9, 129.4, 148.0, 148.7, 153.6 (C-Ar). 31P-NMR (194.4MHz, CDCl3) δ=
26.1 (P). Found, %: C, 59.25; H, 6.79. For C21H29O7P (424.4). Calculated, %: C,
59.43; H, 6.89.
Diethyl (3,4-dimethoxyphenyl)(2,3,4-trimethoxyphenyl)methyl phosphonate (6e).
From 1,2,3-trimethoxy benzene (4e) and trichloroacetimidate 3b, 0.84 g, Yield 76%,
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.07-1.14 (m, 6H, 2 CH3), 3.77 (s, 3
H, OCH3), 3.80 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3), 3.85 (s, 3 H, OCH3), 3.89 (s, 3
H, OCH3), 3.90-4.00 (m, 4 H, 2 CH2), 4.88 (d, JHP = 24.0 Hz, 1 H, CHP), 6.65 (d, J =
9.0 Hz, 1 H, H-Ar), 6.77 (d, J = 9.0 Hz, 1 H, H-Ar), 7.01-7.10 (m, 2 H, H-Ar), 7.58-
13
7.61 (m, 1 H, H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz, CH3),
16.4 (d, JCP = 6.0 Hz, CH3), 39.4 (d, JCP = 141.2 Hz, CHP), 55.6 (OCH3), 55.7
(OCH3), 55.8 (OCH3), 55.9 (OCH3), 56.0 (OCH3), 61.7 (d, JCP = 6.8 Hz, CH2OP),
17

ACCEPTED MANUSCRIPT
61.8 (d, JCP = 6.8 Hz, CH2OP), 107.4, 111.2, 112.9, 113.0, 121.7, 121.8, 124.2, 129.8,
130.0, 142.2, 148.7, 152.8 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ= 26.1 (P). Found,
%: C, 58.01; H, 6.79. For C22H31O8P (454.5). Calculated, %: C, 58.14; H, 6.88.
Diethyl (3,4-dimethoxyphenyl)(2,4,6-trimethoxyphenyl)methyl phosphonate (6f).
From 1,3,5-trimethoxy benzene (4f) and trichloroacetimidate 3b, 0.74 g, Yield 86%,
1
colorless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.08-1.17 (m, 6 H, 2 CH3), 3.74 (s,
3H, OCH3), 3.76 (s, 3H, OCH3), 3.81 (s, 3H, OCH3), 3.83 (s, 3H, OCH3), 3.87 (s,
3H, OCH3), 3.91-4.00 (m, 4 H, 2 CH2), 5.12 (d, JHP = 27.0 Hz, 1 H, CHP), 6.10 (s, 2
H, H-Ar), 6.68-6.71 (m, 1 H, H-Ar), 6.93-7.20 (m, 2 H, H-Ar). 13C-NMR (75.0 MHz,
CDCl3) δ= 16.2 (d, JCP = 6.0 Hz, CH3), 16.3 (d, JCP = 6.0 Hz, CH3), 39.4 (d, JCP
=
144.2 Hz, CHP), 55.2 (OCH3), 55.4 (OCH3), 55.5 (OCH3), 55.6 (OCH3), 55.7
(OCH3), 61.6 (d, JCP = 6.8 Hz, CH2OP), 61.8 (d, JCP = 6.8 Hz, CH2OP), 91.1, 107.6,
31
107.7, 110.7, 113.3, 113.4, 121.8, 130.0, 147.4, 148.9 (C-Ar). P-NMR (194.4MHz,
CDCl3) δ= 27.3. Found, %: C, 57.92; H, 6.62. For C22H31O8P (454.5). Calculated, %:
C, 58.14; H, 6.88.
Diethyl
(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)(4-methoxyphenyl)methyl
phosphonate (7a). From anisole (4a) and trichloroacetimidate 3c, 0.40 g, Yield 69%,
colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.07-1.13 (m, 6 H, 2 CH3), 2.45 (d, J=
3.0 Hz, 1 H, CH), 3.73 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 3.90-4.00 (m, 4 H, 2
CH2), 4.31 (d, JHP = 24.0 Hz, 1 H, CHP), 4.68 (d, J = 3.0 Hz, 2 H, OCH2), 6.81 (d, J =
6.0 Hz, 1 H, H-Ar), 6.92-7.01 (m, 2 H, H-Ar), 7.11 (s, 1 H, H-Ar), 7.39-7.43 (m, 3 H,
13
H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 5.3 Hz, CH3), 16.4 (d, JCP
=
5.3 Hz, CH3), 49.8 (d, JCP = 135.9 Hz, CHP), 55.1 (OCH3), 55.9 (OCH3), 56.8
(OCH2C≡CH), 62.5 (d, JCP = 6.7 Hz, CH2OP), 62.6 (d, JCP = 6.7 Hz, CH2OP), 75.8
18

ACCEPTED MANUSCRIPT
(C≡CH), 78.6 (C≡CH), 113.2, 113.9, 114.4, 121.4, 121.5, 128.9, 129.0, 130.3, 131.1,
31
145.9, 149.5, 158.7 (C-Ar). P-NMR (194.4 MHz, CDCl3) δ=25.4 (P). Found, %: C,
63.02; H, 6.48. For C22H27O6P (418.4). Calculated, %: C, 63.15; H, 6.50.
