A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via an intermediate thiocarbonyl ylide

Article abstract of DOI:10.1016/j.tet.2009.07.074

The reaction of methyl (diethylphosphoryl)dithioformate (6) with diaryldiazomethanes 7a-d in THF at -60 °C to room temperature followed by desulfurization is shown to be a convenient method for the preparation of 2,2-disubstituted 1-(methylsulfanyl)vinyl

Full text of DOI:10.1016/j.tet.2009.07.074

Tetrahedron 65 (2009) 8191–8198
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A new approach to 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates via
an intermediate thiocarbonyl ylide
a
,
a
b
b,
*
*
´
Grzegorz Mloston , Katarzyna Urbaniak , Anthony Linden , Heinz Heimgartner
a
´
´ ´
Department of Organic and Applied Chemistry, University of Ło´dz, Narutowicza 68, PL-90-136 Łodz, Poland
b Institute of Organic Chemistry, University of Zu¨rich, Winterthurerstrasse 190, CH-8057 Zu¨rich, Switzerland
a r t i c l e i n f o
a b s t r a c t
Article history:
The reaction of methyl (diethylphosphoryl)dithioformate (6) with diaryldiazomethanes 7a–d in THF at
ꢀ60 ꢁC to room temperature followed by desulfurization is shown to be a convenient method for the
preparation of 2,2-disubstituted 1-(methylsulfanyl)vinyl phosphonates 8a–d. The analogous reactions
with 2-diazoacenaphthen-1-one (7f) or 2-diazocamphor (7g) in refluxing THF yield selectively the
corresponding (Z)- and (E)-vinyl phosphonates 8f and 8g, respectively. These products can be easily oxi-
dized to the vinylsulfoxides 13 and vinylsulfones 14. On the other hand, methyl (diethylphosphoryl)-
dithioformate (6) and 2-diazo-1,2-diphenylethanone (7e) in boiling THF react to give the 1,3-oxathiole 12.
All these reactions occur via an intermediate thiocarbonyl ylide 11 followed by 1,3-dipolar electro-
cyclization and sulfur extrusion or 1,5-dipolar electrocyclization.
Received 19 March 2009
Received in revised form 23 July 2009
Accepted 24 July 2009
Available online 6 August 2009
Dedicated to Professor Marek Zaidlewicz on
the occasion of his 70th birthday
Ó 2009 Elsevier Ltd. All rights reserved.
1. BuLi
2. Se
3. MeI
SMe
P(OR)2
SMe
P(OR)2
1. Introduction
H2O2
MeSe SMe
P(OR)2
pyridine
The activation of C,C-double bonds by phosphorus and sulfur
functional groups is widely explored in organic synthesis.1–3 The
most important applications relate to their use as dipolarophiles
dienophiles, and Michael acceptors. In the case of 1-(alkylsulfanyl)-
vinyl phosphonates 1, the activation is of the ‘capto-dative’ type.4 The
selective oxidation to 1-sulfinylvinyl phosphonates 2 opens access to
highly activated electron-deficient alkenes, which can also be pre-
pared in enantiomerically pure form. In this case, the stereogenic
center located at the S-atom governs the stereochemical outcome of
the reaction.5 The most frequently applied method for the prepara-
tion of vinyl phosphonates 1 is based on the selenylation/oxidation
O
O
O
1
4
3
H2O2
H2O2
H2O2
O
SO2Me
SMe
P(OR)2
P(OR)2
O
O
2
5
Scheme 1.
sequence of reactions starting with a-(methylsulfanyl)phosphonates
3 (Scheme 1).1,2
Awell-known and general method for the synthesis of substituted
alkenes, especially suitable for sterically congested systems, is the so-
called ‘twofold extrusion’ method developed by Barton.6–9 In this
case, a thiocarbonyl compound is used as a dipolarophile in the re-
action with a diazo compound, the subsequent elimination of N2
leads to a thiirane, which in turn is desulfurized to give the alkene.
The key intermediate in this sequence is a reactive thiocarbonyl ylide,
the precursor of the thiirane.
In a series of recent papers, methyl (dialkylphosphoryl)dithio-
formates were shown to react smoothly as dipolarophiles, e.g., with
diazomethane and thiocarbonyl ylides.10–13
The [2þ3] cycloaddition with diazomethane leads to the un-
stable 1,3,4-thiadiazoline, which extrudes N2 already at ꢀ35 ꢁC, and
in the absence of an intercepting agent, the intermediate thio-
carbonyl ylide undergoes a head-to-head dimerization.11 On the
other hand, it is well established that tetrasubstituted thiocarbonyl
ylides do not dimerize but form thiiranes as products of a 1,3-di-
polar electrocyclization.14,15 Based on these results, we decided to
test the reactivity of methyl (diethylphosphoryl)dithioformate 6
toward disubstituted diazomethanes 7 with the aim of obtaining
the corresponding thiiranes, which by elimination of sulfur could
* Corresponding authors. Tel.: þ48 42 6355761; fax: þ48 42 6655162 (G.M.);
tel.: þ41 44 6354282; fax: þ41 44 6356812 (H.H.).
E-mail addresses: gmloston@uni.lodz.pl (G. Mloston´ ), heimgart@oci.uzh.ch (H.
Heimgartner).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.07.074

8192
G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
be converted to the corresponding 1-(methylsulfanyl)vinyl phos-
phonates 8 (Scheme 2).
substance evidenced the absence of a C]O group. Based on this
information and supported by additional data (13C NMR, MS, ele-
mental analysis), the structure of the 1,3-oxathiole 12 was assigned
to the product (Scheme 4). The formation of 12 is the result of the
1,5-dipolar electrocyclization of the intermediate thiocarbonyl
ylide 11e. This result fits well into the observed formation of 1,3-
oxathiols from 7e and thiobenzophenone as well as cycloaliphatic
thioketones.20
R1
R2
O
SMe
P(OEt)2
S
R1
N2
(EtO)2P
+
-N2, -S
SMe
R2
O
7
6
8
Scheme 2.
Ph
O
S
Ph
Ph
MeS
(EtO)2P
THF
Ph
Ph
N2
O
O
MeS
(EtO)2P
6
+
To the best of our knowledge, vinyl phosphonates of type 8 with
R1, R2¼alkyl or aryl are hitherto only little known.16,17
Ph
S
reflux
-N2
O
O
12 (52%)
11e
7e
2. Results and discussion
Scheme 4.
2.1. Reactions of 6 with diazo compounds
As another a-oxodiazo compound with an aromatic skeleton,
2-diazoacenaphthen-1-one (7f) was used in the reaction with 6.
