Lanthanide-catalyzed selective addition of diethyl phosphite to chalcones

Article abstract of DOI:10.1002/hc.21099

Lanthanide-catalyzed addition of diethyl phosphite with chalcones was achieved under mild conditions. The reaction exhibited good product selectivity using different catalysts. γ-Oxophosphonates were obtained in high yields in the reactions catalyzed by Y

Full text of DOI:10.1002/hc.21099

Heteroatom Chemistry
Volume 24, Number 5, 2013
Lanthanide-Catalyzed Selective Addition
of Diethyl Phosphite to Chalcones
Aijiao Zhang, Lijian Cai, Zhigang Yao, Fan Xu, and Qi Shen
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou
215123, People’s Republic of China
Received 15 February 2013; revised 30 April 2013
optoelectronics, and homogeneous catalysis [2–9],
ABSTRACT: Lanthanide-catalyzed addition of di-
much attention has been focused on efficient strate-
ethyl phosphite with chalcones was achieved
gies to construct carbon–phosphorus bonds [10].
under mild conditions. The reaction exhibited
Among the various routes reported, cross coupling of
good product selectivity using different catalysts.
phosphorus agents with aryl halides or triflates [11–
γ -Oxophosphonates were obtained in high yields in
15] and addition of phosphorus-based nucleophiles
the reactions catalyzed by Yb(OAr)3(THF)2, while
(P-nucleophiles) to activated carbon atoms are the
those catalyzed by [(Me3Si)2N]3La(μ-Cl)Li(THF)3 af-
most direct and efficient routes to form carbon–
forded 1,2-oxaphospholane-5-phosphonates as the
phosphorus bonds. The latter, which includes the
main products in moderate to good yields. This
well-known Pudovik reaction [16–25] and phospha-
methodology provides facile and practical approaches
Michael addition [26], is a more concise route that
to the corresponding organophosphorus compounds
maximizes atom efficiency and results in negligible
ꢀC
with biological interest.
2013 Wiley Periodicals,
waste.
Phospha-Michael addition, which is the con-
Inc. Heteroatom Chem. 24:345–354, 2013; View
this article online at wileyonlinelibrary.com. DOI
10.1002/hc.21099
jugated addition of P-nucleophiles to activated
alkenes, is important in carbon–phosphorus bond
formation and its catalysts, scope, and applica-
tions have been explored. Phosphine [27–32], tri-
alkyl phosphite [33–41], and dialkyl phosphite are
commonly used P-nucleophiles in these addition
reactions. Considering the stability and smell of
phosphorus reagents, dialkyl phosphite is the pre-
ferred choice and is also readily available. Phospha-
Michael addition also requires an olefinic acceptor,
which is typically an α,β-unsaturated ketone [42–46],
ester [45–48], nitrile, or nitroalkene [49–53]. Unlike
the other reactions, those involving α,β-unsaturated
ketones remain a challenge in terms of substrate
scope and product selectivity. For example, the vast
majority of the α,β-unsaturated ketones, used pre-
viously in phospha-Michael addition, was limited to
several specific compounds such as methylvinylke-
tone and cyclic enones, and the steric hindrance was
the only factor discussed in detail affecting the prod-
uct regioselectivity. Recently, Wang and coworkers
INTRODUCTION
The richness and diversity of organophosphorus
compounds have made organophosphorus chem-
istry [1] a subject of intense research over the last
few decades. Accompanied by the increasing use
of organophosphorus compounds in many differ-
ent fields, including medicine, agriculture, organic
Correspondence to: Fan Xu; e-mail: xufan@suda.edu.cn. Qi
Shen; e-mail: qshen@suda.edu.cn
Contract grant sponsor: National Natural Science Foundation
of China.
Contract grant numbers: 21272168, 20972107, and 20872106.
Contract grant sponsor: Project Funded by the Priority Academic
Program Development of Jiangsu Higher Education Institutions.
ꢀC
2013 Wiley Periodicals, Inc.
345

346 Zhang et al.
TABLE 1 Condition Screening for the Catalyzed Reaction of Diethyl Phosphite with Chalconea
Yield (%)b
3a
Entry
Catalyst
Loading (mol%)
Solvent
T (◦C)
1a:2
4a
c
1
2
3
4
5
6
7
8
Yb(OAr1)3(THF)2
2.5
5
5
5
5
5
5
20
15
1
2
2
2
2
2
4
12
THF
THF
THF
THF
THF
THF
THF
THF
THF
25
25
25
25
25
25
25
25
25
18
18
18
18
40
40
40
40
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:3
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:1.2
1:3
21d
92(94d )
70
nde
nde
nde
nde
nde
nde
nde
nde
trace
nde
nde
15
c
c
Yb(OAr1)3(THF)2
Nd(OAr1)3(THF)2
c
La(OAr1)3(THF)2
Yb(OAr2)3(THF)2
Yb(OAr3)3(THF)2
67
84
81
47
nd
59
58
85
67
54
41
13
18
30
f
g
c
La(OAr1)3(THF)2
Yb(OTf)3
9
NaOAr1c
10
11
12
13
14
15
16
17
[(Me3Si)2N]3Yb(μ-Cl)Li(THF)3
[(Me3Si)2N]3Yb(μ-Cl)Li(THF)3
[(Me3Si)2N]3Sm(μ-Cl)Li(THF)3
[(Me3Si)2N]3La(μ-Cl)Li(THF)3
[(Me3Si)2N]3La(μ-Cl)Li(THF)3
[(Me3Si)2N]3La(μ-Cl)Li(THF)3
[(Me3Si)2N]3La(μ-Cl)Li(THF)3
Li[N(TMS)2]
THF
toluene
toluene
toluene
toluene
T/Hh
30
52
71
80
1:3
1:3
1:3
T/Hh
T/Hh
15
aReactions were performed with 1 mmol chalcone 1a in 2 mL of solvent for 5 h.
bIsolated yield.
cAr1 = 2,6-(tBu)2–4-MeC6H2.
d HPLC yield.
eNot detected.
fAr2 = 2,6-(iPr)2C6H3.
gAr3 = 2,6-Me2C6H3.
hToluene:HMPA = 5:1.
reacted diethyl phosphite with chalcones in the pres-
ence of 40 mol% Et2Zn to form γ -oxophosphonates
in high yields with excellent enantioselectivities [54].