Diethyl (3,4-dimethoxyphenyl)(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)methyl
phosphonate (7b). From 1,2-dimethoxy benzene (4b) and trichloroacetimidate 3c,
0.48 g, Yield 76%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.09 (t, J = 6.0 Hz,
6 H, 2 CH3), 2.45 (d, J= 3.0 Hz, 1 H, CH), 3.78 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3),
3.83 (s, 3 H, OCH3), 3.93-3.98 (m, 4 H, 2 CH2), 4.29 (d, JHP = 24.0 Hz, 1 H, CHP),
4.65 (d, J = 3.0 Hz, 2 H, OCH2), 6.75 (d, J = 9.0 Hz, 1 H, H-Ar), 6.83-6.97 (m, 3 H,
H-Ar), 6.99-7.08 (m, 2 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 5.3
Hz, CH3), 16.4 (d, JCP = 5.3 Hz, CH3), 49.9 (d, JCP = 138.9 Hz, CHP), 55.7 (OCH3),
55.8 (2OCH3), 56.8 (OCH2C≡CH), 62.7 (d, JCP = 3.8 Hz, CH2OP), 62.8 (d, JCP = 3.8
Hz, CH2OP), 75.8 (C≡CH), 78.5 (C≡CH), 111.4, 112.7, 112.8, 113.2, 114.4, 121.5,
129.2, 130.8, 145.9, 146.0, 148.2, 149.0 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ=
25.3 (P). Found, %: C, 61.47; H, 6.34. For C23H29O7P (448.5). Calculated, %: C,
61.60; H, 6.52.
Diethyl (2,4-dimethoxyphenyl)(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)methyl
phosphonate (7c). From 1,3-dimethoxy benzene (4c) and trichloroacetimidate 3c,
0.44 g, Yield 71%, colorless oil. 1H-NMR (300.0 MHz,CDCl3) δ= 1.05-1.12 (m, 6 H,
2 CH3), 2.45 (d, J= 3.0 Hz, 1 H, CH), 3.72 (s, 3 H, OCH3), 3.74 (s, 3 H, OCH3), 3.81
(s, 3 H, OCH3), 3.92-4.00 (m, 4 H, 2 CH2), 4.64 (d, J= 3.0 Hz, 2 H, OCH2), 4.92 (d,
JHP = 27.0 Hz, 1 H, CHP), 6.39 (s, 1 H, H-Ar), 6.48 (dd, J= 6.0, 3.0 Hz, 1 H, H-Ar),
6.39-6.48 (m, 2 H, H-Ar), 6.90 (d, J= 9.0 Hz, 1 H, H-Ar), 7.77 (dd, J= 6.0, 3.0 Hz, 1
H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 5.3 Hz, CH3), 16.4 (d, JCP =
19

ACCEPTED MANUSCRIPT
5.3 Hz, CH3), 40.7 (d, JCP = 141.2 Hz, CHP), 55.2 (OCH3), 55.6 (OCH3), 55.8
(OCH3), 56.8 (OCH2C≡CH), 62.3 (d, JCP = 7.6 Hz, CH2OP), 62.4 (d, JCP = 7.6 Hz,
CH2OP), 75.7 (C≡CH), 78.7 (C≡CH), 96.7, 104.4, 113.5, 114.3, 118.0, 121.6, 130.5,
130.6, 131.4, 145.7, 149.3, 157.5 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ= 26.4 (P).
Found, %: C, 61.55; H, 6.47. For C23H29O7P (448.5). Calculated, %: C, 61.60; H,
6.52.
Diethyl (2,5-dimethoxyphenyl)(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)methyl
phosphonate (7d). From 1,4-dimethoxy benzene (4d) and trichloroacetimidate 3c,
0.53 g, Yield 86%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.07-1.15 (m, 6 H,
2 CH3), 2.47 (d, J= 3.0 Hz, 1 H, CH), 3.75 (s, 3 H, OCH3), 3.84 (s, 3 H, OCH3), 3.90
(s, 3 H, OCH3), 3.93-4.06 (m, 4 H, 2 CH2), 4.68 (d, J= 3.0 Hz, 2 H, OCH2), 5.06 (d,
13
JHP = 24.0 Hz, 1 H, CHP), 6.74-6.96 (m, 3 H, H-Ar), 7.04-7.48 (m, 3 H, H-Ar). C-
NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 6.0 Hz, CH3), 16.3 (d, JCP = 6.0 Hz, CH3),
41.1 (d, JCP = 141.2 Hz, CHP), 55.6 (OCH3), 55.9 (OCH3), 56.4 (OCH3), 56.8
(OCH2C≡CH), 62.6 (d, JCP = 4.5 Hz, CH2OP), 62.8 (d, JCP = 4.5 Hz, CH2OP), 75.7
(C≡CH), 78.6 (C≡CH), 112.1, 113.5, 113.6, 114.4, 114.6, 116.0, 116.1, 121.7, 121.8,
130.5, 130.6, 153.6, 153.8 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ= 26.0 (P). Found,
%: C, 61.42; H, 6.39. For C23H29O7P (448.5). Calculated, %: C, 61.60; H, 6.52.
