Asymmetric synthesis of cyclopropyl phosphonates using chiral terpenyl sulfonium and selenonium ylides

Article abstract of DOI:10.1016/j.tetasy.2014.10.002

The asymmetric cyclopropanation of a vinylphosphonate using optically active sulfonium and selenonium ylides derived from (-)-menthol and (+)-limonene was developed. The ylides were generated in situ by the reaction of the corresponding sulfonium or selenonium salt in the presence of potassium carbonate or DBU as a base. The transfer of the CHPh and CHCO₂Et groups into the cyclopropane ring showed moderate diastereoselectivity and excellent enantioselectivity (up to 99:1) for the trans- and cis-products. The absolute configuration of phenyl cyclopropyl was assigned based on comparison to their tolyl analogues.

Full text of DOI:10.1016/j.tetasy.2014.10.002

Tetrahedron: Asymmetry 25 (2014) 1488–1493
Contents lists available at ScienceDirect
Tetrahedron: Asymmetry
journal homepage: www.elsevier.com/locate/tetasy
Asymmetric synthesis of cyclopropyl phosphonates using chiral
terpenyl sulfonium and selenonium ylides
b
b
a
Wanda H. Midura a, , Jacek Scianowski , Anna Banach , Adrian Zaja˛c
⇑
´
a Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz, Poland
b Department of Organic Chemistry, Faculty of Chemistry, Nicolaus Copernicus University, 7 Gagarin Street, 87-100 Torun, Poland
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 16 September 2014
Accepted 7 October 2014
The asymmetric cyclopropanation of a vinylphosphonate using optically active sulfonium and selenonium
ylides derived from (ꢀ)-menthol and (+)-limonene was developed. The ylides were generated in situ by
the reaction of the corresponding sulfonium or selenonium salt in the presence of potassium carbonate
or DBU as a base. The transfer of the CHPh and CHCO2Et groups into the cyclopropane ring showed mod-
erate diastereoselectivity and excellent enantioselectivity (up to 99:1) for the trans- and cis-products. The
absolute configuration of phenyl cyclopropyl was assigned based on comparison to their tolyl analogues.
Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
cyclopropanes were obtained with high diastereoselectivities (dr
90:10–>99:1).9
Sulfur ylides, a well known class of organic compounds, have
been used as alkylidene transfer agents since the early work of
Corey.1 The potential of sulfur ylides for the preparation of opti-
cally active epoxides has been the subject of research in different
laboratories.2,3 Various chalcogenes have been investigated for
either a one pot reaction or two step procedure with pre-isolation
of the chalcogen-onium salt.4
In our previous studies, we prepared a series of acyclic and cyc-
lic terpenyl sulfides and selenides, derived from p-menthane, cara-
ne, and pinane groups, and successfully used them for asymmetric
epoxidation.10 For example, isoselenocineole 1, the selenium ana-
logue of isothiocineole 2, the most effective sulfide used in asym-
metric epoxidation and aziridination, was prepared, and used for
the epoxidation of styrene (dr 39:61, er trans 81:19).
Although initial asymmetric cyclopropanation reactions using
chiral sulfur ylides were not the focus of interest, recently the
chiral ylide route became one of the most important methods.5
Various sulfonium ylides were applied effectively, for example,
camphor-derived sulfonium ylides were used to prepare 1-
aminocyclopropanecarboxylic acids in 44–95% yield, with >99:1
dr and 10–92% ee.6 The reaction of ester-stabilized sulfonium
ylides with cyclopentenone gave the corresponding cyclopropane,
and was a crucial step in the synthesis of the pharmacologically
important compound (+)-LY354740.7 Chiral telluronium ylides
were used in asymmetric cyclopropanations to give chiral cyclo-
propanes in yields of up to 99% with excellent diastereoselectivi-
ties and enantioselectivities.8 The first example of the application
of chiral selenonium ylides in the asymmetric synthesis of enanti-
omerically enriched cyclopropanes was achieved using exo and
endo-camphor-derived selenonium salts. In the reaction with
Herein we decided to test terpenyl selenides and sulfides,
derived from (ꢀ)-menthol and (+)-limonene, in the asymmetric
synthesis of cyclopropyl phosphonates, mediated by the corre-
sponding chiral ylides.
2. Results and discussion
Recently, our interest has been mainly focused on chiral cyclo-
propyl phosphonates,11 as key intermediates in the asymmetric
synthesis of constrained phosphonic analogues of natural and
non-natural amino acids, exhibiting in some cases biological and
therapeutic activity. For this reason, our investigations were
performed using vinyl phosphonates as Michael acceptors. The
reactivity of the olefin was increased by the introduction of a
second electron-withdrawing substituent on the
a-carbon atom
(3: X = CO2Et, 4: X = SO2Ph), which could also be useful in further
application of the obtained cyclopropanes. Benzyl terpenyl sulfo-
nium and selenonium salts 5–9 were prepared by our methodology
based on the reaction of the corresponding sulfides and selenides
with benzyl bromide in the presence of AgBF4.10 The ylide was
generated in situ by the reaction of an appropriate onium salt with
various
a,b-unsaturated carbonyl compounds, trisubstituted
⇑
Corresponding author.