Under comparable conditions, the reaction was complete after 2 h,
and the single product formed (1H NMR) was isolated after chro-
matography. The IR spectrum (KBr) showed a strong C]O absorp-
tion at 1713 cmꢀ1, and the ESI-MS as well as the elemental analysis
confirmed that in this case the vinyl phosphonate 8f was obtained
(Scheme 5). Apparently, the intermediate thiocarbonyl ylide 11f, in
contrast to 11e, undergoes the 1,3-dipolar electrocyclization to give
the thiirane 9f, which spontaneously extrudes sulfur yielding the
isolated product. An explanation of this observation may be the
significantly higher ring strain in the case of the 1,3-oxathiole with
the acenaphthene skeleton. The configuration of 8f presented in
Scheme 5 was confirmed by the X-ray crystal-structure deter-
mination of the corresponding sulfoxide 13f (see below).
The reactions of diaryldiazomethanes 7a–d with 6 are signifi-
cantly slower than with the parent diazomethane and the decolo-
ration of the reaction mixture at ꢀ60 ꢁC was observed only after ca.
30 min. The evolution of N2 started after warming of the mixture to
room temperature. In the case of diphenyldiazomethane (7a), the
crude product was identified as a mixture of thiirane 9a and the
vinyl phosphonate 8a, formed after spontaneous desulfurization
(Scheme 3). The attempted chromatographic separation of 8a and
9a was in vain and, therefore, the mixture was treated with tris-
(diethylamino)phosphine in boiling THF yielding 8a exclusively
(65%). The reactions with the diaryldiazomethanes 7b–d were
carried out in an analogous manner to give the corresponding vinyl
phosphonates 8b–d in satisfactory yields.
a-Oxodiazo compounds were frequently used in reactions with
a
-Diazocamphor (7g) belongs to a class of relatively reactive a-
thiocarbonyl derivatives. In these systems, the intermediate thio-
carbonyl ylides enter two competitive electrocyclizations leading to
either thiiranes (1,3-dipolar electrocyclization) or 1,3-oxathioles
(1,5-dipolar electrocyclization). The reaction course strongly de-
pends on the type of the C]S dipolarophile as well as on the
oxodiazo compounds, and its reactions with aromatic thioketones
7a–d leading to an endo/exo mixture of the corresponding thiiranes
were carried out at room temperature.23 Similarly, the reaction of
7g with 6 occurred smoothly at room temperature with evolution
of N2. After 1 h, the reaction was completed, and the 1H NMR
spectrum of the crude product indicated that a mixture of two
stereoisomeric thiiranes, 9g, was formed, which, without separa-
tion, was desulfurized by treatment with tris(diethylamino)phos-
phine in boiling THF. The sole product obtained thereafter showed
in the 1H NMR spectrum the characteristic absorption of the MeS
group at 2.49 ppm.
substitution pattern of the
a
-oxodiazo compounds.14,18–22
-oxodiazo compounds, the reaction
Due to the low reactivity of
a
of 6 with 2-diazo-1,2-diphenylethanone (‘azibenzil’) 7e was carried
out in boiling THF. The product isolated after typical workup dis-
played in the 1H NMR spectrum signals of the MeS and the EtO
groups as well as for two Ph groups, indicating that a ‘1:1-adduct’
was formed. Furthermore, the IR spectrum (neat) of the oily
MeS
Ar
N
N
Ar
Ar
Ar
rt
MeS
(EtO)2P
THF
N2
+
6
Ar
(EtO)2P
S
Ar
S
-60 oC
-N2
O
O
7a-d
10a-d
11a-d
(Et2N)3P
THF, reflux
SMe
MeS
(EtO)2P
Ar
Ar
Ar
P(OEt)2
O
S
Ar
O
9a-d
8a-d (54-74%)
Ar
Ar
Ar
Ar
(a) Ar = Ph
(c)
(b)
S
=
(d)
=
=
O
Ar
Ar
Scheme 3.

G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
8193
O
MeS
O
THF
6
+
MeS
(EtO)2P
reflux
-N2
-S
S
O
O
N2
(EtO)2P
O
7f
9f
8f (55%)
(Et2N)3P
THF, reflux
THF
SMe
S
rt
SMe
P(OEt)2
O
N2
6
+
P(OEt)2
O
-N2
O
O
O
8g (70%)
7g
9g
Scheme 5.
The formation of the expected vinyl phosphonate 8g was con-
firmed by the CIMS (m/z 347, [Mþ1]þ), elemental analysis, and 13
C
NMR data (Scheme 5). The given (E)-configuration of 8g was con-
firmed by the X-ray crystal structure of the corresponding sulfone
14g (see below).24
2.2. Oxidation of 1-(methylsulfanyl)vinyl phosphonates 8
As already mentioned in the Introduction, vinyl phosphonates
bearing a sulfoxide moiety at C(1) are especially attractive building
blocks in organic synthesis. Furthermore, the sulfoxide group fur-
ther activates the vinyl group and, on the other hand, the presence
of a stereogenic center enables their applications for stereoselective
transformations.5 Further oxidation leads to highly activated vinyl
phosphonates with a sulfonyl group at C(1), which have been used
as dienophiles,25 as Michael acceptors,26 and for cyclopropanation
reactions.27 The diaryl-substituted vinyl phosphonates 8a,b were
sequentially oxidized with mCPBA in dichloromethane. The
experiment carried out with 8a and 1 equiv of the oxidizing reagent
yielded exclusively the sulfoxide 13a (Scheme 6).
A similar reaction with 2.2 equiv of mCPBA led to the corre-
sponding sulfone 14a, which after chromatographic separation and
crystallization delivered crystals suitable for an X-ray crystal-
structure determination (Fig. 1).
The fluorenylidene derivatives 13b and 14b were obtained
analogously. The same oxidation procedure with 1 equiv of
Figure 1. ORTEP plot28 of the molecular structure of 14a (arbitrary numbering of the
atoms; 50% probability ellipsoids).
mCPBA was applied in order to prepare the sulfoxide of the
non-symmetric vinyl phosphonate 8f. The structure of the
crystalline product 13f was also determined by X-ray crystal-
lography (Fig. 2), which showed unambiguously that the
Me
O
Me
SMe
S
SO2
mCPBA
mCPBA
Ar
Ar
Ar
P(OEt)2
O
P(OEt)2
O
P(OEt)2
O
CH2Cl2
CH2Cl2
Ar
Ar
Ar
8a,b
13a,b (70-75%)
14a,b (67-69%)
Ar
=
(b)
(a) Ar = Ph
Ar
O
S
O
O
SO2Me
Me
Me(O) S
n
Me(O)2S
P(OEt)2
O
P(OEt)2
O
O
O
(EtO)2P
(EtO)2P
O
O
O
14g (63%)
13f n = 1 (57%)
14f n = 2 (not isolated)
15a (52%)
Scheme 6.
13g, 13g' (56%)

8194
G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
Figure 3. ORTEP plot28 of the molecular structure of 14g (arbitrary numbering of the
atoms; 50% probability ellipsoids).
Figure 2. ORTEP plot28 of the molecular structure of 13f (arbitrary numbering of the
atoms; 50% probability ellipsoids).