Diethyl
(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)(2,3,4-trimethoxyphenyl)-
methyl phosphonate (7e). From 1,2,3-trimethoxy benzene (4e) and
1
trichloroacetimidate 3c, 0.59 g, Yield 89%, colorless oil. H-NMR (300.0 MHz,
CDCl3) δ= 1.01-1.08 (m, 6 H, 2 CH3), 2.43 (d, J= 3.0 Hz, 1 H, CH), 3.71 (s, 3 H,
OCH3), 3.74 (s, 3 H, OCH3), 3.77 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.82-3.93 (m,
4 H, 2 CH2), 4.60 (d, J= 3.0 Hz, 2 H, OCH2), 4.86 (d, JHP = 27.0 Hz, 1 H, CHP), 6.49
20

ACCEPTED MANUSCRIPT
(d, J= 9.0 Hz, 1 H, H-Ar), 6.64 (d, J= 9.0 Hz, 1 H, H-Ar), 6.84-7.04 (m, 2 H, H-Ar),
7.47-7.51 (m, 1 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 5.3 Hz,
CH3), 16.3 (d, JCP = 5.3 Hz, CH3), 41.2 (d, JCP = 141.9 Hz, CHP), 55.7 (OCH3), 55.8
(OCH3), 56.7 (OCH2C≡CH), 60.5 (OCH3), 61.0 (OCH3), 62.6 (d, JCP = 3.8 Hz,
CH2OP), 62.8 (d, JCP = 3.8 Hz, CH2OP), 75.8 (C≡CH), 78.5 (C≡CH), 105.3, 107.4,
113.3, 114.4, 124.0, 130.8, 130.9, 142.1, 145.9, 149.5, 151.4, 153.0 (C-Ar). 31P-NMR
(194.4 MHz, CDCl3) δ=25.9 (P). Found, %: C, 60.14; H, 6.45. For C24H31O8P
(478.5). Calculated, %: C, 60.25; H, 6.53.
Diethyl
(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)(2,4,6-trimethoxyphenyl)-
methyl phosphonate (7f). From 1,3,5-trimethoxy benzene (4f) and
1
trichloroacetimidate 3c, 0.42 g, Yield 63%, colorless oil. H-NMR (300.0 MHz,
CDCl3) δ= 1.08-1.18 (m, 6 H, 2 CH3), 2.45 (d, J= 3.0 Hz, 1 H, CH), 3.75 (s, 3 H,
OCH3), 3.79 (s, 3 H, OCH3), 3.81 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 3.86-3.99 (m,
4 H, 2 CH2), 4.64 (d, J= 3.0 Hz, 2 H, OCH2), 5.12 (d, JHP = 30.0 Hz, 1 H, CHP), 6.11
13
(s, 2 H, H-Ar), 6.83-6.92 (m, 2 H, H-Ar), 7.16 (s, 1 H, H-Ar). C-NMR (75.0 MHz,
CDCl3) δ= 16.2 (d, JCP = 6.8 Hz, CH3), 16.3 (d, JCP = 6.8 Hz, CH3), 39.3 (d, JCP
=
145.7 Hz, CHP), 55.2 (OCH3), 55.6 (2OCH3), 55.7 (OCH3), 56.8 (OCH2C≡CH), 62.2
(d, JCP = 7.6 Hz, CH2OP), 62.4 (d, JCP = 7.6 Hz, CH2OP), 75.6 (C≡CH), 78.58
(C≡CH), 91.0. 106.8, 106.9, 113.7, 114.0, 121.7, 121.8, 130.8, 130.9, 145.5, 149.0,
160.6 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ=27.4 (P). Found, %: C, 60.18; H,
6.44. For C24H31O8P (478.5). Calculated, %: C, 60.25; H, 6.53.
Diethyl (4-(allyloxy)-3-methoxyphenyl)(4-methoxyphenyl)methyl phosphonate
(8a). From anisole (4a) and trichloroacetimidate 3d, 0.55 g, Yield 95%, colorless oil.