E-mail address: whmidura@cbmm.lodz.pl (W.H. Midura).
http://dx.doi.org/10.1016/j.tetasy.2014.10.002
0957-4166/Ó 2014 Elsevier Ltd. All rights reserved.

W.H. Midura et al. / Tetrahedron: Asymmetry 25 (2014) 1488–1493
1489
the electrophile, performed in the presence of potassium carbonate
or DBU as a base. The results of the asymmetric cyclopropanation
are presented in Table 1.
Inspection of the data contained in Table 1 shows that the
cyclopropanation of vinyl phosphonates 3 and 4 occurred with
moderate to good yield. The trans/cis ratio was determined by anal-
ysis of the 31P and 1H NMR spectra of the crude products and in
some cases, confirmed by HPLC to establish the ratio of the enan-
tiomers.12 In the case of phosphoryl acrylate 3 we observed almost
no diastereoselectivity. For vinyl phosphonate 4 the ratio of trans/
cis diastereomers was much higher, approximately 4:1, however, it
was not caused by the terpenyl moiety in the ylide, since almost
the same ratio was observed for the reaction with the racemic ylide
(entry 6).
Much more interesting observations were obtained from the
analysis of the enantiomers. Evidently, their ratio depends on the
chiral substituent bonded to the sulfonium or selenonium salts
used in the reaction. Menthol-derived selenonium salts 5 and 9
provided cyclopropanation of the Michael acceptor 4 (entry 8) with
approximately 27% ee. Application of the benzyl sulfonium salt of
Table 1
Cyclopropanation—transfer of CHPh
O
O
X
X
(EtO)2P
(EtO)2P
+
H
Ph
H
O
Ph
X
(EtO)2P
salt, base
b
a
O
O
X
X
(EtO)2P
(EtO)2P
+
3 : X = CO2Et
4 : X = SO2Ph
H
Ph
H
Ph
10 : X = CO2Et
11 : X = SO2Ph
a
ent-
b
ent-
Entry
Salt
Michael
acceptor
Reaction
condition
Total yield (%)
trans/cis
Ratio of trans
enantiomers l/h
Ratio of cis
enantiomers l/h
Me
Ph
Ph
BF4
BF4
S
S
1
2
3
3
DBU, MeCN
62
93
52.2:47.8b
50.0/50.0
50.0/50.0
50.0/50.0
Ph
55.6:44.4a
54.1:45.9b
Me
K2CO3, CH2Cl2
50.0/50.0
43.5/56.5
Ph
BF4
3
4
3
3
K2CO3, CH2Cl2
54
82
47.0:53.0a
57.0:43.0a
40.3/59.7
9.0/91.0
Se
Ph
Me
5
BF4
DBU, acetone
DBU, acetone
6.8/93.2
S
6
Ph
BF4
5
3
20
56.0:44.0a
5.9/94.1
9.4/90.6
Se
7
Ph
Me
Ph
6
7
S
4
4
DBU, MeCN
90
20
76.8:23.2a
80.0:20.0a
50.0/50.0
50.0/50.0
BF4
Ph
BF4
Ph
8
c
c
K2CO3, CH2Cl2
—
—
Se
Me
BF4
Ph
8
9
4
4
DBU, MeCN
DBU, MeCN
53
79
76.2:23.8a
63.3/36.7
2.2/97.8
78.5/21.5
1.0/99.0
Se
Me
9
77.8:22.2a
81.0:19.0b
S
BF4
Ph
6
l—Lower Rf in HPLC; h—higher Rf in HPLC.
a
The ratio of diastereomers determined by NMR.
The ratio of diastereomers determined by HPLC.
Inseparable impurities disturbed the precise determination of the enantiomeric ratio.
b
c

1490
W.H. Midura et al. / Tetrahedron: Asymmetry 25 (2014) 1488–1493
isothiocineole 6 gave enantioselectivities of 82–98% ee for the sul-
fonium salt (entries 4 and 9) and 88–92% ee for the selenonium salt
7 prepared from isoselenocineole (entry 5).
be rationalized by considering the preference of the electrophile
to approach the more favored conformation of the ylide, as pro-
posed by Aggarwal3b to explain the high enantioselectivity of
asymmetric epoxidation and aziridination (Scheme 2).