This is the only example of phospha-Michael addi-
tion using dialkyl phosphite as a nucleophile and
chalcone as an olefinic acceptor to synthesize bio-
logically active γ -oxophosphonates [55–57].
Cl)Li(THF)3. Although lanthanide-catalyzed enan-
tioselective reactions have been well studied, less at-
tention was paid to the catalyst-controlled product-
selective reactions involving lanthanide complexes
and successful examples were rather limited.
RESULTS AND DISCUSSION
During our recent investigation of lanthanide-
catalyzed Pudovik reactions, we found that lan-
thanide amides were highly efficient catalysts for
the hydrophosphonylation of aromatic aldehydes to
form α-hydroxy phosphonates [24]. However, lan-
thanide complexes have not yet been used as cat-
alysts in phospha-Michael addition. Here, we re-
port preliminary results showing that lanthanide
aryloxides Ln(OAr)3(THF)2 and lanthanide amides
[(Me3Si)2N]3Ln(μ-Cl)Li(THF)3 show high catalytic
activity in the phospha-Michael addition of di-
ethyl phosphite and chalcones. Moreover, these
lanthanide catalysts show unprecedented product
selectivity: γ -oxophosphonates were afforded in
high yields with Ln(OAr)3(THF)2 as the catalyst,
whereas 1,2-oxaphospholane-5-phosphonates were
obtained as major products using [(Me3Si)2N]3Ln(μ-
We first investigated the catalytic activity of
Yb(OAr1)3(THF)2 [Ar1 = 2,6-(tBu)2–4-MeC6H2] for
the reaction using chalcone 1a and diethyl phos-
phite as model substrates (Table 1). Diethyl (3-oxo-
1,3-diphenylpropyl)phosphonate 3a, the 1,4-adduct
from this reaction, was obtained in 21% yield when
2.5 mol% of Yb(OAr1)3(THF)2 was used (Table 1,
entry 1). When the catalyst loading was increased
to 5 mol%, the reaction proceeded effectively and
the yield increased dramatically to 94% (Table 1,
entry 2). To reveal the reason for the activity of
Yb(OAr1)3(THF)2, Yb(OTf)3 and NaOAr1 were also
used as catalysts. The reaction did not proceed with
Yb(OTf)3 (Table 1, entry 8), which is a strong Lewis
acid, while NaOAr1 (15 mol%) gave the correspond-
ing γ -oxophosphonate in 59% yield (Table 1, entry
Heteroatom Chemistry DOI 10.1002/hc

Lanthanide-Catalyzed Selective Addition of Diethyl Phosphite to Chalcones 347
TABLE 2 Yb(OAr1)3(THF)2-Catalyzed Reactions of Substi-
tuted Chalcones with Diethyl Phosphitea
1-position bearing electron-withdrawing groups was
somewhat higher than that of those bearing electron-
donating groups.
Tetracoordinate lanthanide amides [(Me3Si)2
N]3Ln(μ-Cl)Li(THF)3 [59–63], which are the
chloride-bridged “ate” complexes derived from
Ln[N(SiMe3)2]3 but more readily available than
the latter, are efficient catalysts for several useful
transformations such as aldol condensation [64],
polymerization of methyl methacrylate [61, 62],
aza-Henry reaction [65], guanylation of amines
[66], Pudovik reaction [24], and phospha-Brook
rearrangement [67]. During the catalyst screening,
we found that [(Me3Si)2N]3Yb(μ-Cl)Li(THF)3 also
works well as a catalyst for the above phospha-
Michael addition to afford γ -oxophosphonate 3a in
good yield (Table 1, entry 10). We then optimized
the central metal of this catalyst. Increasing the
ionic radius of Ln(III) from the heavy rare earth Yb
to light rare earth La led to a progressive decrease
in the yield of 3a. Conversely, a gradual increase in
the yield of diethyl (2-ethoxy-2-oxido-3,5-diphenyl-
1,2-oxaphospholan-5-yl)phosphonate 4a, another
product that can be formed via sequential phospha-
Michael/Pudovik reaction of chalcone with diethyl
phosphite, was observed (Table 1, entries 11–13).