1H-NMR (300.0 MHz, CDCl3) δ= 1.09-1.15 (m, 6 H, 2 CH3), 3.75 (s, 3 H, OCH3),
21

ACCEPTED MANUSCRIPT
3.85 (s, 3 H, OCH3), 3.96-4.06 (m, 4 H, 2 CH2), 4.31 (d, JHP = 24.0 Hz, 1 H, CHP),
4.53 (d, J= 3.0 Hz, 2 H, OCH2CH=CH2), 5.24 (d, J= 12 Hz, 1 H, OCH2CH=CH2),
5.36 (d, J= 18 Hz, 1 H, OCH2CH=CH2), 6.00-6.09 (m, 1 H, OCH2CH=CH2), 6.83-
13
6.86 (m, 3 H, H-Ar), 6.99-7.11 (m, 2 H, H-Ar), 7.42-7.44 (m, 2 H, H-Ar). C-NMR
(75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 49.8
(d, JCP = 138.9 Hz, CHP), 55.2 (OCH3), 55.9 (OCH3), 62.5 (d, JCP = 6.8 Hz, CH2OP),
62.8 (d, JCP = 6.8 Hz, CH2OP), 69.9 (OCH2CH=CH2), 113.1, 113.2, 113.5 (C-Ar),
117.8 (OCH2CH=CH2), 121.5, 121.6, 129.1, 130.0, 130.3, 130.4, 133.4
31
(OCH2CH=CH2), 147.1, 149.3, 158.7 (C-Ar). P-NMR (194.4 MHz, CDCl3) δ=25.5
(P). Found, %: C, 62.82; H, 6.93. For C22H29O6P (420.4). Calculated, %: C, 62.85; H,
6.95.
Diethyl
(4-(allyloxy)-3-methoxyphenyl)(3,4-dimethoxyphenyl)methyl
phosphonate (8b). From 1,2-dimethoxy benzene (4b) and trichloroacetimidate 3d,
0.54 g, Yield 87%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.11 (t, J = 6.0 Hz,
6 H, 2 CH3), 3.80 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 3.83 (s, 3 H, OCH3), 3.90-3.99
(m, 4 H, 2 CH2), 4.28 (d, JHP = 24.0 Hz, 1 H, CHP), 4.53 (d, J= 3.0 Hz, 2 H,
OCH2CH=CH2), 5.21 (d, J= 12 Hz, 1 H, OCH2CH=CH2), 5.29 (d, J= 18 Hz, 1 H,
OCH2CH=CH2), 6.00-6.09 (m, 1 H, OCH2CH=CH2), 6.77-6.80 (m, 2 H, H-Ar), 6.97-
13
7.08 (m, 4 H, H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 5.3 Hz, CH3),
16.4 (d, JCP = 5.3 Hz, CH3), 50.0 (d, JCP = 138.2 Hz, CHP), 55.7 (OCH3), 55.8
(OCH3), 55.9 (OCH3), 62.3 (d, JCP = 7.6 Hz, CH2OP), 62.7 (d, JCP = 7.6 Hz, CH2OP),
69.8 (OCH2CH=CH2), 111.2, 112.7, 113.1, 113.2 (C-Ar), 117.8 (OCH2CH=CH2),
121.5, 121.6, 121.7, 129.5, 133.3 (OCH2CH=CH2), 147.1, 147.2, 148.1, 149.1 (C-Ar).
31P-NMR (194.4 MHz, CDCl3) δ= 25.4 (P). Found, %: C, 61.16; H, 6.80. For
C23H31O7P (450.5). Calculated, %: C, 61.33; H, 6.94.
22

ACCEPTED MANUSCRIPT
Diethyl
(4-(allyloxy)-3-methoxyphenyl)(2,4-dimethoxyphenyl)methyl
phosphonate (8c). From 1,3-dimethoxy benzene (4c) and trichloroacetimidate 3d,
0.49 g, Yield 78%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.05-1.12 (m, 6 H,
2 CH3), 3.75 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.82 (s, 3 H, OCH3), 3.92-4.09 (m,
4 H, 2 CH2), 4.49 (d, J= 3.0 Hz, 2 H, OCH2CH=CH2), 4.91 (d, JHP = 27.0 Hz, 1 H,
CHP), 5.18 (d, J= 12 Hz, 1 H, OCH2CH=CH2), 5.31 (d, J= 15 Hz, 1 H,
OCH2CH=CH2), 5.96-6.04 (m, 1 H, OCH2CH=CH2), 6.39-6.48 (m, 2 H, H-Ar), 6.75
(d, J= 9.0 Hz, 1 H, H-Ar), 6.96-7.08 (m, 2 H, H-Ar), 7.77 (d, J= 6.0 Hz, 1 H, H-Ar).