In order to gain further insight into the configuration of
the obtained cyclopropanes, cyclopropanation of enantiomerically
pure (S)-(+)-(1-diethoxyphosphoryl) vinyl p-tolyl sulfoxide 12 was
performed.13 The reaction of 12 with benzylmethylphenylsulfo-
nium salt in the presence of DBU gave only trans-diastereomers
13, which were oxidized to the sulfone trans-110 and analyzed by
HPLC. Based on the established mechanism,13b the absolute
configuration of the major diastereomer in this experiment was
assigned as (S,R). This allowed us to relate the configuration
of trans-110 with the retention factor: lower Rf—(S,R), higher
Rf—(R,S), assuming that the small structural difference between
11 and 110 should not affect their polarity (Scheme 1).
Encouraged by the results obtained for the benzylidene transfer
reaction, we performed the synthesis of the corresponding salts
with an ethyl acetate substituent. Thus, isoselenocineole 1 and
isothiocineole 2 were treated with 2-bromo ethyl acetate in the
presence of the silver salt (AgBF4) to give the corresponding sele-
nonium 14 and sulfonium 15 salts. The reaction was carried out
using two methods; by Aggarwal’s methodology (path A) and by
our method without the solvent addition (path B) (Scheme 3).
The cyclopropanation of phosphonates 3 and 4 with transfer of
the CHCO2Et group is presented in Table 2.
The high stereoselectivity observed in reactions with a ylide
containing a strong electron withdrawing substituent (CO2Et) sug-
gests the absence, or insignificant participation of epimerization of
the betaine intermediate proposed by Aggarwal (Scheme 4).5b This
was probably due to the presence of the second electron with-
Based on this assumption it appeared that the menthol-derived
selenonium ylide gave (S,R)-11, but the major cyclopropane
11, formed using an isothiocineole derived ylide, had an (R,S)-
configuration. The stereochemical outcome of these reactions can
O
O
Tol-p
O
Tol-p
Me
Ph
Tol-p
S
Ph
BF4
S
S
S
(EtO)2P
(EtO)2P
(EtO)2P
O
O
O
Ph
(R,S)-13
δP 18.8
Ph
1.8 : 1a
12
(S,R)-13
δP 19.0
MCPBA
O
O
SO2Tol-p
SO2Tol-p
(EtO)2P
(EtO)2P
δP
Ph
Ph
14.2
(S,R)-11'
(R,S)-11'
h Rf
64.2 : 35.8
l Rf
Scheme 1.
O
O
O
O
O
P(OEt)2
p-Tol
p-Tol
S
S
P(OEt)2
O
S
P(OEt)2
O
9
O
+
p-Tol
S
O
Ph
Ph
Ph
trans
11
(R,S)-
(S,R)-11
91
:
Scheme 2.
BrCH2COOEt, AgBF4
4h, r.t.
BrCH2COOEt, AgBF4
H2O/CH2Cl2, 24h, r.t.
Se
Se
Se
BF4
45%
BF4
44%
CO2Et
CO2Et
1
14
14
BrCH2COOEt, AgBF4
4h, r.t.
BrCH2COOEt, AgBF4
H2O/CH2Cl2, 24h, r.t.
S
S
BF4
23%
BF4
21%
S
CO2Et
CO2Et
15
2
15
path A
path B
Scheme 3. Synthesis of isoselenocineole and isothiocineole.

W.H. Midura et al. / Tetrahedron: Asymmetry 25 (2014) 1488–1493
1491
Table 2
Cyclopropanation—transfer of CHCO2Et group
O
O
X
X
(EtO)2P
(EtO)2P
+
+
H
O
H
CO2Et
(EtO)2P
X
salt, base
CO2Et
b
O
(EtO)2P
a
O
X
X
(EtO)2P
3 : X = CO2Et
4 : X = SO2Ph
H
H
CO2Et
16: X = CO2Et
17
CO2Et
: X = SO2Ph
b
ent-
ent-a
Entry
Salt
Michael
Reaction
Total yield (%)
trans/cis
Ratio of cis
Ratio of trans
acceptor
condition
enantiomers l/h
enantiomers l/h
Me
60.0:40.0a
60.0:40.0a
—
—
CO2Et
CO2Et
Br
Br
S
S
1
2
3
3
K2CO3, CH2Cl2
DBU, MeCN
<10
72
Me
Me
50.0/50.0
50.0/50.0
Me
3
3
DBU, MeCN
91
62.0:38.0a
99.0/1.0
99.0/1.0
S
BF4
CO2Et
15
4
5
6
3
4
4
DBU, MeCN
DBU, MeCN
DBU, MeCN
86
72
84
65.0:35.0a
71.4:28.6a
70.4:29.6a
98.0/2.0
50.0/50.0
4.2/95.8
99.0/1.0
50.0/50.0
5.0/95.0
Se
BF4
CO2Et
Me
14
CO2Et
Br
SH
Me
S
BF4
15
CO2Et
7
4
DBU, MeCN
75
72.5:27.5a
1.6/98.4
2.5/97.5
Se
BF4
CO2Et
14
l—lower Rf in HPLC; h—higher Rf in HPLC.
a
The ratio of diastereomers determined by NMR.