3. Conclusion
The described results show that the reaction of methyl (diethyl-
phosphoryl)dithioformate with disubstituted diazomethanes
sulfoxide group and the C]O group are cis-oriented. Therefore,
this configuration was also assigned to 8f. The attempted oxi-
dation of 8f with ca. 2 equiv of mCPBA in CH2Cl2 solution at
room temperature, instead of affording the expected sulfone
14f, led to a mixture of products, which could be separated
neither by crystallization, nor by chromatography (PLC plates,
SiO2). Therefore, the amount of the oxidizing agent was in-
creased to ca. 3 equiv. Under these conditions, oxidation of
both reactive centers, i.e., the sulfur atom (to give a SO2 unit)
and the C]C bond (to yield the oxirane ring) was achieved, and
product 15a was isolated by simple crystallization from MeOH
in quite good yield (52%). The IR spectrum (KBr) of 15a showed
no absorption band at ca. 1550 cmꢀ1, which was present in 13a,
13f, and 14a. Apparently, the reactivities of the S]O group and
the C]C bond in 13f are comparable, in contrast to other
sulfoxides of type 13 described in this study, and therefore, the
oxidation does not occur chemoselectively. Oxiranes possessing
a substitution pattern similar to 15a are rather rare; however,
similar derivatives, prepared by threefold oxidation of the
corresponding vinylsulfanes via a one-pot procedure, were
reported in a recent paper.29
The oxidation of the camphor derivative 8g at room tempera-
ture with 2.5 equiv of mCPBA led to the sulfone 14g. The 1H NMR
analysis showed that only one product was formed in the reaction,
and the determination of the structure by means of X-ray crystal-
lography proved that in contrast to the acenaphthen-1-one de-
rivatives (e.g., 13f), the C]O group and the phosphonate group are
cis-oriented (Fig. 3). The compound in the crystal is enantiomeri-
cally pure and the absolute configuration of the molecule was de-
termined independently by the diffraction experiment. The
opens
a convenient access to 2,2-disubstituted 1-(methyl-
sulfanyl)vinyl phosphonates. These products can be easily oxidized
to give the corresponding sulfoxides and sulfones. All of the pre-
pared vinyl phosphonates are attractive Michael acceptors and
reagents for cycloaddition reactions. The enantiomerically pure
camphor derivative 14g can potentially be used as a catalyst in
asymmetric synthesis. Unexpectedly, the products obtained from
2-diazoacenaphthen-1-one and 2-diazocamphor show different
configurations of the new C]C bond, which is (Z) in the first case,
but (E) in the camphor derivative. Remarkably, the acenaphthen-1-
one derived sulfoxide 13f does not undergo chemoselective oxi-
dation to the expected sulfone 14f, and with an increased amount
of mCPBA, it was converted to 15a, a very rare 2-phosphoryl-2-
sulfonyl-substituted oxirane.
4. Experimental
4.1. General comments
The 1H and 13C NMR spectra were recorded with a Bruker AC-300
(1H at 300.1 MHz, 13C at 75.5 MHz, 31P at 121.5 MHz) or Bruker
Avance II Plus 700 (1H at 700 MHz,13C at 176 MHz, 31P at 283.6 MHz)
or Varian Gemini 200 (1H at 200 MHz, 13C at 50 MHz, 31P at 81 MHz)
spectrometer using CDCl3 as a solvent. Chemical shifts (d) are
reported in parts per million downfield from internal TMS. The
multiplicities of the 13C signals were assigned with the aid of DEPT
spectra. IR spectrawere recorded in KBr pellets oras films on a Nexus
FTIR spectrometer. CI and ESI mass spectra were taken on an LKB-
2091, Finnigan MAT-90 or Finnigan MAT-95 instrument. Elemental
analyses were performed in the Analytical Laboratory of the Uni-
molecule has the expected 4R,7S-configuration. The [a]D-value of
´
´
the enantiomerically pure product 14g was determined to þ157.5
versity of Zu¨rich or the Polish Academy of Science in qodz. Melting
points were determined in capillaries on a Mel-Temp. II apparatus
(Aldrich) and are uncorrected. Column chromatography was carried
(CH2Cl2).
On the other hand, the oxidation of 8g at room temperature
with 1 equiv of mCPBA afforded a different product, which was
identified as a ca. 3:2 mixture of two stereoisomeric sulfoxides 13g/
13g0. Apparently, the oxidation reaction occurs in a non-stereo-
selective manner. An explanation of this result may be the trans
location of the MeS group with regard to the C]O group and,
therefore, the discrimination caused by the camphor skeleton can
be neglected. Further oxidation of the mixture 13g/13g0 yielded the
sulfone 14g as the sole product.
out using silica gel (Merck 60, 0.063–0.200 mm). Thin layer chro-
matography (TLC) was performed on Merck 5554 aluminum backed
SiO2 plates; products were visualized by UV light. THF was distilled
from the blue solution of sodium benzophenone ketyl.
Diphenyldiazomethane (7a), 9-diazo-9H-fluorene (7b), 9-diazo-
9H-xanthene (7c), 9-diazo-9H-thioxanthene (7d),
(7e), 2-diazoacenaphthen-1-one (7f), and -diazocamphor (7g)
were prepared by oxidation of the corresponding hydrazone with
a-diazobenzil
a

G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
8195
nickel peroxide or yellow mercury oxide according to the literature
procedure.30,31 Methyl (diethylphosphoryl)dithioformate (6) was
prepared from diethyl phosphite and carbon disulfide following
a known protocol.32
Mp 58–60 ꢁC. 1H NMR:
d
1.10 (t, JHH¼7.2 Hz, 2 CH3CH2O), 2.16 (d,
4JHP¼0.7 Hz, CH3S), 3.70–4.15 (m, 2 CH3CH2O), 7.25–7.28 (m, 4
CHarom), 7.50–7.60 (m, 2 CHarom), 7.85–8.05 (m, 2 CHarom). 13C NMR:
d
16.1 (2 CH3CH2O), 19.4 (CH3S), 62.0 (2 CH3CH2O), 125.3, 125.9,
126.4, 126.7, 127.5, 127.9, 129.6, 130.1 (8 CHarom), 133.9, 135.6, 136.3,
151.0, 151.2, 155.4, 155.8 (4 Carom, P–C]C). 31P NMR:
15.05. IR (KBr,
4.2. Reaction of diazo compounds 7a–d with ethyl
(diethylphosphoryl)dithioformate (6)
d
cmꢀ1): 2980m, 2924m, 1571w, 1534w, 1456m, 1438m, 1238s
(P]O), 1053vs and 1026vs (P–O–C), 969s, 745s, 562m. CIMS (NH3),
m/z (%): 393 (100, [Mþ1]þ), 350 (6), 349 (28), 348 (7), 347 (30).