13C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 4.5 Hz, CH3), 16.4 (d, JCP = 4.5 Hz,
CH3), 41.6 (d, JCP = 141.2 Hz, CHP), 55.1 (OCH3), 55.2 (OCH3), 55.6 (OCH3), 62.3
(d, JCP = 6.8 Hz, CH2OP), 62.4 (d, JCP = 6.8 Hz, CH2OP), 69.8 (OCH2CH=CH2), 98.7,
104.4, 106.1, 113.4, 113.5 (C-Ar), 117.6 (OCH2CH=CH2), 121.7, 121.8, 130.1, 130.2,
31
130.5, 133.4 (OCH2CH=CH2), 146.9 (C-Ar). P-NMR (194.4 MHz, CDCl3) δ= 26.5
(P). Found, %: C, 61.26; H, 6.82. For C23H31O7P (450.5). Calculated, %: C, 61.33; H,
6.94.
Diethyl
(4-(allyloxy)-3-methoxyphenyl)(2,5-dimethoxyphenyl)methyl
phosphonate (8d). From 1,4-dimethoxy benzene (4d) and trichloroacetimidate 3d,
0.45 g, Yield 71%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.06-1.15 (m, 6 H,
2 CH3), 3.79 (s, 3 H, OCH3), 3.80 (s, 3 H, OCH3), 3.84 (s, 3 H, OCH3), 3.91-4.05 (m,
4 H, 2 CH2), 4.57 (d, J= 3.0 Hz, 2 H, OCH2CH=CH2), 5.04 (d, JHP = 24.0 Hz, 1 H,
CHP), 5.27 (d, J= 9 Hz, 1 H, OCH2CH=CH2), 5.38 (d, J= 18 Hz, 1 H,
OCH2CH=CH2), 6.01-6.14 (m, 1 H, OCH2CH=CH2), 6.79-6.82 (m, 3 H, H-Ar), 7.04-
13
7.54 (m, 3 H, H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 6.0 Hz, CH3),
16.3 (d, JCP = 6.0 Hz, CH3), 41.3 (d, JCP = 141.2 Hz, CHP), 55.7 (OCH3), 55.9
(OCH3), 56.5 (OCH3), 62.5 (d, JCP = 7.6 Hz, CH2OP), 62.8 (d, JCP = 7.6 Hz, CH2OP),
23

ACCEPTED MANUSCRIPT
69.9 (OCH2CH=CH2), 112.1, 113.1, 113.6, 116.0 (C-Ar), 117.8 (OCH2CH=CH2),
121.9, 126.8, 129.7, 133.5 (OCH2CH=CH2), 147.0, 149.1, 151.0, 151.1, 153.6 (C-Ar).
31P-NMR (194.4 MHz, CDCl3) δ= 26.1 (P). Found, %: C, 61.14; H, 6.73. For
C23H31O7P (450.5). Calculated, %: C, 61.33; H, 6.94.
Diethyl
(4-(allyloxy)-3-methoxyphenyl)(2,3,4-trimethoxyphenyl)methyl
phosphonate (8e). From 1,2,3-trimethoxy benzene (4e) and trichloroacetimidate 3d,
0.58 g, Yield 86%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.10-1.16 (m, 6 H,
2 CH3), 3.80 (s, 3 H, OCH3), 3.85 (s, 3 H, OCH3), 3.87 (s, 3 H, OCH3), 3.97 (s, 3 H,
OCH3), 4.00-4.16 (m, 4 H, 2 CH2), 4.90 (d, JHP = 24.0 Hz, 1 H, CHP), 4.56 (d, J= 6.0
Hz, 2 H, OCH2CH=CH2), 5.25 (d, J= 9.0 Hz, 1 H, OCH2CH=CH2), 5.36 (d, J= 15.0
Hz, 1 H, OCH2CH=CH2), 5.99-6.12 (m, 1 H, OCH2CH=CH2), 6.68 (d, J= 9.0 Hz, 1
H, H-Ar), 6.78 6.68 (d, J= 9.0 Hz, 1 H, H-Ar), 7.00-7.14 (m, 2 H, H-Ar), 7.69 (d, J =
13
9.0 Hz, 1 H, H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 4.5 Hz, 2CH3),
16.3 (d, JCP = 4.5 Hz, 2CH3), 41.4 (d, JCP = 141.9 Hz, CHP), 55.8 (OCH3), 55.9
(OCH3), 60.3 (OCH3), 60.7 (OCH3), 62.4 (d, JCP = 6.8 Hz, CH2OP), 62.6 (d, JCP = 6.8
Hz, CH2OP), 69.9 (OCH2CH=CH2), 107.4, 113.3, 113.4 (C-Ar), 117.8
(OCH2CH=CH2), 121.6, 121.9, 123.4, 124.3, 130.2(C-Ar), 133.4 (OCH2CH=CH2),
142.2, 149.2, 152.8 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ= 26.2 (P). Found, %: C,
59.83; H, 6.89. For C24H33O8P (480.5). Calculated, %: C, 59.99; H, 6.92.