3. Conclusion
O
O
O
H
(EtO)2P
SO2Ar
(EtO)2P
(EtO)2P
SO2Ar
SR2
SO2Ar
A series of cyclopropanations using terpene selenides derived
from (ꢀ)-menthol and (+)-limonene was examined. It has been
shown that the corresponding salts obtained from cyclic isoseleno-
cineole gave better enantioselectivities than the salt obtained from
methyl menthyl selenides, derived from menthol. A comparison of
the reactivities of the salts obtained from isoselenocineole with
those formed using its sulfur analogue isothiocineole, proves the
similar diastereoselectivity and enantioselectivity of these two
reactants. In both cases, excellent enantioselectivity was observed,
especially for the cyclopropanation with the salt containing an
acetate moiety in its structure.
X
H
H
EtO2C
EtO2C
EtO2C
SR2
SR2
A
B
C
Scheme 4. Plausible carboanionic species.
drawing substituent in the Michael acceptor, which better stabi-
lized the carboanionic species A.
Some information about the configuration of cyclopropanes 17
was obtained by the same method, which was applied for phenyl-
cyclopropane 11. In this case, we analyzed, by HPLC, the mixture of
sulfones 170, formed via oxidation of the corresponding sulfoxides
19, which were obtained earlier, applying the cyclopropanation of
enantiomerically pure (S)-(+)-(1-diethoxyphosphoryl) vinyl p-tolyl
sulfoxide 18 with EDSA (Scheme 5).11c
4. Experimental
4.1. General
1H, 13C and 31P NMR spectra were recorded on a Bruker Avance
III 600, Bruker Avance III 500, Bruker Avance III 400, and Bruker AC
200 Spectrometer, using deuterochloroform as solvent. Mass spec-
In this case, cis-(1S,2S)-170 and trans-(1S,2R)-170 were also the
less polar enantiomers, which suggests such configuration should
be assigned to the minor enantiomers of 17.

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W.H. Midura et al. / Tetrahedron: Asymmetry 25 (2014) 1488–1493
O
O
Tol-p
Tol-p
O
Me
Ph
Tol-p
S
CO2Et Br
S
S
(EtO)2P
(EtO)2P
S
(EtO)2P
O
O
O
CO2Et
(1S,2R)-19
CO2Et
13 : 8
3 : 1
18
(1S,2S)-19
δP 19.0
δP 17.5
O
Tol-p
O
Tol-p
S
(EtO)2P
S
(EtO)2P
O
O
CO2Et
CO2Et
19
(1R,2S)-
δP 17.0
19
(1R,2R)-
δP 18.8
mcpba
17'
(1S,2S)-17'
17'
(1R,2S)-
(1R,2R)-17'
h Rf
(1S,2R)-
l Rf
l Rf
h Rf
δP 15.4
Scheme 5.
δP 13.4
tra were recorded on Finnigan MAT95. IR spectra were recorded on
Ati Mattson FTIR Spectrometer. The optical rotations were mea-
sured on a Perkin–Elmer 241 MC photopolarimeter in acetone
solution. The microanalyses were performed on Elemental Ana-
lyzer EA 1108. TLC was carried out on silica gel plates (Merck
F254) and silica gel 60 (70–230 ASTM) was used for chromatogra-
phy. THF was freshly distilled over potassium/benzophenone.
ppm. 77Se NMR (76.3 MHz, CDCl3) d: 529.53 ppm. IR (cmꢀ1, film):
3583, 2924, 2854, 1711, 1462, 1377, 1303, 1068. Anal. Calcd for
C14H25O2BF4Se: C, 42.99; H, 6.44. Found: C, 43.18; H, 6.39.
4.2.4. (1R,4R,5R,6R)-6-(2-Ethoxy-2-oxoethyl)-4,7,7-trimethyl-6-
thiabicyclo[3.2.1]octan-6-ium tetrafluoroborate 15
Method A: yield 21%; method B: yield 23%; white solid; mp
110–112 °C, [
a]
21 = ꢀ32.0 (c 0.45, CHCl3). 1H NMR (400 MHz,
D
4.2. General procedure for the synthesis of sulfonium and sele-
nonium salts
CDCl3) d: 1.22 (d, JHH = 7.2 Hz, 3H, CH3), 1.35 (t, JHH = 7.2 Hz, 3H,
CH3), 1.59 (d, JHH = 20.0 Hz, 1H), 1.67 (s, 3H, CH3), 1.75–1.84
(m, 3H), 1.85 (s, 3H, CH3), 2.42–2.45 (m, 2H), 2.51–2.59 (m, 2H),
4.32 (q, JHH = 6.8 Hz, 3H), 4.44 (d, JHH = 17.2 Hz, 1H), 4.61
(d, JHH = 16.8 Hz, 1H) ppm. 13C NMR (100.6, CDCl3) d: 13.9 (CH3);
17.5 (CH3); 22.2 (CH2); 23.0 (CH3); 25.0 (CH2); 25.3 (CH3); 31.7
(CH); 32.0 (CH2); 40.6 (CH2); 50.2 (CH); 63.9 (CH2); 66.1 (CH);
71.7 (C); 165.5 (C) ppm. IR (cmꢀ1, film): 3583, 2923, 2854, 1738,
1462, 1377, 1028. Anal. Calcd for C14H25O2BF4S: C, 48.85; H, 7.32.