To our knowledge, 2-oxido-1,2-oxaphospholanes
displays potential biological activity [68–76]. The
preparation of these P(V)-heterocyclic molecules
has already attracted considerable attention [77–83],
but complex and inaccessible substrates were used
in most approaches. Limited literature described
the synthesis of (2-oxido-1,2-oxaphospholan-5-
yl)phosphonates, which can be used as flame
retardants in epoxy resins, via the reaction of dialkyl
phosphites with vinyl ketones or aldehydes in the
presence of sodium and the yields were not satis-
factory [84–86]. Therefore, we conceived the idea
of developing efficient and practical methods for
the synthesis of 2-oxido-1,2-oxaphospholanes under
mild conditions. Further screening of conditions
revealed that increasing the reaction temperature
and the quantity of diethyl phosphite made 1,2-
oxaphospholane a main product (Table 1, entry
14). Notably, when La(OAr1)3(THF)2 was used as
the catalyst, 4a was not detected even upon the
addition of three equivalents of diethyl phosphite
(Table 1, entry 7). Using a mixed solvent of toluene
and hexamethylphosphoramide (HMPA, volume
ratio 5:1) considerably improved the yield of 4a
(Table 1, entry 15). When the catalyst loading was
increased to 4 mol%, the catalytic performance was
further enhanced (Table 1, entry 16). The control
reaction using Li[N(TMS)2] (12 mol%) as a catalyst
gave γ -oxophosphonate and 1,2-oxaphospholane in
Entry
Ar4
Ar5
Product Yield (%)b
1
2
3
4
5
6
7
8
Ph
2-CH3C6H4
2-CH3OC6H4
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
4-BrC6H4
1-naphthyl
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
92
92
87
93
89
90
92
86
86
80
96
95
85
3g
3h
3i
9
4-CH3C6H4
4-CH3OC6H4
4-ClC6H4
4-BrC6H4
4-ClC6H4
10
11
12
13
Ph
Ph
Ph
3j
3k
3l
4-ClC6H4
3m
aReactions were performed with 1 mmol chalcone and 1.2 mmol
diethyl phosphite in 2 mL of THF for 5 h. Ar1 = 2,6-(tBu)2–4-MeC6H2.
bIsolated yield.
9), indicating that the activity of Yb(OAr1)3(THF)2
may result from the cooperation of lanthanide cation
and aryloxide anion. Several different lanthanides
were then investigated to examine the effect of the
cation on catalytic activity (Table 1, entries 2–4).
The aryloxide complex of Yb, the lanthanide with
the smallest ionic radius and strongest Lewis acid-
ity of those tested, gave the best result. According
to our previous work [58], the steric hindrance of
the aryloxide ligand has a large influence on the
reactivity of Ln(OAr)3(THF)2. Therefore, we tested
Yb(OAr)3(THF)2 with different Ar groups. The re-
sults showed that the more bulky Ar, the higher the
catalytic activity of Ln(OAr)3(THF)2 (Table 1, entries
2,5, and 6). This conclusion is consistent with that
obtained previously and it may be because the elon-
gated Ln–O bond distance caused by the more bulky
aryloxide ligand increases the Lewis acidity of the
Ln cation.
Considering the above results, we decided to
use Yb(OAr1)3(THF)2 as the catalyst in the reac-
tions of various substituted chalcones and diethyl
phosphite. Table 2 shows that all the substrates ex-
amined in this study underwent phospha-Michael
addition smoothly, with effective conversion occur-
ring within 5 h in the presence of 5 mol% cata-
lyst at room temperature, to afford the correspond-
ing γ -oxophosphonates in high yields. The reaction
was general for chalcones with the phenyl ring at
3-position bearing substituents at ortho- and para-
positions, regardless of their electronic nature. The
reactivity of chalcones with the phenyl group at
Heteroatom Chemistry DOI 10.1002/hc

348 Zhang et al.
TABLE 3 [(Me3Si)2N]3La(μ-Cl)Li(THF)3-Catalyzed Reactions of Substituted Chalcones with Diethyl Phosphitea
Entry
Ar6
R1
Time (h)
Product
Yield (%)b
Ratio of Isomers (major : minor)c
1
2
3
4
5
6
7
8
Ph
4-ClC6H4
4-BrC6H4
4-CH3C6H4
4-CH3OC6H4
4-(CH3)2NC6H4
2-CH3C6H4
1-naphthyl
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
5
5
5
5
5
4a
4b
4c
4d
4e
4f
80
86
80
58
66
60
53
35
61
65
61
71
79
1.1:1
1.3:1
2.5:1
1.8:1
1.4:1
2.4:1
8.4:1
8.3:1
1.0:1
3.1:1
1.6:1
1.9:1
4.1:1
5
10
12
10
10
10
5
4g
4h
4i
9
4-CH3OC6H4
4-ClC6H4
4-BrC6H4
4-ClC6H4
Me
10
11
12
13
Ph
Ph
4-ClC6H4
Ph
4j
4k
4l
5
4m
aReactions were performed with 1 mmol chalcone and 3 mmol diethyl phosphite in 2 mL of solvent (toluene/HMPA = 5/1).
bIsolated yields.
cDetermined by 31P NMR spectroscopy.
SCHEME 1 Proposed mechanism for the lanthanide-catalyzed addition of diethyl phosphite to chalcone.
yields of 30% and 15%, respectively (Table 1, entry
17), indicating the importance of the lanthanide ion
in the catalyst.
the activity of chalcones with the aryl at 3-position
bearing electron-withdrawing groups was higher
than that of those bearing electron-donating groups.
4-Phenylbut-3-en-2-one reacted similarly to chal-
cones (Table 1, entry 13). The 31P nuclear magnetic
resonance (NMR) spectra indicated that the reaction
affords the product as a mixture of cis and trans
isomers. However, unambiguous assignment of
each diastereomer had no success.
According to the distinctive properties of
[(Me3Si)2N]3La(μ-Cl)Li(THF)3, the proposed mech-
anism (Scheme 1) for this reaction may involve rapid
deprotonation of diethyl phosphite to release amine
and form intermediate A, which is probably the cat-
alytically active species. The coordination of the lan-
To demonstrate the generality of this
route to 1,2-oxaphospholane, the process was
extended to a serial of substituted chalcones
using [(Me3Si)2N]3La(μ-Cl)Li(THF)3 as a repre-
sentative lanthanide catalyst. The corresponding
1,2-oxaphospholane-5-phosphonates were obtained
in moderate to high yields, as summarized in
Table 3. When the aryl at 3-position of chalcone
was 1-naphthyl or 2-methylphenyl, relatively lower
yields were obtained even after a prolonged reaction
time (Table 1, entries 7 and 8), indicating obvious
steric effects. An electronic effect was also observed:
Heteroatom Chemistry DOI 10.1002/hc

Lanthanide-Catalyzed Selective Addition of Diethyl Phosphite to Chalcones 349
SCHEME 2 Transformation of 3a into 4a.