Diethyl
(4-(allyloxy)-3-methoxyphenyl)(2,4,6-trimethoxyphenyl)methyl
phosphonate (8f). From 1,3,5-trimethoxy benzene (4f) and trichloroacetimidate 3d,
0.31g, Yield 47%, colorless oil. 1H-NMR (300.0 MHz, CDCl3) δ= 1.14-1.23 (m, 6 H,
2 CH3), 3.76 (s, 3 H, OCH3), 3.81 (s, 9 H, 3 OCH3), 3.86-4.03 (m, 4 H, 2 CH2), 4.59
(d, J= 6.0 Hz, 2 H, OCH2CH=CH2), 4.86 (d, JHP = 24.0 Hz, 1 H, CHP), 5.27 (d, J=
24

ACCEPTED MANUSCRIPT
12.0 Hz, 1 H, OCH2CH=CH2), 5.39 (d, J= 18.0 Hz, 1 H, OCH2CH=CH2), 6.01-6.12
(m, 1 H, OCH2CH=CH2), 6.18 (s, 2 H, H-Ar), 6.78-6.94 (m, 2 H, H-Ar), 7.19 (s, 1 H,
13
H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.2 (d, JCP = 4.5 Hz, CH3), 16.3 (d, JCP
=
4.5 Hz, CH3), 41.3 (d, JCP = 141.2 Hz, CHP), 55.3 (OCH3), 55.6 (OCH3), 55.7
(OCH3), 56.4 (OCH3), 62.3 (d, JCP = 6.8 Hz, CH2OP), 62.6 (d, JCP = 6.8 Hz, CH2OP),
69.9 (OCH2CH=CH2), 91.0. 106.8, 106.9, 114.1, 114.3 (C-Ar), 117.7
(OCH2CH=CH2), 121.8, 121.9, 130.6, 130.7 (C-Ar), 133.3 (OCH2CH=CH2), 135.7,
31
145.3, 149.1, 160.2 (C-Ar). P-NMR (194.4MHz, CDCl3) δ= 27.3 (P). Found, %: C,
59.69; H, 6.83. For C24H33O8P (480.5). Calculated, %: C, 59.99; H, 6.92.
General procedure for the preparation of diethyl α-alkenyl α-aryl
methylphosphonates 9a-d and 10a-d, and diethyl α-(oxoalkyl) α-aryl
methylphosphonates 11a-d and 12a-d.
TMSOTf (0.03 mL, 0.14 mmol) was added to a solution of trichloroacetimidate 3a-d
(1.4 mmol) and alkene C-nucleophiles (allyl trimethylsilane or styrene) or
trimethylsioxy alkene C-nucleophiles (1-trimethylsiloxycyclohexene or 1-phenyl-1-
trimethylsiloxy-ethylene) (1.4 mmol) in dichloromethane (40 mL). The reaction
mixture was stirred at room temperature for 4 h. The reaction mixture was neutralized
with solid sodium bicarbonate, filtered and concentrated under reduced pressure. The
residue was purified by flash chromatography1:2 pet.ether/ethylacetate to give diethyl
α-alkenyl α-aryl methylphosphonates 9a-d and 10a-d and diethyl α-(oxoalkyl) α-aryl
methylphosphonates 11a-d and 12a-d as a colourless oil.
Diethyl
1-(4-methoxyphenyl)but-3-enylphosphonate
(9a).
From
Allyl
1
trimethylsilane, 0.54 g, Yield 78%, colorless oil. H-NMR (300.0 MHz, CDCl3) δ=
1.14 (t, J= 6.0 Hz, 3 H, CH3), 1.23 (t, J = 6.0 Hz, 3 H, CH3), 2.65-2.87 (m, 2 H,
25

ACCEPTED MANUSCRIPT
CH2CH=CH2), 2.99-3.12 (m, 1 H, CHP), 3.81 (s, 3 H, OCH3), 3.91-4.10 (m, 4 H, 2
CH2), 4.93 (d, J= 12.0 Hz, 1 H, CH2CH=CH2), 5.01 (d, J= 18.0 Hz, 1 H,
CH2CH=CH2), 5.57-5.70 (m, 1 H, CH2CH=CH2), 6.68-6.75 (m, 2 H, H-Ar), 7.34-
13
7.45 (m, 2 H, H-Ar). C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz, CH3),
16.4 (d, JCP = 6.0 Hz, CH3), 34.9 (d, JCP = 2.3 Hz, CH2CH=CH2), 43.6 (d, JCP = 138.2
Hz, CHP), 55.7 (OCH3), 61.8 (d, JCP = 7.6 Hz, CH2), 62.5 (d, JCP = 7.6 Hz, CH2),
113.9, 114.4, 116.7, 127.5, 129.2 (C-Ar), 130.3 (d, JCP = 6.8, CH2CH=CH2), 135.5 (d,
31
JCP = 15.9, CH2CH=CH2), 158.7 (C-Ar). P-NMR (194.4MHz, CDCl3) δ= 28.5 (P).
Found, %: C, 60.21; H, 7.64. For C15H23O4P (298.2). Calculated, %: C, 60.39; H,
7.77.