Found: C, 49.03; H, 7.26.
4.2.1. Method A
The chalcogenide (2.0 mmol) was dissolved in dichloromethane
(1 ml) after which benzyl bromide (4.0 mmol) and a solution of sil-
ver triflate (2.0 mmol) in water (2 ml) were added. The resulting
biphasic mixture was stirred at rt for 1 day. Water (5 ml) and
dichloromethane (5 ml) were then added and the layers were sep-
arated. The aqueous organic layer was extracted with dichloro-
methane (3 ꢁ 3 ml). The combined organic layer was dried over
MgSO4 and the solvent was removed under reduced pressure.
The crude product was dissolved in the minimum amount of
dichloromethane and then added dropwise to rapidly stirred
diethyl ether (10 ml). The precipitate was filtered and washed with
diethyl ether (3 ꢁ 10 ml).
4.3. General procedure for a cyclopropanation
4.3.1. Method A
In a round-bottom flask equipped with a magnetic stirrer bar,
2 mmol of vinyl phosphonates 3 or 4 and 2.2 mmol of the appropri-
ate sulfonium or selenonium salt were placed in 10 mL of CH2Cl2.
To this suspension were added 0.3 g of K2CO3 and the mixture stir-
red vigorously overnight. Filtration and evaporation of the solvent
afforded a crude residue, which was purified by chromatography.
4.2.2. Method B
AgBF4 (2.5 mmol) was carefully added to a mixture of chalco-
genide (2.5 mmol) and benzyl bromide (6.3 mmol) at 0 °C under
an argon atmosphere. The resulting mixture was stirred at rt for
4 h. The crude product was dissolved in dichloromethane (10 ml)
and filtered through Celite. The solvent was removed under
reduced pressure, then diethyl ether (10 ml) was added and dec-
anted. The precipitate was washed with diethyl ether (3 ꢁ 10 ml).
4.3.2. Method B
In a round-bottom flask equipped with a magnetic stirrer bar,
2 mmol of vinyl phosphonates 3 or 4 and 2.2 mmol of the appropri-
ate sulfonium or selenonium salt were dissolved in 10 mL of
CH3CN or acetone. To this solution 2.2 mmol of DBU was added
and the mixture stirred vigorously overnight. After evaporation
of the solvent the residue was purified by chromatography.
4.2.3. (1R,4R,5R,6R)-6-(2-Ethoxy-2-oxoethyl)-4,7,7-trimethyl-6-
selenabicyclo[3.2.1]octan-6-ium tetrafluoroborate 14
Method A: Yield 45%; method B: yield 44%; white solid; mp
113–114 °C, [
a
]
22 = ꢀ238.5 (c 0.55, CHCl3). 1H NMR (400 MHz,
4.3.3. Ethyl 1-(diethoxyphosphoryl)-2-phenylcyclopropane-
carboxylate 10
D
CDCl3) d: 1.23 (d, JHH = 7.2 Hz, 3H, CH3), 1.36 (t, JHH = 7.2 Hz, 3H,
CH3), 1.67–1.73 (m, 5H), 1.77–1.91 (m, 5H), 2.41 (s, 1H), 2.46
(s, 1H), 2.61 (d, JHH = 2.1 Hz, 1H), 2.69 (d, JHH = 13.6 Hz, 1H),
4.26–4.34 (m, 3H), 4.48 (d, JHH = 16.0 Hz, 1H), 4.61 (s, 1H) ppm.