Anal. Calcd for C19H21O3PS2 (392.48): C 58.15, H 5.39, S 16.34;
found: C 58.17, H 5.28, S 16.04.
To a solution of 228.3 mg (1 mmol) of dithioformate 6 in 1 mL of
dry THF at ꢀ65 ꢁC, 1 mmol of the corresponding diazo compound 7
was added. After 30 min, complete decoloration of the reaction
mixture was observed. The mixture was allowed to warm to room
temperature while stirring. The solvent was evaporated and the
residue, after chromatographic purification, was desulfurized by
treatment with tris(diethylamino)phosphine in boiling THF
(1–1.5 h). After evaporation of the solvent, the crude mixture was
purified by column chromatography or by preparative layer chro-
matography on plates precoated with silica gel using hexane/ethyl
acetate 3:2 (for 8a,b,d) or 4:1 (for 8c). Analytically pure products
8a–d were obtained by crystallization from hexane at 0–5 ꢁC.
4.3. Reaction of a-oxodiazo compounds 7e,f,g with methyl
(diethylphosphoryl)dithioformate (6)
To a solution of 228.3 mg (1 mmol) of 6 in 1 mL of boiling THF,
1 mmol of the corresponding diazo compound 7 was added. The
mixture was heated under reflux for 1.5 h. The reaction with 7g was
carried out at room temperature for 1 h. After this time, complete
decoloration of the reaction mixtures was observed. The solvent
was evaporated and the residue was purified chromatographically
(SiO2) using dichloromethane (for 12), ethyl acetate (for 8f), and
a mixture of methanol and dichloromethane 2:98 (for 8g) as the
eluent. Analytically pure 8f was obtained by crystallization from
hexane at 0–5 ꢁC. The products 12 and 8g were obtained as yel-
lowish oils.
4.2.1. [1-(Methylsulfanyl)-2,2-diphenylvinyl]phosphonic acid diethyl
ester (8a). Yield: 235 mg (65%). Colorless crystals. Mp 56–58 ꢁC. 1H
NMR:
d
1.11 (t, JHH¼7.0 Hz, 2 CH3CH2O), 2.14 (s, CH3S), 3.80–3.90 (m,
CH3CH2O), 3.93–4.06 (m, CH3CH2O), 7.23–7.36 (m, 10 CHarom). 13C
3
NMR:
d
16.0 (d, JCP¼6.8 Hz, 2 CH3CH2O), 19.4 (CH3S), 62.4 (d,
2JCP¼6.8 Hz, 2 CH3CH2O), 125.0 (d, JCP¼190.0 Hz, P–C]C), 127.7,
1
128.1, 128.3, 128.4, 129.4, 129.7 (10 CHarom), 142.2, 142.3, 142.4 (2
4.3.1. [2-(Methylsulfanyl)-4,5-diphenyl-[1,3]oxathiol-2-yl]phos-
Carom), 160.4 (d, JCP¼ca. 15 Hz, P–C]C). 31P NMR:
d
13.71. IR (KBr,
phonic acid diethyl ester (12). Yield: 220 mg (52%). Pale yellow oil.
2
cmꢀ1): 2982m, 2959m, 1553m, 1489m, 1443m, 1389m, 1239vs
(P]O), 1167m, 1055vs and 1027vs (P–O–C), 971s, 941s, 705s, 562s.
ESI-MS, m/z (%): 385 (100, [MþNa]þ). Anal. Calcd for C19H23O3PS
(362.43): C 62.97, H 6.40, S 8.85; found: C 62.99, H 5.86, S 8.84.
1H NMR:
d
1.40 (t, JHH¼7.1 Hz, 2 CH3CH2O), 2.50 (d, JHP¼0.9 Hz,
4
CH3S), 4.36–4.42 (m, 2 CH3CH2O), 7.21–7.36 (m, 10 CHarom). 13C
3
NMR:
d
13.5 (CH3S), 16.5 (d, JCP¼4.7 Hz, 2 CH3CH2O), 64.8
2
2
(d, JCP¼6.9 Hz, CH3CH2O), 65.2 (d, JCP¼7.0 Hz, CH3CH2O), 98.3
(d, 1JCP¼196.6 Hz, P–Cq), 127.5, 128.2, 128.3, 128.7, 128.8, 129.1 (10
3
4.2.2. [(Fluoren-9-ylidene)(methylsulfanyl)methyl]phosphonic acid
diethyl ester (8b). Yield: 210 mg (58%). Yellow crystals. Mp 62–
CHarom), 112.3, 129.8, 130.9 (3 Cq), 141.9 (d, JCP¼8.8 Hz, Cq). 31P
NMR: d
10.8. IR (film, cmꢀ1): 2980m, 2927m, 2867m, 1636m,
64 ꢁC. 1H NMR:
d
1.29 (t, JHH¼7.0 Hz, 2 CH3CH2O), 2.47 (d,
1599m, 1496m, 1444m, 1260s (P]O), 1051vs and 1025vs (P–O–C),
976s, 953s, 754s, 695s. CIMS (NH3), m/z (%): 423 (35, [Mþ1]þ), 391
(27), 375 (100), 271 (13), 240 (12), 239 (63), 214 (33), 197 (17), 156
(14). Anal. Calcd for C20H23O4PS2 (422.51): C 56.86, H 5.49, S 15.18;
found: C 56.85, H 5.70, S 14.97.
4JHP¼1.0 Hz, CH3S), 4.15–4.29 (m, 2 CH3CH2O), 7.21–7.39 (m, 4
CHarom), 7.57–7.65 (m, 2 CHarom), 8.43 (d, JHH¼7.8 Hz,1 CHarom), 8.59
(d, JHH¼7.7 Hz, 1 CHarom). 13C NMR:
d
16.2 (d, JCP¼6.2 Hz, 2
3
2
CH3CH2O), 21.8 (CH3S), 63.4 (d, JCP¼6.6 Hz, 2 CH3CH2O), 118.9,
119.6, 127.2, 127.7, 127.8, 127.9, 129.7, 129.9 (8 CHarom), 130.3, 136.7,
136.8, 137.8, 140.8, 141.9, 149.5, 151.0 (4 Carom, P–C]C). 31P NMR:
4.3.2. (Z)-[(Methylsulfanyl)(2-oxoacenaphthen-1-ylidene)methyl]-
d
12.43. IR (KBr, cmꢀ1): 2981m, 2925m, 1599w, 1525w, 1474w,
phosphonic acid diethyl ester (8f). Yield: 200 mg (55%). Yellow
1447s, 1244s (P]O), 1051vs and 1025vs (P–O–C), 970s, 782s, 735s.
CIMS (NH3), m/z (%): 363 (7), 362 (20), 361 (100, [Mþ1]þ), 315 (9).