thanide center in species A with the carbonyl group
may both activate the chalcone and lead to a close
contact between the enone and P-nucleophile. Inter-
mediate B is then formed by phospha-Michael ad-
dition, followed by proton exchange with another
phosphite to release γ -oxophosphonate 3 and re-
generate A. A then undergoes a Pudovik reaction
with 3 to form intermediate C, which subsequently
cyclizes by intramolecular ester exchange to give
1,2-oxaphospholane-5-phosphonate 4 and regener-
ate A. The analyses of the crude products of the
reaction with 3a as a substrate (Scheme 2) indi-
cated that most of 3a is transformed into 4a, ver-
ifying that 3a is the intermediate during the for-
mation of 4a. When Ln(OAr)3(THF)2 is used as a
catalyst, the deprotonation equilibrium of diethyl
phosphite may be reversed because of the relatively
strong acidity of ArOH (Scheme 3). The concentra-
tion of A in the reaction mixture may be low and the
phosphorus-nucleophilic attack is hindered. Finally,
the second catalytic cycle involving the relatively dif-
ficult Pudovik reaction of steric bulky ketone may be
inhibited.
SCHEME 3 Plausible deprotonation equilibrium of diethyl
phosphite in the presence of Ln(OAr)3(THF)2.
dard Schlenk techniques. Ln(OAr)3(THF)2 [87,
88], Ln[N(SiMe3)2]3 [89], and [(Me3Si)2N]3Ln(μ-
Cl)Li(THF)3 [61–63] were synthesized according
to the literature method. Chalcones were pre-
pared according to published procedures [90]. Di-
ethyl phosphite was purchased from Lianyungang
Shengnan Chemical Co., Lianyungang, Jiangsu
Province, China. 1H and 13C NMR spectra were
obtained on Varian INOVA-400 and System-300
spectrometers using tetramethylsilane (TMS) as an
internal reference. Infrared (IR) spectra were ob-
tained on a Nicolet FT-IR 1000 spectrophotometer.
High resolution mass spectrometry (HRMS) data
were obtained on a Micromass GCT instrument.
Representative Procedure for the Synthesis of
γ -Oxophosphonate
In conclusion, efficient phospha-Michael ad-
dition of diethyl phosphite with chalcones was
achieved in the presence of catalytic amounts
of lanthanide complexes under mild conditions.
The reaction exhibited good product selectiv-
ity using different catalysts. γ -Oxophosphonates
could be obtained in high yields in the re-
A mixture of chalcone (210 mg, 1 mmol), di-
ethyl phosphite (165 mg, 1.2 mmol), and Yb(OAr1)3
(THF)2 [Ar1 = 2,6-(tBu)2–4-MeC6H2] (50 mg, 0.05
mmol) in tetrahydrofuran (2.0 mL) was stirred for
5 h at 25◦C. Water was added and the mixture was
extracted with ethyl acetate. The combined organic
layers were dried over anhydrous Na2SO4, concen-
trated in vacuo, and purified by chromatography on
silica gel [eluant: EtOAc/petroleum ether (60–90◦C)
1:2] to afford pure product 3a (318 mg, 92%) as a
colorless oil.
actions catalyzed by Yb(OAr1)3(THF)2 [Ar1
=
2,6-(tBu)2–4-MeC6H2], whereas those catalyzed
by [(Me3Si)2N]3La(μ-Cl)Li(THF)3 afforded 1,2-
oxaphospholane-5-phosphonates as the major prod-
ucts in moderate to good yields. This catalyst-
controlled product selectivity induced by lanthanide
complexes provided facile and practical approaches
to produce the corresponding organophosphorus
compounds with biological interest.
Representative Procedure for the Synthesis of
1,2-Oxaphospholane-5-Phosphonate
A mixture of chalcone (210 mg, 1 mmol), diethyl
phosphite (415 mg, 3 mmol), and [(Me3Si)2N]3La(μ-
Cl)Li(THF)3 (35 mg, 0.04 mmol) in mixed solvent
of toluene/HMPA (5:1, 2.0 mL) was stirred for 5 h
at 40◦C. Water was added and the mixture was ex-
tracted with ethyl acetate. The combined organic lay-
ers were dried over anhydrous Na2SO4, concentrated
EXPERIMENTAL
General Remarks
All operations involving air- and moisture-sensitive
compounds were carried out under an in-
ert atmosphere of purified argon using stan-
Heteroatom Chemistry DOI 10.1002/hc

350 Zhang et al.
in vacuo, and purified by chromatography on silica
gel [eluant: EtOAc/petroleum ether (60–90◦C) 1:1] to
afford pure product 4a (350 mg, 80%) as a colorless
oil.
3 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.11 (t, J = 7.2 Hz,
3 H) ppm.
Diethyl 1-(4-chlorophenyl)-3-oxo-3-phenylpropyl-
1
phosphonate (3f) [54]. H NMR (400 MHz, CDCl3):
Diethyl
3-oxo-1,3-diphenylpropylphosphonate
δ = 7.93 (d, J = 8.0 Hz, 2 H), 7.56 (t, J = 7.2 Hz, 1 H),
7.47–7.26 (m, 6 H), 4.14–4.05 (m, 2 H), 3.99–3.89 (m,
2 H), 3.83–3.61 (m, 3 H), 1.29 (t, J = 7.2 Hz, 3 H),
1.13 (t, J = 7.2 Hz, 3 H) ppm.