13C NMR (100.6 MHz, CDCl3) d: 13.9 (CH3); 17.6 (CH3); 22.0
(CH2); 23.7 (CH3); 25.9 (CH2); 26.2 (CH3); 31.3 (CH); 33.7 (CH2);
37.7 (CH2); 50.6 (CH); 63.8 (CH2); 67.6 (CH); 74.7 (C); 166.3 (C)
trans-7: 31P NMR (81 MHz, CDCl3) d: 22.6 ppm. 1H NMR
(200 MHz, CDCl3) d: 0.86 (t, 3H, POCH2CH3, JHH = 7.1 Hz), 1.36 (t,
3H, POCH2CH3, JHH = 7.1 Hz), 1.40 (t, 3H, COCH2CH3, JHH = 7.1 Hz),
1.87 (ddd, 1H, CHcis, JHH = 5.0, JHH = 9.1, JPH = 14.1 Hz), 2.19 (m,
1H, CHtrans), 3.07 (ddd, 1H, CHPh, JHH = 7.5, JHH = 9.1, JPH = 16.7 Hz),
3.83 (q, 2H, COCH2CH3, JHH = 7.1 Hz), 4.13–4.34 (m, 4H, POCH2CH3),

W.H. Midura et al. / Tetrahedron: Asymmetry 25 (2014) 1488–1493
1493
7.24–7.30 (m, 5H, C6H5). 13C NMR (125 MHz, CDCl3) d: 14.5
(t, 3JHH = 7.1 Hz, 3H, CH3CH2O), 1.24 (t, 3JHH = 7.0 Hz, 3H, CH3CH2O),
1.30 (t, JHH = 7.0 Hz, 3H, CH3CH2O), 1.92–2.16 (m, 2H, CH2), 3.04
3
3
3
(s, OCH2CH3); 16.3 (d, JC,P = 7 Hz, OCH2CH3); 16.4 (d, JC,P = 7 Hz,
1
OCH2CH3); 27.4 (s, PCCH2); 29.6 (d, JC,P = 187.6 Hz, PC); 29.9
(ddd, 1H, JHH = 7.7, 8.2, JPH = 9.1 Hz), 3.88–4.07 (m, 4H, CH2OP),
2
3
(s, CHPh); 62.1 (d, JC,P = 5.5 Hz, POCH2CH3); 62.4 (s, OCH2); 62.6
4.16 (q, JHH = 7.1 Hz, 2H, CH2O), 7.50–7.82 (m, 3H, C6H5),
2
3
(d, JC,P = 3.7 Hz, POCH2CH3); 127.2, 128.0, 129.1, 134.7 (d, JC,P
1.8 Hz); 165.4 (CO2). IR (film) 1740, 1220, 1024. Anal. Calcd for
16H23O5P: C, 58.89; H, 7.10. Found: C, 58.64; H, 7.22.
=
7.95–8.00 (m, 2H, C6H5). 13C NMR (125 MHz, CDCl3) d: 13.9
3
3
(s, CH3CH2O); 15.9 (d, JPC = 7.5 Hz, CH3CH2OP); 16.0 (d, JPC = 7.0
1
C
Hz, CH3CH2OP); 29.6 (s, CH2); 42.6 (d, JPC = 173.3 Hz); PCS); 62.1
2
2
(s, CH3CH2O); 63.6 (d, JPC = 5.9 Hz CH3CH2OP); 63.7 (d, JPC = 5.7
Hz, CH3CH2OP); 127.8, 129.1, 136.7, 144.5, 167.9 (d, J = 4.5 Hz).
Anal. Calcd for C16H23O7PS: C, 49.23; H, 5.94. Found: C, 49.21; H,
5.68.
4.3.4. Diethyl 1-[(phenyl sulfonyl)-2-phenylcyclopropane]-phos-
phonate 11
trans-8: [
a
]
22 = ꢀ47.2 (c 0.15, acetone); 31P NMR (81 MHz,
D
CDCl3) d: 14.3 ppm. 1H NMR (200 MHz, CDCl3) d: 0.89 (t, 3H,
POCH2CH3, JHH = 7.1 Hz), 1.09 (t, 3H, POCH2CH3, JHH = 7.1 Hz),
1.19–1.30 (m, 1H, CHH), 2.17–2.36 (m, 2H, CHPh and CHH),
3.41–3.95 (m, 4H, POCH2CH3), 7.20–7.68 (m, 8H, C6H5), 7.96–8.06
(1S,2S) cis-17: [
a
]
D
21 = ꢀ42.8 (c 0.23, acetone); 31P NMR (81 MHz,
CDCl3) d: 15.4 ppm. 1H NMR (200 MHz, CDCl3) d: 1.16 (t, 3H,
CH3CHO), 1.20 (t, 3H, CH3CHO), 1.34 (t, 3H, CH3CHO), 1.84 (ddd,
1H, JHH = 5.5, 8.9, JPH = 9.0 Hz), 2.31 (ddd, 1H, JHH = 5.5, 7.7,
JPH = 11.2 Hz), 2.82 (ddd, 1H, JHH = 7.7, 8.9, JPH = 16.6 Hz), 3.94–
4.07 (m, 4H, CH2OP), 4.22–4.27 (q, 2H, CH2O) 7.55–7.69 (m, 3H,
C6H5), 7.98–8.05 (m, 2H, C6H5). 13C NMR (125 MHz, CDCl3) d:
(m, 2H, C6H5). 13C NMR (125 MHz, CDCl3) d: 16.0 (d, JC,P = 6.2 Hz,
POCH2CH3); 16.4 (d, JC,P = 6.7 Hz, OCH2CH3); 28.4 (s, PCCH2);
31.9 (s, CHPh); 39.6 (d, JC,P = 177.9 Hz, PC); 62.1 (d, JC,P = 5.5 Hz,
POCH2CH3); 62.6 (d, JC,P = 5.7 Hz, POCH2CH3); 127.2, 128.0,
3
3
1
2
2
3
13.9 (s, CH3CH2O); 15.9 (d, JPC = 6.8 Hz, CH3CH2OP); 16.0
(d, JPC = 6.7 Hz, CH3CH2OP); 29.6 (s, CH2); 42.6 (d, JPC = 173.3 Hz
PCS); 62.1 (s, CH3CH2O); 63.6 (d, JPC = 5.9 Hz CH3CH2OP); 63.7
(d, JPC = 5.7 Hz, CH3CH2OP); 127.8, 129.1, 138.5, 142.5, 166.5
3
3
1
129.1, 129.3, 134.7 (d, JC,P = 1.8 Hz); 138.2, 143.8, 165.4 (CO2). IR
2
(film) 1745, 1330, 1225, 1024. Anal. Calcd for C19H23O2PS: C,
57.86; H, 5.88. Found: C, 57.41; H, 5.68.