Anal. Calcd for C19H21O3PS (360.42): C 63.32, H 5.87, S 8.90; found:
C 63.09, H 5.65, S 8.83.
crystals. Mp 67–70 ꢁC. 1H NMR:
d
1.39, 1.40 (2t, JHH¼7.1 Hz, 2
CH3CH2O), 2.63 (d, JHP¼0.8 Hz, CH3S), 4.33–4.41 (m, 2 CH3CH2O),
7.56–8.17 (m, 5 CHarom), 8.45–8.63 (m, 1 CHarom). 13C NMR:
d
16.4 (d,
3JCP¼6.5 Hz, 2 CH3CH2O), 20.1 (CH3S), 63.6 (d, JCP¼6.6 Hz, 2
CH3CH2O), 121.7, 124.9, 127.1, 128.0, 128.3, 131.1 (6 CHarom), 130.4,
131.2, 132.1, 133.7, 140.8, 145.3 (4 Carom, P–C]C), 190.0 (C]O). 31P
2
4.2.3. [(Methylsulfanyl)(xanthen-9-ylidene)methyl]phosphonic acid
diethyl ester (8c). Yield: 280 mg (74%). Yellow crystals. Mp 57–59 ꢁC.
NMR: d
11.7. IR (KBr, cmꢀ1): 2984m, 2928m, 2906m, 1717s (C]O),
1H NMR:
d
1.11, 1.12 (2t, JHH¼7.1 Hz, 2 CH3CH2O), 2.24 (d, 4JHP¼0.9 Hz,
1541m, 1491m, 1442m, 1256m, 1241s (P]O), 1051s and 1030s
(P–O–C), 966s, 837m, 771s, 568s. ESI-MS, m/z (%): 401 [MþK]þ, 385
[MþNa]þ. Anal. Calcd for C18H19O4PS (362.39): C 59.66, H 5.28, S
8.85; found: C 59.44, H 5.35, S 8.63.
CH3S), 3.94–4.03 (m, 2 CH3CH2O), 7.17–7.38 (m, 6 CHarom), 8.15 (dd,
JHH¼7.9 Hz, 5JHP¼1.5 Hz, 1 CHarom), 8.46 (d, JHH¼8.0 Hz,1 CHarom). 13
C
3
NMR:
d
16.0 (d, JCP¼6.9 Hz, 2 CH3CH2O), 19.8 (CH3S), 62.6 (d,
2JCP¼6.9 Hz, 2 CH3CH2O), 115.6, 116.2, 122.3, 122.7, 129.5, 129.8,
129.9,130.3 (8 CHarom),119.8 (d, 1JCP¼192.5 Hz, P–C]C),123.7,123.9,
124.5, 124.6, 147.2, 147.4, 152.9, 153.3 (4Cq arom, P–C]C). 31P NMR:
4.3.3. (E)-[(Methylsulfanyl)(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-
2-ylidene)methyl]phosphonic acid diethyl ester (8g). Yield: 244 mg
d
16.55. IR (KBr, cmꢀ1): 2984m, 2923m,1596s,1590s,1529m,1445vs,
(70%). Pale yellow oil. 1H NMR:
d 0.84, 0.97, 0.98 (3s, 3 CH3), 1.23–
1320m, 1251vs (P]O), 1055vs and 1031vs (P–O–C), 970s, 774s,
577m, 549m. CIMS (NH3), m/z (%): 379 (8), 378 (24), 377 (100,
[Mþ1]þ), 333 (8), 331 (16). Anal. Calcd for C19H21O4PS (376.41): C
60.63, H 5.62, S 8.52; found: C 60.52, H 5.50, S 8.27.
1.33 (m, 2 CH3CH2O), 1.35–2.13 (m, 2 CH2), 2.49 (s, CH3S), 3.19–3.22
(m, CH), 4.19–4.29 (m, 2 CH3CH2O). 13C NMR:
d 9.6 (CH3), 16.2 (d,
3
3JCP¼7.1 Hz, CH3CH2O), 16.3 (d, JCP¼7.2 Hz, CH3CH2O), 18.2 (CH3),
18.8 (broad, CH3), 20.7 (CH3), 25.6, 30.6 (2 CH2), 45.6 (Cq), 54.3 (d,
3JCP¼11.4 Hz, CH), 60.4 (Cq), 63.0, 63.1 (2d, 2JCP¼6.7 Hz, 2 CH3CH2O),
1
2
4.2.4. [(Methylsulfanyl)(thioxanthen-9-ylidene)methyl]phosphonic
acid diethyl ester (8d). Yield: 212 mg (54%). Pale yellow crystals.
130.8 (d, JCP¼185.3 Hz, P–C]C), 158.4 (d, JCP¼10.7 Hz, P–C]C),
3
201.8 (d, JCP¼6.3 Hz, C]O). 31P NMR:
d
10.38. IR (film, cmꢀ1):

8196
G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
2960s, 2928s, 2827m, 1734s (C]O), 1574m, 1475m, 1443m, 1252
(P]O), 1164m, 1062vs and 1027vs (P–O–C), 964s, 744m. CIMS
(NH3), m/z (%): 347 (100, [Mþ1]þ). Anal. Calcd for C16H27O4PS
(346.43): C 55.47, H 7.85, S 9.26; found: C 55.44, H 6.96, S 8.92.
(isobutane), m/z (%): 377 (100, [Mþ1]þ). Anal. Calcd for C19H21O4PS
(376.41): C 60.63, H 5.62, S 8.52; found: C 60.71, H 5.83, S 8.57.
4.4.4. [(Fluoren-9-ylidene)(methanesulfonyl)methyl]phosphonic acid
diethyl ester (14b). Yield: 262 mg (67%). Orange crystals. Mp 110–
112 ꢁC. 1H NMR:
d
1.26 (t, JHH¼7.0 Hz, 2 CH3CH2O), 3.49 (s, CH3SO2),
4.4. Oxidation of 1-(methylsulfanyl)vinylphosphonates
8a,b,f,g with mCPBA
4.16–4.28 (m, 2 CH3CH2O), 7.18–7.24 (m, 2 CHarom), 7.36–7.38 (m, 2
CHarom), 7.47, 7.50, 8.25, 8.35 (4d, JHH¼7.7 Hz, 4 CHarom). 13C NMR:
3
d
15.9 (d, JCP¼5.3 Hz, 2 CH3CH2O), 43.6 (s, CH3SO2), 63.7 (d,
A solution of 1 mmol of the corresponding vinyl phosphonate
8a,b,f,g in 20 mL of dichloromethane was placed in a flask equipped
with a magnetic stirring bar and cooled in a ice bath to ꢀ5 ꢁC. While
stirring, a corresponding amount (2.5 mmol in reactions with 8a,
8b, and 8g and 3.5 mmol in the reaction with 8f) of commercial
(77%) mCPBA was added portion-wise and stirring was continued
for 0.5–1 h. After this time, the mixture was shaken with a satu-
rated aqueous solution of NaHCO3, then with a 5% solution of NaOH,
and with brine. The organic layer was dried with MgSO4 and the
solvent was evaporated in vacuo. The residue was purified chro-
matographically (SiO2) (except 15a), and analytically pure products
were obtained by crystallization from a mixture of petroleum ether
with a small amount of dichloromethane (for 13a, 14a, 13f, and
14g), from diethyl ether (for 13b and 14b), and from methanol at 0–
5 ꢁC (for 15a). The product 13g was obtained as a yellowish oil.