1
(3a) [54]. H NMR (400 MHz, CDCl3): δ = 7.94 (d,
J = 7.6 Hz, 2 H), 7.55 (t, J = 7.2 Hz, 1 H), 7.46–7.42
(m, 4H), 7.31–7.20 (m, 3 H), 4.17–3.87 (m, 4 H),
3.81–3.63 (m, 3 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.08 (t,
J = 7.2 Hz, 3 H) ppm.
Diethyl 1-(4-bromophenyl)-3-oxo-3-phenylpropyl-
1
phosphonate (3g) [54]. H NMR (400 MHz, CDCl3):
Diethyl 3-oxo-3-phenyl-1-o-tolylpropylphospho-
nate (3b). White solid, melting point (mp) 95–96◦C.
1H NMR (400 MHz, CDCl3): δ = 7.94 (d, J = 7.6 Hz,
2 H), 7.55 (t, J = 7.2 Hz, 1 H), 7.46–7.42 (m, 3 H),
7.17–7.08 (m, 3 H), 4.27–4.18 (m, 1 H), 4.12–4.02 (m,
2 H), 3.88–3.79 (m, 2 H), 3.72–3.58 (m, 2 H), 2.55 (s,
3 H), 1.29 (t, J = 7.2 Hz, 3 H), 1.04 (t, J = 7.2 Hz,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 196.3 (d,
J = 13.6 Hz), 137.6 (d, J = 7.7 Hz), 136.3, 134.2 (d,
J = 6.8 Hz), 133.1, 130.2, 128.4, 127.9, 127.4 (d, J =
4.2 Hz), 126.8 (d, J = 2.7 Hz), 125.9 (d, J = 2.6 Hz),
62.8 (d, J = 6.7 Hz), 61.7 (d, J = 7.2 Hz), 39.5, 33.8
(d, J = 139.6 Hz), 20.0, 16.2 (d, J = 6.0 Hz), 16.0 (d,
J = 5.6 Hz) ppm. HRMS (electrospray ionization,
ESI): calcd. for C20H25O4P [M + H]+ 361.1563,
found 361.1577. IR: ν = 2982, 2903, 1689, 1596,
δ = 7.93 (d, J = 7.6 Hz, 2 H), 7.57 (t, J = 7.2 Hz, 1 H),
7.47–7.27 (m, 6 H), 4.15–3.87 (m, 4 H), 3.84–3.60 (m,
3 H), 1.29 (t, J = 7.2 Hz, 3 H), 1.13 (t, J = 7.2 Hz,
3 H) ppm.
Diethyl 1-(naphthalen-1-yl)-3-oxo-3-phenylpropyl-
1
phosphonate (3h) [54]. H NMR (400 MHz, CDCl3):
δ = 8.40 (d, J = 8.0 Hz, 1 H), 7.95 (d, J = 7.6 Hz, 2 H),
7.83 (d, J = 8.0 Hz, 1 H), 7.75–7.43 (m, 8 H), 4.94 (d,
J = 22.4 Hz, 1 H), 4.12–4.06 (m, 2 H), 3.91 (dd, J =
10.4, 6.8 Hz, 2 H), 3.78–3.68 (m, 1 H), 3.42–3.36 (m,
1 H), 1.26 (t, J = 7.2 Hz, 3 H), 0.79 (t, J = 7.2 Hz,
3 H) ppm.
Diethyl 3-oxo-1-phenyl-3-p-tolylpropylphospho-
nate (3i). White solid, mp 76–77◦C. 1H NMR
(300 MHz, CDCl3): δ = 7.84 (d, J = 8.1 Hz, 2 H),
7.45–7.42 (m, 2 H), 7.31–7.22 (m, 5 H), 4.10–3.86
(m, 4 H), 3.80–3.63 (m, 3 H), 2.39 (s, 3 H), 1.28 (t,
J = 7.2 Hz, 3 H), 1.08 (t, J = 7.2 Hz, 3 H) ppm. 13C
NMR (75 MHz, CDCl3): δ = 196.1 (d, J = 14.6 Hz),
144.2, 136.2, 136.1, 134.3, 129.4, 128.6, 128.3, 127.3,
63.0 (d, J = 7.1 Hz), 62.1 (d, J = 7.3 Hz), 39.2 (d,
J = 139 Hz), 39.1, 21.8, 16.5 (d, J = 4.1 Hz), 16.3 (d,
J = 5.0 Hz) ppm. HRMS (ESI): calcd. for C20H25O4P
[M + H]+ 361.1563, found 361.1568. IR: ν = 3061,
2979, 2909, 2889, 1678, 1606, 1501, 1458, 1393,
1493, 1447, 1392, 1251, 961, 776, 734, and 713 cm−1
Diethyl 1-(2-methoxyphenyl)-3-oxo-3-phenylpropyl-
phosphonate (3c) [54]. H NMR (400 MHz, CDCl3):
δ = 7.94 (d, J = 7.6 Hz, 2 H), 7.53 (t, J = 7.2 Hz,
1 H), 7.45–7.41 (m, 3 H), 7.19 (t, J = 7.6 Hz, 1 H),
6.90–6.86 (m, 2 H), 4.66–4.57 (m, 1 H), 4.11–4.08 (m,
2 H), 3.95–3.69 (m, 4 H), 3.87 (s, 3 H), 1.27 (t, J =
7.2 Hz, 3 H), 1.09 (t, J = 7.2 Hz, 3 H) ppm.
.