2
(s, C@O).
4.3.5. Diethyl 1-(diethoxyphosphoryl)cyclopropane-1,2-dicarb-
oxylate 16
References
trans-15: Colorless oil. 31P NMR (81 MHz, CDCl3) d: 19.9 ppm.
3
1H NMR (200 MHz, CDCl3) d: 1.26 (t, JHH = 7.0 Hz, 3H, CH3CH2O),
1. Corey, E. J.; Chaykovsky, M. J. Am. Chem. Soc. 1965, 87, 1345–1364.
2. (a) Furukawa, N.; Sugihara, Y.; Fujihara, H. J. Org. Chem. 1989, 54, 4222–4224;
(b) Julienne, K.; Metzner, P.; Henryon, V. J. Chem. Soc., Perkin Trans. 1 1999, 731–
735. and references cited therein.
3. (a) Illa, O.; Namutebi, M.; Saha, C.; Ostovar, M.; Chen, C. C.; Haddow, M. F.;
Nocquet-Thibault, S.; Lusi, M.; McGarrigle, E. M.; Aggarwal, V. K. J. Am. Chem.
Soc. 2013, 135, 11951–11966; (b) Illa, O.; Arshad, M.; Ros, A.; McGarrigle, E. M.;
Aggarwal, V. K. J. Am. Chem. Soc. 2010, 132, 1828–1830; (c) Aggarwal, V. K.;
Winn, C. L. Acc. Chem. Res. 2004, 37, 611–620.
3
3
1.27 (t, JHH = 7.0 Hz, 3H, CH3CH2O), 1.34 (t, JHH = 7.0 Hz, 3H,
CH3CH2OP), 1.37 (t, 3JHH = 7.0 Hz, 3H, CH3CH2OP), 1.70
(ddd, JHH = 8.5 Hz, JHH = 4.5 Hz, JPH = 16.2 Hz, 1H, PCCHH), 1.92
(ddd, JHH = 4.5 Hz, JHH = 6.2 Hz, JPH = 13.1 Hz, 1H, PCCHH), 2.45
3
3
3
2
3
3
3
3
3
(ddd, JHH = 6.2 Hz, JHH = 8.5 Hz, JPH = 15.4 Hz, 1H, PCCH),
4.10–4.25 (m, 8H, 2ꢁCH2OP, 2ꢁCH2O). 13C NMR (125 MHz, CDCl3)
4. (a) McGarrigle, E. M.; Myers, E. L.; Illa, O.; Shaw, M. A.; Riches, S. L.; Aggarwal, V.
K. Chem. Rev. 2007, 107, 5841–5883; (b) Drabowicz, J.; Lewkowski, J.;
3
d: 14.0 (d, JPC = 5.5 Hz, CH3CH2OP); 14.1 (s, CH3CH2O); 16.3
´
(s, CH3CH2O); 17.8 (s, PCCH2); 24.6 (s, CHCO2); 29.8
Scianowski, J. Selenium Compounds with Valency Higher than Two in
1
Organoselenium Chemistry In Wirth, T., Ed.; Wiley-VCH: Weinheim, 2012;
pp 191–256.
(d, JPC = 176.9 Hz, PC); 61.5 (s, CH2O); 62.4 (s, CH2O); 62.7
2
2
(d, JPC = 5.6 Hz, CH2OP); 63.4 (d, JPC = 5.6 Hz, CH2OP); 166.1
5. (a) Bartoli, G.; Bencivenni, G.; Dalpozzo, R. Synthesis 2014, 46, 979–1029; (b)
Riches, S. L.; Saha, C.; Filgueira, N. F.; Grange, E.; McGarrigle, E. M.; Aggarwal, V.
K. J. Am. Chem. Soc. 2010, 132, 7626–7630; (c) Pellissier, H. Tetrahedron 2008,
64, 7041–7095; (d) Sun, X. L.; Tang, Y. Acc. Chem. Res. 2008, 41, 937–948.
6. Zhou, R.; Deng, X.; Zheng, J.; Sheng, Q.; Sun, X.; Tang, Y. Chin. J. Chem. 2011, 29,
995–1000.