2JCP¼5.3 Hz, 2 CH3CH2O), 119.5, 120.0, 127.6, 128.2, 130.5, 131.3,
132.8, 133.1 (8 CHarom), 129.9 (d, 1JCP¼180.3 Hz, P–C]C), 136.2 (d,
3JCP¼15.9 Hz, Carom), 136.8 (d, JCP¼7.0 Hz, Carom), 142.6, 143.4 (2
3
Carom), 160.6 (d, JCP¼3.5 Hz, P–C]C). 31P NMR:
d 9.01. IR (KBr,
2
cmꢀ1): 2983m, 2910w,1600w,1523s,1448m,1316vs,1251vs (P]O),
1142vs, 1040vs, 1013s (P–O–C), 989s, 976s, 767s, 740s, 570s. CIMS
(isobutane), m/z (%): 393 (100, [Mþ1]þ). Anal. Calcd for C19H21O5PS
(392.41): C 58.16, H 5.39, S 8.17; found: C 58.21, H 5.27, S 8.20.
4.4.5. (Z)-[(Methanesulfinyl)(2-oxoacenaphthen-1-ylidene)methyl]-
phosphonic acid diethyl ester (13f). Yield: 215 mg (57%). Orange
crystals. Mp 138–140 ꢁC. 1H NMR:
d
1.36, 1.37 (2t, JHH¼7.0 Hz, 2
CH3CH2O), 3.25 (s, CH3SO), 4.32–4.36 (m, 2 CH3CH2O), 7.75–7.77 (m,
2 CHarom), 7.98 (d, JHH¼7.0 Hz, 1 CHarom), 8.02 (d, JHH¼8.4 Hz,
1 CHarom), 8.16 (d, JHH¼7.7 Hz, 1 CHarom), 8.78 (d, JHH¼7.7 Hz, 1
CHarom). 13C NMR:
d
16.2, 16.3 (2d, JCP¼6.4 Hz, 2 CH3CH2O), 39.8
3
2
2
4.4.1. [1-(Methanesulfinyl)-2,2-diphenylvinyl]phosphonic acid diethyl
ester (13a). Yield: 265 mg (70%). Colorless crystals. Mp 93–96 ꢁC.
(CH3SO), 62.8 (d, JCP¼6.2 Hz, CH3CH2O), 64.0 (d, JCP¼5.4 Hz,
CH3CH2O), 122.2, 127.6, 127.9, 128.7, 128.8, 132.3 (6 CHarom), 129.6 (d,
1H NMR:
d
0.98, 1.29 (2 t, JHH¼7.0 Hz, 2 CH3CH2O), 3.16 (s, CH3SO),
3JCP¼6.5 Hz, 1 Carom), 129.8 (d, JCP¼2.8 Hz, 1 Carom), 130.5, 142.9 (2
4
2
1
3.76–4.25 (m, 2 CH3CH2O), 7.11–7.13 (m, 2 CHarom), 7.32–7.41 (m, 8
Carom), 145.1 (d, JCP¼5.0 Hz, P–C]C), 146.9 (d, JCP¼163.3 Hz,
CHarom). 13C NMR:
d
15.8, 16.2 (2d, JCP¼7.0 Hz, 2 CH3CH2O), 39.4
P–C]C), 192.5 (d, JCP¼19.4 Hz, C]O). 31P NMR:
d 9.26. IR (KBr,
3
3
2
(s, CH3SO), 62.4, 62.5 (2d, JCP¼5.3 Hz, 2 CH3CH2O), 127.8, 128.2,
cmꢀ1): 2983m, 2926w, 1703s (C]O), 1624m, 1553m, 1435m, 1246s
(P]O), 1063vs and 1033vs (P–O–C), 964s, 949s, 566m. CIMS (iso-
butane), m/z (%): 379 (100, [Mþ1]þ). Anal. Calcd for C18H19O5PS
(378.39): C 57.14, H 5.06, S 8.47; found: C 57.11, H 5.03, S 8.41.
1
129.4, 129.5, 129.9 (10 CHarom), 135.4 (d, JCP¼170.7 Hz, P–C]C),
140.2 (d, 3JCP¼15.8 Hz, Carom), 140.5 (d, 3JCP¼7.0 Hz, Carom), 166.4 (d,
2JCP¼8.8 Hz, P–C]C). 31P NMR:
d
10.80. IR (KBr, cmꢀ1): 3059m,
2980m, 1550m, 1490m, 1444m, 1251s (P]O), 1050vs and 1028vs
(P–O–C), 1005m, 958m, 705m. CIMS (isobutane), m/z (%): 379 (100,
[Mþ1]þ). Anal. Calcd for C19H23O4PS (378.43): C 60.30, H 6.13,
S 8.47; found: C 60.33, H 6.11, S 8.21.
4.4.6. (Z)-[30-Methanesulfonyl-2-oxo(acenaphthen-2-spiro-20-ox-
iran)-30-yl]phosphonic acid diethyl ester (15a). Yield: 205 mg (52%).
Pale yellow crystals. Mp 148–150 ꢁC. 1H NMR:
d 1.22, 1.42 (2t,
JHH¼7.0 Hz,
2 CH3CH2O), 3.51 (s, CH3SO2), 4.14, 4.42 (2dq,
3
4.4.2. [1-(Methanesulfonyl)-2,2-diphenylvinyl]phosphonic acid diethyl
2JH,H¼7.0 Hz, JH,P¼7.5 Hz, 2 CH3CH2O), 7.60–7.82 (m, 2 CHarom),
ester (14a). Yield: 272 mg (69%). Colorless crystals. Mp 122–124 ꢁC.
