Furyl-Substituted Mixed Phosphonium-Iodonium Ylides in the Synthesis of Annelated P-Containing Heterocyclic Compounds

Article abstract of DOI:10.1002/ejoc.201500876

Photochemical reactions between stabilized furyl-substituted phosphonium-iodonium ylides and terminal acetylenes led to the formation of new P-containing heterocyclic compounds. For the heterocyclization of 2-furyl-substituted ylides, we observed an unprecedented electrophilic ipso attack onto the α position of the furan ring in a carbocationic intermediate, leading - via a spiro intermediate - to the rearranged product with a 2,3-shift in the furan ring.

Full text of DOI:10.1002/ejoc.201500876

FULL PAPER
DOI: 10.1002/ejoc.201500876
Furyl-Substituted Mixed Phosphonium–Iodonium Ylides in the Synthesis of
Annelated P-Containing Heterocyclic Compounds
Elena D. Matveeva,*[a,b] Dmitrii S. Vinogradov,[a] Tatyana A. Podrugina,[a]
Tatiana D. Nekipelova,[a,c] Andrey V. Mironov,[a] Rolf Gleiter,[d] and Nikolay S. Zefirov[a,b]
Keywords: Ylides / Phosphorus / Heterocycles / Cyclization / Rearrangement / Photochemistry
Photochemical reactions between stabilized furyl-substituted
phosphonium–iodonium ylides and terminal acetylenes led
ylides, we observed an unprecedented electrophilic ipso at-
tack onto the α position of the furan ring in a carbocationic
to the formation of new P-containing heterocyclic com- intermediate, leading – via a spiro intermediate – to the re-
pounds. For the heterocyclization of 2-furyl-substituted
arranged product with a 2,3-shift in the furan ring.
tochemical conditions give phosphinolines as the principal
products.[2]
Introduction
Until recently, λ5-phosphinolines – structural analogues
The proposed mechanism of the heterocyclization in-
of quinoline – had seldom appeared in the literature.[1] Our volves cationic intermediates A and B. Intermediate B un-
discovery of the photochemical heterocyclization of mixed dergoes electrophilic aromatic substitution to give the final
phosphonium–iodonium ylides 1 with a variety of acetyl- phosphinoline (i.e., 2).[2] Taking into account the ease of
enes opened a new route to these relatively unknown annel- electrophilic substitution for five-membered heterocyclic
ated P-containing heterocycles 2 (Scheme 1). Indeed, the systems such as furan and thiophene, we studied
heterocyclization reactions of different stabilized phosphon- mono-heterosubstituted phosphonium–iodonium ylides 3a
ium–iodonium ylides with a variety of alkynes under pho- and 3b in photochemical reactions with alkynes and ob-
Scheme 1. Formation of λ5-phosphinolines.
tained the corresponding phosphininofurans or phos-
[a] Moscow State Lomonosov University,
Department of Chemistry,
phininothiophenes with structures 4a and 4b, respectively
(Scheme 2).[3]
Lenin Hills, 1, 119992 Moscow, Russsia
E-mail: matveeva@med.chem.msu.ru
http://www.chem.msu.ru
[b] Institute of Physiologically Active Compounds,
Russian Academy of Science,
142432Chernogolovka, Moscow region, Russia
http://zefirov.ipac.ac.ru/
[c] Emanuel Institute of Biochemical Physics, Russian Academy of
Sciences,
ul Kosygina 4, 119334 Moscow, Russia
http://www.researchgate.net/profile/Tatiana_Nekipelova
[d] Organisch-Chemisches Institut der Universitaet Heidelberg,
Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
http://www.uni-heidelberg.de/institute/fak12/OC/gleiter/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201500876.
Scheme 2. Formation of phosphininothiophenes and phosphinino-
furans.
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Furyl-Substituted Mixed Phosphonium–Iodonium Ylides
However, we observed a great difference in reactivity be-
As noted above, furyl-substituted ylides 3a (Scheme 2)
tween furyl-containing ylides 3a and any other ylides, such are much more reactive than phenyl-, pyrazolyl-, and thien-
as 1 or 3b.[3] The furyl-substituted ylides (i.e., 3a) show an yl-substituted ylides (3b). In fact, we have previously noted
unexpectedly high reactivity, and react vigorously in day- that the reactions of furyl-substituted ylides 3a with acetyl-
light and even in the dark to give the phosphininofuran enes can proceed even without UV irradiation.[3] Our pre-