Diethyl 1-(3,4-dimethoxyphenyl)but-3-enylphosphonate (9b). From Allyl
trimethylsilane, 0.52 g, Yield 88%, colourless oil. 1H-NMR (300.0 MHz, CDCl3) δ=
1.12 (t, J = 9.0 Hz, 3 H, CH3), 1.28 (t, J = 9.0 Hz, 3 H, CH3), 2.61-2.78 (m, 2 H,
CH2), 2.96-3.07 (m, 1 H, CHP), 3.75 (s, 3 H, OCH3), 3.84 (s, 3 H, OCH3), 3.91-4.10
(m, 4 H, 2 CH2), 4.91 (d, J= 12.0 Hz, 1 H, CH2CH=CH2), 4.99 (d, J= 18.0 Hz, 1 H,
CH2CH=CH2), 5.55-5.68 (m, 1 H, CH), 6.78- 6.87 (m, 3 H, H-Ar). 13C-NMR (75.0
MHz,CDCl3) δ= 16.3 (d, JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 34.2 (d, JCP
= 3.0 Hz, CH2CH=CH2), 44.1 (d, JCP = 138.2 Hz, CHP), 55.8 (OCH3), 55.9 (OCH3),
61.8 (d, JCP = 7.6 Hz, CH2), 62.6 (d, JCP = 7.6 Hz, CH2), 111.0, 112.5, 116.7, 121.7
(C-Ar), 128.0 (d, JCP = 7.6 Hz, CH2CH=CH2), 135.5 (d, JCP = 15.9 Hz, CH2CH=CH2),
31
148.2, 148.8 (C-Ar). P-NMR (194.4MHz, CDCl3) δ= 28.4 (P). Found, %: C, 58.48;
H, 7.62. For C16H25O5P (328.3). Calculated, %: C, 58.53; H, 7.67.
Diethyl (1-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)but-3-en-1-yl)phosphonate
1
(9c). From Allyl trimethylsilane, 0.37 g, Yield 76% colourless oil. H-NMR (300.0
MHz, CDCl3) δ= 1.19 (t, J = 9.0 Hz, 3 H, CH3), 1.29 (t, J = 9.0 Hz, 3 H, CH3), 2.48
26

ACCEPTED MANUSCRIPT
(d, J= 3.0 Hz, 1 H, CH), 2.67-2.82 (m, 2 H, CH2), 3.01-3.08 (m, 1 H, CHP), 3.75 (s, 3
H, OCH3), 3.80-4.09 (m, 4 H, 2 CH2), 4.72 (d, J = 3.0 Hz, 2 H, OCH2), 4.93 (d, J= 9.0
Hz, 1 H, CH2CH=CH2), 5.01 (d, J= 15.0 Hz, 1 H, CH2CH=CH2), 5.58-5.69 (m, 1 H,
CH), 6.80-6.95 (m, 3 H, H-Ar).13C-NMR (75.0 MHz,CDCl3) δ= 16.3 (d, JCP = 6.0 Hz,
CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 34.2 (d, JCP = 3.0 Hz, CH2CH=CH2), 44.1 (d, JCP =