1
Diethyl 3-oxo-3-phenyl-1-p-tolylpropylphospho-
nate (3d). Colorless oil. 1H NMR (400 MHz, CDCl3):
δ = 7.94 (d, J = 7.2 Hz, 2 H), 7.54 (t, J = 7.2 Hz, 1 H),
7.43 (t, J = 7.6 Hz, 2 H), 7.32 (dd, J = 8.0, 2.0 Hz,
2 H), 7.09 (d, J = 7.6 Hz, 2 H), 4.12–4.02 (m, 2 H),
3.98–3.87 (m, 2 H), 3.78–3.61 (m, 3 H), 2.28 (s, 3 H),
1.28 (t, J = 7.2 Hz, 3 H), 1.10 (t, J = 7.2 Hz, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 196.6 (d, J =
15.5 Hz), 137.0 (d, J = 3.5 Hz), 136.7, 133.4, 132.8
(d, J = 7.5 Hz), 129.3, 129.2 (d, J = 7.0 Hz), 128.7,
128.2, 63.1 (d, J = 7.7 Hz), 62.1 (d, J = 7.9 Hz),
39.2, 38.7 (d, J = 140 Hz), 21.2, 16.5 (d, J = 6.4 Hz),
16.4 (d, J = 6.3 Hz) ppm. HRMS (ESI): calcd. for
C20H25O4P [M + H]+ 361.1563, found 361.1559. IR:
ν = 2971, 2931, 1690, 1515, 1466, 1380, 1234, 1025,
1237, 1049, 950, 812, 755, and 700 cm−1
.
Diethyl 3-(4-methoxyphenyl)-3-oxo-1-phenylpro-
pylphosphonate (3j) [54]. 1H NMR (400 MHz,
CDCl3): δ = 7.93 (d, J = 8.4 Hz, 2 H), 7.44 (d, J =
7.2 Hz, 2 H), 7.31–7.21 (m, 3 H), 6.90 (d, J = 8.8 Hz,
2 H), 4.10–3.89 (m, 4 H), 3.84 (s, 3 H), 3.76–3.58 (m,
3 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.07 (t, J = 7.2 Hz,
3 H) ppm.
Diethyl 3-(4-chlorophenyl)-3-oxo-1-phenylpropyl-
1
phosphonate (3k) [54]. H NMR (400 MHz, CDCl3):
δ = 7.88 (d, J = 8.0 Hz, 2 H), 7.42–7.40 (m, 4 H),
7.32–7.21 (m, 3 H), 4.10–3.85 (m, 4 H), 3.76–3.60 (m,
3 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.07 (t, J = 7.2 Hz, 3 H)
ppm.
Diethyl 3-(4-bromophenyl)-3-oxo-1-phenylpropyl-
phosphonate (3l). White solid, mp 73–74◦C. 1H NMR
(400 MHz, CDCl3): δ = 7.80 (d, J = 8.8 Hz, 2 H), 7.58
(d, J = 8.4 Hz, 2 H), 7.43–7.41 (m, 2 H), 7.38–7.27
(m, 3 H), 4.11–4.03 (m, 2 H), 3.98–3.87 (m, 2 H),
3.74–3.59 (m, 3 H), 1.28 (t, J = 7.2 Hz, 3 H), 1.07 (t,
953, 817, 757, and 690 cm−1
.
Diethyl 1-(4-methoxyphenyl)-3-oxo-3-phenylpro-
pylphosphonate (3e) [54]. 1H NMR (400 MHz,
CDCl3): δ = 7.94 (d, J = 7.6 Hz, 2 H), 7.55 (t, J =
7.6 Hz, 1 H), 7.46–7.35 (m, 4 H), 6.83 (d, J = 8.4 Hz,
2 H), 4.11–3.87 (m, 4 H), 3.76 (s, 3 H), 3.74–3.63 (m,
Heteroatom Chemistry DOI 10.1002/hc

Lanthanide-Catalyzed Selective Addition of Diethyl Phosphite to Chalcones 351
J = 7.2 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3)
2 H), 1.42–0.98 (m, 9 H) ppm. 31P NMR (121 MHz,
CDCl3): δ = 40.8 (d, J = 30.3 Hz, minor diastere-
omer), 38.5 (d, J = 13.3 Hz, major diastereomer),
18.2 (d, J = 13.3 Hz, major diastereomer), 16.2 (d,
J = 30.3 Hz, minor diastereomer) ppm. HRMS
(ESI): calcd. for C21H27BrO6P2 [M + H]+ 517.0539,
found 517.0530. IR: ν = 3063, 2988, 2908, 2852,
1600, 1492, 1446, 1393, 1283, 1033, 864, 822, 793,
δ = 195.6 (d, J = 15.4 Hz), 135.9 (d, J = 7.3 Hz),
135.4, 132.1, 129.7, 129.3 (d, J = 7.2 Hz), 128.7 (d,
J = 2.4 Hz), 127.5 (d, J = 3.1 Hz), 63.2 (d, J = 7.7 Hz),
62.2 (d, J = 7.8 Hz), 39.2, 39.1 (d, J = 140 Hz), 16.5 (d,
J = 6.5 Hz), 16.3 (d, J = 6.2 Hz) ppm. HRMS (ESI):
calcd. for C19H22BrO4P [M + H]+ 425.0512, found
425.0501. IR: ν = 3061, 2991, 2929, 1685, 1586, 1500,
1433, 1397, 1251, 1031, 951, 862, 810, 788, 732, and
764, and 699 cm−1
.
701 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-p-tolyl-5-phenyl-1,2-
oxaphospholan-5-yl)phosphonate (4d). Colorless oil.