7.92–8.10 (m, 2 CHarom), 8.15 (d, JHH¼8.2 Hz, 1 CHarom), 8.55 (d,
1H NMR:
d
1.15 (t, JHH¼7.2 Hz, 2 CH3CH2O), 3.19 (s, CH3SO2), 3.80–
JHH¼7.1 Hz, 1 CHarom). 13C NMR:
d
16.0 (d, JCP¼5.7 Hz, CH3CH2O),
3
4.20 (m, 2 CH3CH2O), 7.22–7.45 (m, 10 CHarom). 13C NMR:
d
16.0
16.5 (d, 3JCP¼5.2 Hz, CH3CH2O), 29.5 (d, 2JC,P¼42.0 Hz, C(30)-oxiran),
42.3 (CH3SO2), 43.5 (d, 1JC,P¼408.0 Hz, C(20)-oxiran), 64.8, 65.0 (2d,
2JCP¼6.8 Hz, 2 CH3CH2O), 122.7, 125.8, 127.5, 128.1, 128.5, 132.3 (6
CHarom), 126.5, 129.9, 130.3, 143.0 (4 Carom), 193.3 (C]O). 31P NMR:
(d, 3JCP¼7.0 Hz, 2 CH3CH2O), 45.5 (s, CH3SO2), 63.2 (d, 2JCP¼7.0 Hz, 2
CH31CH2O), 127.9, 128.1, 129.5, 130.1, 130.3, 130.5 (10 CHarom), 133.4
3
(d, JCP¼184.8 Hz, P–C]C), 140.7 (d, JCP¼15.8 Hz, Carom), 141.3
(d, JCP¼5.3 Hz, Carom), 169.4 (d, JCP¼5.2 Hz, P–C]C). 31P NMR:
d
8.00. IR (KBr, cmꢀ1): 3000m, 2986m, 1745vs (C]O), 1605m,
3
2
d
9.41. IR (KBr, cmꢀ1): 3000m, 2980m, 1556m, 1488m, 1446m,
1493m,1441m,1321vs,1273s (P]O),1149vs,1051vs and 1020vs (P–
O–C), 971s, 780s, 520s. ESI-MS, m/z (%): 433 (100, [MþNa]þ). Anal.
Calcd for C18H19O7PS (410.39)$0.5H2O: C 51.55, H 4.81, S 7.65;
found: C 51.69, H 4.67, S 7.57.
1311vs, 1258s (P]O), 1142vs, 1050vs and 1027vs (P–O–C), 966s,
828s, 704s, 554s, 520s. CIMS (isobutane), m/z (%): 395 (100,
[Mþ1]þ). Anal. Calcd for C19H23O5PS (394.43): C 57.86, H 5.88, S 8.13;
found: C 57.78, H 5.86, S 8.17.
4.4.7. (E)-[(Methanesulfinyl)(4,7,7-trimethyl-3-oxobicyclo[2.2.1]hept-
2-ylidene)methyl]phosphonic acid diethyl ester (13g). Yield: 204 mg
(56%). Yellowish oil. The product was obtained as a mixture of two
4.4.3. [(Fluoren-9-ylidene)(methanesulfinyl)methyl]phosphonic acid
diethyl ester (13b). Yield: 283 mg (75%). Yellow crystals. Mp 66–
68 ꢁC. 1H NMR:
d
1.29, 1.36 (2t, JHH¼7.0 Hz, 2 CH3CH2O), 3.26
diastereoisomers A and B. 1H NMR:
d
0.82, 0.88 (2s, CH3, AþB), 1.00,
(s, CH3SO), 4.22–4.35 (m, 2 CH3CH2O), 7.24–7.27 (m, 2 CHarom), 7.38–
1.03 (2s, 2 CH3, AþB), 1.31 (t, JHH¼7.2 Hz, 2 CH3CH2O, AþB), 1.50–
2.40 (m, 2 CH2, AþB), 2.95 (s, CH3SO, AþB), 4.05–4.48 (m, 2
7.40 (m,
2
CHarom), 7.54 (d, JHH¼7.7 Hz,
2 CHarom), 7.79
(d, JHH¼8.4 Hz, 1 CHarom), 8.54 (d, JHH¼7.7 Hz, 1 CHarom). 13C NMR:
CH3CH2O, CH, AþB). 13C NMR:
d
9.1 (CH3SO, AþB), 16.0, 16.1 (CH3,
3
d
16.2 (d, JCP¼7.0 Hz, 2 CH3CH2O), 38.2 (s, CH3SO), 62.5, 63.5 (2d,
AþB), 17.8 (CH3, AþB), 20.9, 21.0 (2 CH3CH2O, AþB), 25.2, 26.9 (CH2,
AþB), 29.4, 29.7 (CH2, AþB), 41.1, 41.4 (CH3SO, AþB), 44.8, 45.6 (Cq,
AþB), 47.4 (d, 4JCP¼11.1 Hz, CH, A), 48.7 (d, 4JCP¼11.8 Hz, CH, B), 56.1,
56.2 (Cq, AþB), 63.0, 63.2, 63.4, 63.5 (4d, 2 CH3CH2O, AþB), 137.6 (d,
1JCP¼172.8 Hz, P–C]C, A), 137.8 (d, 1JCP¼173.9 Hz, P–C]C, B), 159.7
(P–C]C, AþB), 203.2 (d, 3JCP¼8.2 Hz, C]O, A), 203.4 (d, 3JCP¼8.9 Hz,
2JCP¼5.3 Hz, 2 CH3CH2O), 119.4, 119.9, 127.7, 127.8, 129.7, 130.7, 131.6,
1
131.8 (8 CHarom), 134.9 (d, JCP¼167.2 Hz, P–C]C), 135.7
3
3
(d, JCP¼7.0 Hz, Carom), 137.1 (d, JCP¼17.6 Hz, Carom), 142.4, 142.5
(2 Carom), 155.1 (d, JCP¼7.0 Hz, P–C]C). 31P NMR:
d 10.32. IR (KBr,
2
cmꢀ1): 2982m, 2927w, 1602m, 1534m, 1447s, 1250s (P]O), 1096 m,
1059vs, 1043vs, 1015vs (P–O–C), 980s, 788s, 731s, 565s. CIMS
C]O, B). 31P NMR: 7.33, 7.61. IR (film, cmꢀ1): 2983s, 2960s, 2930s,
d

G. Mloston´ et al. / Tetrahedron 65 (2009) 8191–8198
8197
2872s, 1743s (C]O), 1644m, 1595m, 1477m, 1392m, 1254s (P]O),
1162m, 1054s and 1015s (P–O–C), 962s, 877m, 830m, 756m. ESI-MS,
m/z (%): 385 (100, [MþNa]þ), 311 (6). Anal. Calcd for C16H27O5PS
(362.43): C 53.02, H 7.51, S 8.85; found: C 52.78, H 7.35, S 8.73.
1.000, total reflections measured 26,908, symmetry independent re-
flections 6054, reflections with I>2 (I) 4346, reflections used in re-
finement 6053, parameters refined 239; R(F) [I>2s(I)
s
reflections]¼0.0555, wR(F2) [all data]¼0.1206 (w¼[
s
2(Fo2)þ
(0.0437P)2þ0.8184P]ꢀ1, where P¼(Fo2þ2F2c)/3), goodness of fit 1.094,
4.4.8. (E)-[(Methanesulfonyl)(4,7,7-trimethyl-3-oxobicyclo[2.2.1]-
final Dmax
tinction coefficient¼0.0042(7).