137.4 Hz, CHP), 55.9 (OCH3), 56.8 (OCH2C≡CH), 61.9 (d, JCP = 7.6 Hz, CH2), 62.7
(d, JCP = 7.6 Hz, CH2), 75.7 (C≡CH), 78.6 (C≡CH), 112.9, 114.3, 116.8, 121.6 (C-Ar),
129.5 (d, JCP = 7.6 Hz, CH2CH=CH2), 135.3 (d, JCP = 16.6 Hz, CH2CH=CH2), 146.0,
149.5 (C-Ar). 31P-NMR (194.4 MHz, CDCl3) δ=28.3 (P). Found, %: C, 61.25; H,
7.03. For C18H25O5P (352.4). Calculated, %: C, 61.36; H, 7.15.
Diethyl 1-(4-(allyloxy)-3-methoxyphenyl)but-3-enylphosphonate (9d). From Allyl
1
trimethylsilane, 0.26 g, Yield 62% colourless oil. H-NMR (300.0 MHz, CDCl3) δ=
1.11 (t, J = 6.0 Hz, 3 H, CH3), 1.29 (t, J = 6.0 Hz, 3 H, CH3), 2.64-2.78 (m, 2 H,
CH2), 2.94-3.07 (m, 1 H, CHP), 3.74 (s, 3 H, OCH3), 3.91-4.09 (m, 4 H, 2 CH2), 4.58
(d, J= 3.0 Hz, 2 H, OCH2CH=CH2), 4.92 (d, J= 12.0 Hz, 1 H, CH2CH=CH2), 5.00 (d,
J= 18.0 Hz, 1 H, CH2CH=CH2), 5.26 (d, J= 12 Hz, 1 H, OCH2CH=CH2), 5.38 (d, J=
18 Hz, 1 H, OCH2CH=CH2), 5.52-5.68 (m, 1 H, CH2CH=CH2), 6.03-6.12 (m, 1 H,
OCH2CH=CH2), 6.81- 6.89 (m, 3 H, H-Ar). 13C-NMR (75.0 MHz,CDCl3) δ= 16.3 (d,
JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 34.2 (d, JCP = 2.3 Hz, CH2CH=CH2),
44.1 (d, JCP = 188.2 Hz, CHP), 55.9 (OCH3), 61.7 (d, JCP = 7.6 Hz, CH2), 62.6 (d, JCP
= 7.6 Hz, CH2), 69.9 (OCH2CH=CH2), 112.9, 113.3, 116.7 (C-Ar), 117.8
(OCH2CH=CH2), 121.7 (C-Ar), 128.5 (d, JCP = 7.6 Hz, CH2CH=CH2), 133.4
(OCH2CH=CH2), 135.4 (d, JCP = 15.9 Hz, CH2CH=CH2), 147.1, 149.3 (C-Ar). 31P-
NMR (194.4 MHz, CDCl3) δ=28.3 (P). Found, %: C, 60.89; H, 7.51. For C18H27O5P
(354.2). Calculated, %: C, 61.01; H, 7.68.
27

ACCEPTED MANUSCRIPT
Diethyl 1-(4-methoxyphenyl)-3-phenylallylphosphonate (10a). From styrene, 0.70
1
g, Yield 72%, colourless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.17 (t, J = 6.0 Hz, 3
H, CH3), 1.29 (t, J = 6.0 Hz, 3 H, CH3), 3.81 (s, 3 H, OCH3), 3.86-3.94 (m, 1 H,
CHP), 4.00-4.16 (m, 4 H, 2 CH2), 6.49-6.62 (m, 2 H, CH=CHPh), 6.90-6.96 (m, 2 H,
H-Ar), 7.21-7.41 (m, 7 H, H-Ar). 13C-NMR (75.0 MHz, CDCl3) δ= 16.3 (d, JCP = 6.0
Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 48.4 (d, JCP = 138.2 Hz, CHP), 55.3 (OCH3),
62.6 (d, JCP = 7.6 Hz, CH2), 62.8 (d, JCP = 7.6 Hz, CH2), 114.1 (C-Ar), 124.9 (d, JCP =
9.0 Hz, CH=CHPh), 126.4, 127.6, 127.8, 128.5, 130.1, 130.2 (C-Ar), 133.4 (d, JCP =
13.6 Hz, CH=CHPh), 136.9, 158.8 (C-Ar). 31P-NMR (194.4MHz, CDCl3) δ=25.1 (P).
Found, %: C, 66.78; H, 7.15. For C20H25O4P (360.4). Calculated, %: C, 66.66; H,
6.99.
Diethyl 1-(3,4-dimethoxyphenyl)-3-phenylallylphosphonate (10b). From styrene,
1
0.43 g, Yield 75% colourless oil. H-NMR (300.0 MHz, CDCl3) δ= 1.19 (t, J = 6.0
Hz, 3 H, CH3), 1.31 (t, J = 6.0 Hz, 3 H, CH3), 3.76 (s, 3 H, OCH3), 3.83 (s, 3 H,
OCH3), 3.83-3.92 (m, 1 H, CHP), 4.00-4.16 (m, 4 H, 2 CH2), 6.52-6.65 (m, 2 H,
CH=CHPh), 6.86-7.06 (m, 3 H, H-Ar), 7.27-7.41 (m, 5 H, H-Ar). 13C-NMR (75.0
MHz, CDCl3) δ= 16.3 (d, JCP = 6.0 Hz, CH3), 16.4 (d, JCP = 6.0 Hz, CH3), 49.1 (d, JCP
= 138.2 Hz, CHP), 55.7 (OCH3), 55.9 (OCH3), 62.5 (d, JCP = 7.6 Hz, CH2), 62.7 (d,
JCP = 7.6 Hz, CH2), 111.5, 112.7, 121.4, (C-Ar), 125.1 (d, JCP = 9.0 Hz, CH=CHPh),
126.4, 127.6, 128.5, 130.4, 130.6 (C-Ar), 133.7 (d, JCP = 13.6 Hz, CH=CHPh), 136.8,
148.2, 148.9. 31P-NMR (194.4MHz, CDCl3) δ= 25.0 (P). Found, %: C, 64.54; H, 6.86.
For C21H27O5P (390.4). Calculated, %: C, 64.61; H, 6.97.
Diethyl 1-(3-methoxy-4-(prop-2-yn-1-yloxy)phenyl)-3-phenylallyl phosphonate
1
(10c). From styrene, 0.35 g, Yield 61% colourless oil. H-NMR (300.0 MHz,
CDCl3) δ= 1.12 (t, J = 6.0 Hz, 3 H, CH3), 1.33 (t, J= 6.0 Hz, 3 H, CH3), 2.51 (s, 1 H,
28