1H NMR (400 MHz, CDCl3): δ = 7.58–7.03 (m, 9 H),
4.24–3.40 (m, 7 H), 3.24–2.66 (m, 2 H), 2.22 (s, 3 H),
1.33–1.03 (m, 7 H), 0.90–0.87 (m, 2 H) ppm. 31P
NMR (121 MHz, CDCl3): δ = 41.8 (d, J = 30.1 Hz,
minor diastereomer), 39.8 (d, J = 12.6 Hz, major
diastereomer), 18.4 (d, J = 12.6 Hz, major diastere-
omer), 16.5 (d, J = 30.1 Hz, minor diastereomer)
ppm. HRMS (ESI): calcd. for C22H30O6P2 [M + H]+
453.1590, found 453.1590. IR: ν = 3060, 2978, 2910,
2867, 1602, 1495, 1448, 1397, 1242, 1054, 972, 817,
Diethyl 1,3-bis(4-chlorophenyl)-3-oxopropylphos-
phonate (3m). Colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.77 (d, J = 6.8 Hz, 2 H), 7.33–7.27
(m, 4 H), 7.18–7.17 (m, 2 H), 4.02–3.98 (m, 2 H),
3.88–3.78 (m, 2 H), 3.72–3.54 (m, 3 H), 1.20 (t, J =
7.2 Hz, 3 H), 1.03 (t, J = 7.2 Hz, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 194.9 (d, J = 15.2 Hz), 139.8,
134.6, 134.4 (d, J = 6.9 Hz), 133.1 (d, J = 3.5 Hz),
130.5 (d, J = 6.5 Hz), 129.4, 128.9, 128.6, 63.0 (d,
J = 6.9 Hz), 62.1 (d, J = 7.1 Hz), 38.9, 38.4 (d, J =
140 Hz), 16.3 (d, J = 5.8 Hz), 16.2 (d, J = 5.5 Hz)
ppm. HRMS (ESI): calcd. for C19H21Cl2O4P [M +
H]+ 415.0627, found 415.0618. IR: ν = 2983, 2911,
1690, 1589, 1491, 1385, 1245, 1094, 1050, 829, and
794, 746, and 702 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-(4-methoxyphenyl)-
5-phenyl-1,2-oxaphospholan-5-yl)phosphonate (4e).
797 cm−1
Diethyl
.
Colorless oil. H NMR (400 MHz, CDCl3): δ = 7.66–
1
(2-ethoxy-2-oxido-3,5-diphenyl-1,2-
6.84 (m, 9 H), 4.34–3.48 (m, 10 H), 3.29–2.70 (m,
2 H), 1.43–1.12 (m, 7 H), 1.01–0.98 (m, 2 H) ppm. 31P
NMR (121 MHz, CDCl3): δ = 43.1 (d, J = 29.8 Hz,
minor diastereomer), 40.9 (d, J = 12.6 Hz, major
diastereomer), 19.6 (d, J = 12.6 Hz, major diastere-
omer), 17.6 (d, J = 29.8 Hz, minor diastereomer)
ppm. HRMS (ESI): calcd. for C22H30O7P2 [M + H]+
469.1540, found 469.1557. IR: ν = 2990, 1608, 1511,
oxaphospholan-5-yl)phosphonate (4a). Colorless oil.
1H NMR (300 MHz, CDCl3): δ = 7.67–7.29 (m, 10 H),
4.35–3.48 (m, 7 H), 3.33–2.74 (m, 2 H), 1.44–1.36 (m,
3 H), 1.32–0.93 (m, 6 H) ppm. 31P NMR (121 MHz,
CDCl3): δ = 42.7 (d, J = 30.1 Hz, major diastere-
omer), 40.7 (d, J = 12.6 Hz, minor diastereomer),
19.5 (d, J = 12.6 Hz, minor diastereomer), 17.6
(d, J = 30.1 Hz, major diastereomer) ppm. HRMS
(ESI): calcd. for C21H28O6P2 [M + H]+ 439.1434,
found 439.1436. IR: ν = 3061, 3030, 2983, 2932,
2870, 1602, 1496, 1449, 1392, 1260, 1024, 764, and
1460, 1251, 1029, 859, 758, and 698 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-(4-dimethylamino-
phenyl)-5-phenyl-1,2-oxaphospholan-5-yl)phospho-
nate (4f). Yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.58–6.59 (m, 9 H), 4.25–3.38 (m, 7 H), 3.21–2.62
(m, 2 H), 2.85 (s, 6 H), 1.35–0.92 (m, 9 H) ppm. 31P
NMR (121 MHz, CDCl3): δ = 42.2 (d, J = 29.2 Hz,
major diastereomer), 40.3 (d, J = 12.6 Hz, minor
diastereomer), 18.6 (d, J = 12.6 Hz, minor diastere-
omer), 16.6 (d, J = 29.2 Hz, major diastereomer)
ppm. HRMS (ESI): calcd. for C23H33NO6P2 [M +
H]+ 482.1856, found 482.1857. IR: ν = 2920, 1608,
699 cm−1
Diethyl (2-ethoxy-2-oxido-3-(4-chlorophenyl)-5-
phenyl-1,2-oxaphospholan-5-yl)phosphonate (4b).
.
1
Colorless oil. H NMR (400 MHz, CDCl3): δ = 7.66–
7.29 (m, 9 H), 4.38–3.47 (m, 7 H), 3.31–2.69 (m, 2 H),
1.43–0.98 (m, 9 H) ppm. 31P NMR (121 MHz, CDCl3):
δ = 42.1 (d, J = 30.3 Hz, minor diastereomer), 39.8
(d, J = 12.7 Hz, major diastereomer), 19.3 (d,
J = 12.7 Hz, major diastereomer), 17.4 (d, J =
30.3 Hz, minor diastereomer) ppm. HRMS (ESI):
calcd. for C21H27ClO6P2 [M + H]+ 473.1044, found
473.1047. IR: ν = 3061, 2983, 2907, 1493, 1447,
1579, 1509, 1448, 1245, 1023, 863, and 701 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-o-tolyl-5-phenyl-1,2-
oxaphospholan-5-yl)phosphonate (4g). Colorless oil.