7. Aggarwal, V. K.; Grange, E. Chem. Eur. J. 2006, 12, 568–575.
8. (a) Liao, W. W.; Li, K.; Tang, Y. J. Am. Chem. Soc. 2003, 125, 13030–13031; (b)
Zheng, J. C.; Liao, W. W.; Tang, Y.; Sun, X. L.; Dai, L. X. J. Am. Chem. Soc. 2005,
127, 12222–12223.
9. Wang, H. Y.; FeiYang, F.; Li, X. L.; Yan, X. M.; Huang, Z. Z. Chem. Eur. J. 2009, 15,
3784–3789.
10. (a) Banach, A.; Scianowski, J.; Ozimek, P. Phosphorus, Sulfur 2014, 189, 274–284;
(b) Banach, A. Scianowski, J; Uzarewicz, M.; Wojtczak, A. ‘manuscript in
preparation’.
11. (a) Midura, W. H.; Rzewnicka, A. Synlett 2014, 2213–2216; (b) Midura, W. H.;
Rzewnicka, A. Tetrahedron: Asymmetry 2013, 24, 937–941; (c) Midura, W. H.;
2
3
(d, JPC = 5.0 Hz, C@O); 169.3 (d, JPC = 3.0 Hz, C@O) (lit.14).
cis-16: colorless oil. 31P NMR (81 MHz, CDCl3) d: 19.3 ppm. 1H
3
NMR (200 MHz, CDCl3) d: 1.27 (t, JHH = 7.0 Hz, 3H, CH3CH2O),
3
3
1.28 (t, JHH = 7.0 Hz, 3H, CH3CH2O), 1.29 (t, JHH = 7.0 Hz, 3H,
CH3CH2OP), 1.37 (t, 3JHH = 7.0 Hz, 3H, CH3CH2OP), 1.69
3
3
3
(ddd, JHH = 4.5 Hz, JHH = 8.0 Hz, JPH = 9.0 Hz, 1H, PCCHH), 1.94
(ddd, JHH = 4.5 Hz, JHH = 7.7 Hz, JPH = 15.0 Hz, 1H, PCCHH), 2.59
2
3
3
3
3
3
(ddd, JHH = 7.7 Hz, JHH = 8.0 Hz, JPH = 9.0 Hz, 1H, PCCH), 4.08–
4.26 (m, 8H, 2ꢁCH2OP, 2ꢁCH2O). 13C NMR (125 MHz, CDCl3)
´
3
d: 14.1 (d, JPC = 10.0 Hz, CH3CH2OP); 16.3 (s, CH3CH2O); 16.4
´
1
(s, CH3CH2O); 17.9 (s, PCCH2); 25.3 (s, PCCH); 26.5 (d, JPC = 193.0
2
Hz, PC); 62.7 (s, CH3CH2O); 62.9 (d, JPC = 6.3 Hz, CH3CH2OP); 63.3
(d, 2JPC = 6.4 Hz, CH3CH2OP); 64.4 (s, CH3CH2O); 167.5
_
Krysiak, J. A.; Rzewnicka, A.; Supeł, A.; Łyzwa, P. Tetrahedron 2013, 69, 730–
2
3
(d, JPC = 6.2 Hz, C@O); 168.7 (d, JPC = 7.0 Hz, C@O). IR (film)
1740, 1220, 1024. Anal. Calcd for C13H23O7P: C, 48.45; H, 7.19.
Found: C, 48.36; H, 7.21.
737; (d) Krysiak, J.; Midura, W. H.; Wieczorek, W.; Sieron´ , L.; Mikołajczyk, M.
Tetrahedron: Asymmetry 2010, 21, 1486–1493; (e) Midura, W. H.; Mikołajczyk,
M. Tetrahedron Lett. 2002, 43, 3061–3065.
12. For some experiments, HPLC was performed on mixture of diastereomers.
13. (a) Midura, W. H.; Krysiak, J.; Mikołajczyk, M.; Wieczorek, M. W.; Majzner, W.
R. Chem. Commun. 1998, 1109–1110; (b) Midura, W. H.; Krysiak, J. A.; Cypryk,
M.; Mikołajczyk, M.; Wieczorek, M. W.; Filipczak, A. D. Eur. J. Org. Chem. 2005,
653–662.
4.3.6. Diethyl-[(phenyl sulfonyl)-2-carboethoxycyclopropane]-
phosphonate 17
(1S,2R) trans-16: [
a]
21 = ꢀ33.7 (c 0.32, acetone); 31P NMR
D
14. Wa˛sek, K.; Ke˛dzia, J.; Krawczyk, H.; Wojciechowski, J.; Wolf, W. M. ARKIVOC
2010, IX, 146–154.
(81 MHz, CDCl3) d: 13.4 ppm. 1H NMR (200 MHz, CDCl3) d: 1.15