/
s
0.001, Dr (max; min)¼0.29; ꢀ0.30 e Åꢀ3, secondary ex-
hept-2-ylidene)methyl]phosphonic acid diethyl ester (14g). Yield:
20
240 mg (63%). Yellowish crystals. Mp 128–130 ꢁC. [
a]
¼þ157.5
Crystal data for 13f: C18H19O5PS, M¼378.38, crystallized from
CH2Cl2/hexane, orange, prism, crystal dimensions 0.12ꢂ0.15
ꢂ0.25 mm, monoclinic, space group P21/c, Z¼4, reflections for cell
D
(CH2Cl2). 1H NMR:
CH3CH2O), 1.45–2.50 (m, 2 CH2), 3.30 (s, CH3SO2), 3.88–4.02 (m,
CH), 4.05–4.52 (m, 2 CH3CH2O). 13C NMR:
9.7 (CH3), 16.4 (broad,
d
0.88, 0.98, 1.01 (3s, 3 CH3), 1.32 (t, JHH¼7.1 Hz, 2
d
determination 27,091, 2q
range for cell determination 4–60ꢁ,
CH3), 18.2 (CH3), 21.2 (2 CH3CH2O), 25.7, 30.8 (2 CH2), 44.7
(CH3SO2), 45.6 (Cq), 53.9 (d, 3JCP¼10.5 Hz, CH), 57.9 (Cq), 64.07, 64.14
a¼15.1731(2) Å, b¼7.8235(1) Å, c¼15.6336(3) Å,
b
¼109.9740(9),
V¼1744.18(5) Å3,
T¼250(1) K,
DX¼1.441 g cmꢀ3
,
m
(MoKa)¼
(2d, JCP¼6.5, 6.0 Hz, 2 CH3CH2O), 134.1 (d, 1JCP¼181.5 Hz, P–C]C),
0.303 mmꢀ1, scan type
(min; max) 0.819; 0.964, total reflections measured 49,825, sym-
f
and
u
, 2q(max)¼60ꢁ, transmission factors
2
3
166.5 (P–C]C), 204.8 (d, JCP¼7.5 Hz, C]O). 31P NMR:
d
5.07. IR
(KBr, cmꢀ1): 2987m, 2972m, 2920m, 1747s (C]O), 1592m, 1323vs,
1254vs (P]O), 1143s, 1052s and 1021s (P–O–C), 994s, 984s, 960s,
780m, 568m. ESI-MS, m/z (%): 401 (100, [MþNa]þ). Anal. Calcd for
C16H27O6PS (378.43): C 50.78, H 7.19, S 8.47; found: C 50.75, H 7.25,
S 8.41.
metry independent reflections 5085, reflections with I>2
reflections used in refinement 5084, parameters refined 229; R(F)
s(I) 3462,
[I>2
s
(I)
reflections]¼0.0473,
wR(F2)
[all
data]¼0.1347
(w¼[
s
2(Fo2)þ(0.0658P)2þ0.5114P]ꢀ1, where P¼(Fo2þ2F2c)/3), good-
ness of fit 1.046, final Dmax
/s
0.001, Dr (max; min)¼0.57;
ꢀ0.53 e Åꢀ3
.
4.5. X-ray crystal-structure determination of 14a, 13f, and 14g
Crystal data for 14g: C16H27O6PS, M¼378.42, crystallized from
CH2Cl2/hexane, pale yellow, prism, crystal dimensions
0.17ꢂ0.20ꢂ0.30 mm, tetragonal, space group P43, Z¼4, reflections
All measurements for 14a were performed on a Bruker SMART-
CCD area-detector diffractometer using graphite-monochromated
for cell determination 33,269, 2q range for cell determination 4–
Mo K
a
radiation (
l
0.71073 Å). Data reduction was performed with
55ꢁ, a¼10.2390(2) Å, c¼18.7150(5) Å, V¼1962.03(8) Å3, T¼160(1) K,
the Bruker SAINT software.33 The intensities were corrected for
Lorentz and polarization effects, and an absorption correction
based on the multi-scan method34 was applied. All measurements
for 13f and 14g were made on a Nonius KappaCCD area-detector
DX¼1.281 g cmꢀ3
,
m
(MoK
a
)¼0.273 mmꢀ1
, scan type f and u,
2
q(max)¼55ꢁ, transmission factors (min; max) 0.883; 0.956, total
reflections measured 25,655, symmetry independent reflections
4453, reflections with I>2s(I) 3783, reflections used in refinement
diffractometer35 using graphite-monochromated Mo K
a
radiation
4453, parameters refined 223; restraints 1, R(F) [I>2s(I)
(l
0.71073 Å) and, in the case of 14g, an Oxford Cryosystems
reflections]¼0.0369, wR(F2) [all data]¼0.0866 (w¼[
s
2(Fo2)þ
Cryostream 700 cooler. Data reduction was performed with HKL
Denzo and Scalepack.36 The intensities were corrected for Lorentz
and polarization effects, and an absorption correction based on the
multi-scan method37 was applied. Equivalent reflections were
merged in all cases, except for the Friedel pairs in 14g. The data
collection and refinement parameters are given below38 and views
of the molecules are shown in Figures 1–3. The structures were
solved by direct methods using SIR92,39 which revealed the posi-
tions of all non-H-atoms. The non-H-atoms were refined aniso-
tropically. All of the H-atoms were placed in geometrically
calculated positions and refined by using a riding model where
each H-atom was assigned a fixed isotropic displacement param-
eter with a value equal to 1.2Ueq of its parent C-atom (1.5Ueq for the
methyl groups). The refinement of the structures was carried out on
F2 using full-matrix least-squares procedures, which minimized the
(0.0422P)2þ0.4138P]ꢀ1, where P¼(Fo2þ2F2c)/3), goodness of fit 1.036,
final Dmax
/s
0.001, Dr (max; min)¼0.20; ꢀ0.23 e Åꢀ3
.
Acknowledgements
The authors thank the Polish Ministry of Science and Higher
Education for a grant (# N N204 130335) (G.M., K.U.); financial
support by F. Hoffmann-La Roche AG, Basel, is also gratefully
acknowledged (H.H.). The authors are grateful to Dr. M.D. Wo¨rle,
Laboratorium fu¨r Anorganische Chemie, ETH Zu¨rich, for collecting
the diffraction data for 14a, and to S. Blumentritt, Institute of
Organic Chemistry, University of Zu¨rich, for assistance with the
crystal-structure determinations.
function
S
w(Fo2ꢀF2c)2. A correction for secondary extinction was
References and notes
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which confidently confirms that the refined model corresponds
with the true enantiomorph. Neutral atom scattering factors for
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H-atoms were taken from Ref. 42. Anomalous dispersion effects
were included in Fc;43 the values for f0 and f00 were those of Ref. 44.
The values of the mass attenuation coefficients are those of Ref. 45.
All calculations were performed using the SHELXL9746 program.
Crystal data for 14a: C19H23O5PS, M¼394.42, crystallized from
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