1H NMR (400 MHz, CDCl3): δ = 7.76–7.15 (m, 9 H),
4.39–3.80 (m, 6 H), 3.77–3.30 (m, 2 H), 2.96–2.73
(m, 1 H), 2.43–2.29 (m, 3 H), 1.40–1.02 (m, 9 H)
ppm. 31P NMR (121 MHz, CDCl3): δ = 42.9 (d, J =
30.5 Hz, major diastereomer), 39.9 (d, J = 11.4 Hz,
minor diastereomer), 19.7 (d, J = 11.4 Hz, minor
1386, 1246, 1095, 1029, 861, 795, 766, and 701 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-(4-bromophenyl)-5-
phenyl-1,2-oxaphospholan-5-yl)phosphonate (4c).
1
Colorless oil. H NMR (400 MHz, CDCl3): δ = 7.65–
7.21 (m, 9 H), 4.33–3.50 (m, 7 H), 3.29–2.71 (m,
Heteroatom Chemistry DOI 10.1002/hc

352 Zhang et al.
diastereomer), 17.6 (d, J = 30.5 Hz, major diastere-
omer) ppm. HRMS (ESI): calcd. for C22H30O6P2 [M
+ H]+ 453.1590, found 453.1598. IR: ν = 3061, 2982,
2930, 2870, 1603, 1493, 1448, 1391, 1262, 1019, 795,
Diethyl
(2-ethoxy-2-oxido-3,5-bis(4-chlorophe
(4l).
nyl)-1,2-oxaphospholan-5-yl)phosphonate
White solid, mp 153–154◦C. 1H NMR (400 MHz,
CDCl3): δ = 7.68–7.26 (m, 8 H), 4.33–3.46 (m, 7 H),
3.24–2.66 (m, 2 H), 1.42–0.99 (m, 9 H) ppm. 31P
NMR (121 MHz, CDCl3) δ = 40.9 (d, J = 29.0 Hz,
minor diastereomer), 38.6 (d, J = 12.1 Hz, major
diastereomer), 17.7 (d, J = 12.1 Hz, major diastere-
omer), 15.8 (d, J = 29.0 Hz, minor diastereomer)
ppm. HRMS (ESI): calcd. for C21H26Cl2O6P2 [M +
H]+ 507.0654, found 507.0647. IR: ν = 3061, 2985,
2907, 2868, 1598, 1492, 1443, 1392, 1261, 1032, 948,
761, and 699 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-(naphthalen-1-yl)-5-
phenyl-1,2-oxaphospholan-5-yl)phosphonate (4h).
White solid, mp 118–119◦C. 1H NMR (400 MHz,
CDCl3): δ = 8.43–7.36 (m, 12 H), 5.05–4.94 (m, 1 H),
4.44–4.27 (m, 2 H), 3.99–3.83 (m, 5 H), 3.21–3.07 (m,
1 H), 1.50–0.79 (m, 9 H) ppm. 31P NMR (121 MHz,
CDCl3): δ = 39.3 (d, J = 27.3 Hz, minor diastere-
omer), 38.7 (d, J = 11.1 Hz, major diastereomer),
18.6 (d, J = 11.1 Hz, major diastereomer), 16.9 (d,
J = 27.3 Hz, minor diastereomer) ppm. HRMS
(ESI): calcd. for C25H30O6P2 [M + H]+ 489.1590,
found 489.1591. IR: ν = 2981, 1494, 1446, 1248,
821, and 746 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-phenyl-5-methyl-1,2-
oxaphospholan-5-yl)phosphonate (4m). Colorless oil.
1H NMR (300 MHz, CDCl3): δ = 7.31–7.20 (m, 5 H),
4.27–3.83 (m, 6 H), 3.73–3.30 (m, 1 H), 3.02–2.79 (m,
1 H), 2.49–2.30 (m, 1 H), 1.66–1.58 (m, 3 H), 1.33–
1.18 (m, 7 H), 0.99–0.94 (m, 2 H) ppm. 31P NMR
(121 MHz, CDCl3): δ = 43.4 (d, J = 33.3 Hz, mi-
nor diastereomer), 40.9 (d, J = 13.8 Hz, major di-
astereomer), 22.3 (d, J = 13.8 Hz, major diastere-
omer), 21.4 (d, J = 33.3 Hz, minor diastereomer)
ppm. HRMS (ESI): calcd. for C16H26O6P2 [M + H]+
377.1277, found 377.1280. IR: ν = 3030, 2983, 2934,
2871, 1602, 1497, 1450, 1391, 1245, 970, 813, 761,
1021, 848, 803, 780, 740, and 700 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-phenyl-5-(4-methoxy-
phenyl)-1,2-oxaphospholan-5-yl)phosphonate (4i).
1
Colorless oil. H NMR (400 MHz, CDCl3): δ = 7.50–
6.85 (m, 9 H), 4.26–3.37 (m, 10 H), 3.25–2.65 (m,
2 H), 1.36–0.86 (m, 9 H) ppm. 31P NMR (121 MHz,
CDCl3): δ = 42.8 (d, J = 31.7 Hz, minor diastere-
omer), 40.8 (d, J = 13.2 Hz, major diastereomer),
19.7 (d, J = 13.2 Hz, major diastereomer), 17.8 (d,
J = 31.7 Hz, minor diastereomer) ppm. HRMS
(ESI): calcd. for C22H30O7P2 [M + H]+ 469.1540,
found 469.1559. IR: ν = 2981, 2931, 1609, 1499,
and 700 cm−1
.
1440, 1385, 1251, 1029, 949, 862, 794, and 700 cm−1
.
Diethyl (2-ethoxy-2-oxido-3-phenyl-5-(4-chloro-
phenyl)-1,2-oxaphospholan-5-yl)phosphonate (4j).
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Colorless oil. 1H NMR (400 MHz, CDCl3): δ =
7.62–7.27 (m, 9 H), 4.35–2.69 (m, 9 H), 1.43–0.94
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