products. This unexpected and surprising difference is in vious study of the reactions of triphenyl-substituted mixed
sharp contrast to the behaviour of thienyl-substituted ylides 1 with phenylacetylene by steady-state photolysis
ylides, and demands a more detailed study of their reactiv- showed that the rate of the reaction was increased by the
ity with acetylenes. Therefore, in this paper we present a presence of catalytic amounts of acid.[5] Hence, it is reason-
detailed investigation of the reactivity and product compo- able to assume that the reason for the anomalous behaviour
sition for the reactions of various furyl-substituted ylides of furyl-substituted ylides 3a is the presence of trace
with acetylenes.
amounts of acidic impurities, which can have a catalytic ef-
fect. This is reasonable, because mixed ylides 3a were all
obtained as the tetrafluoroborates from the reaction mix-
tures by the addition of HBF4. In other words, the presence
Results and Discussion
We synthesized of a series of furyl-substituted mixed of trace amounts of acid in furyl-substituted ylides 3a may
ylides 14–16 containing different stabilizing groups (i.e., R be enough to initiate the heterocyclization processes.
= COPh, COOMe, P(O)(OEt)2; Scheme 3) to reproduce
and to extend our previous data, paying special attention
to the purity of the ylides used. This might be important,
because the synthesis of mixed ylides requires the use of
acid.
To test this hypothesis, 2-furyl-substituted ylides 14
(Table 1) were carefully purified from traces of acid by rins-
ing with diethyl ether, or by recrystallization from this sol-
vent. We found that these thoroughly purified ylides 14 re-
act with alkynes only under UV irradiation for 15–30 min,
similarly to any other ylides.
Aryl,heteroaryl-substituted phosphines 5–7, which were
obtained in 36–70% yield,[4] were further converted into the
corresponding phosphonium salts (i.e., 8–10; Scheme 3).
Phosphoranes 11–13 were obtained by deprotonation of the
respective phosphonium salts using strong bases and were
oxidized without purification to give the corresponding
phosphonium–iodonium ylides (i.e., 14–16) using (diacet-
oxyiodo)benzene and treatment with HBF4. All the com-
pounds synthesized are summarized in Table 1. Since phos-
phoranes 11e, 12c, 12d, and 13c are unstable, they were used
without further purification. The structures of phos-
phoranes 11e, 12c, 12d, and 13c were confirmed by their
1H and 31P NMR spectroscopic data. The structures of the
phosphonium salts and mixed ylides were confirmed using
NMR and IR spectroscopy, elemental analysis, and HRMS.
In our recent work, we showed that the heterocyclization
of benzoyl-substituted ylides with 2-thienyl (3b) and 3-
thienyl groups at the phosphorus atom with alkynes gave
different products: phosphinino[2,3-b]thiophene 4b for the
2-thienyl-substituted ylide (i.e., 3b), and phosphinino[3,2-b]-
and -[3,4-c]thiophenes for the 3-thienyl-substituted ylide.[2]
Taking into account this analogy, we expected the forma-
tion of different products for 2-furyl-substituted ylides 14
compared to their 3-furyl-substituted counterparts 16.
The reaction of 2-furyl-substituted ylides 14 with phenyl-
acetylene and (4-methoxyphenyl)acetylene under UV irra-
diation (366 nm) gave mixtures containing at least three or
four principal fractions, which could be separated by col-
umn chromatography. One of these was the expected phos-
phininofuran fraction. The second fraction contained “di-
meric” heterocycles, which will be discussed later. The third
fraction contained phosphonium salts 22, and the fourth
fraction phosphonium-substituted furans 21c and 21d [for
the reaction of ylides 14c and 14d with (4-methoxyphenyl)-
acetylene, see Table 2]. We have previously discussed mech-
anistic pathways leading to the formation of phosphonium
salts 22 in the course of photodecomposition of phosphon-
ium–iodonium ylides.[5] Schemes for the formation of phos-
phonium-substituted furans 21c and 21d were presented
and discussed in our previous papers.[3]
Table 1. Yields of phosphonium salts and the corresponding mixed
ylides.
Z
Het
Phosphonium salt, Mixed ylide,
yield [%]
yield [%]
–CO–Ph
–COOMe
–PO(OEt)2
–CO–Ph
–COOMe 5-methyl-2-furyl
–CO–Ph 3-furyl
2-furyl
2-furyl
2-furyl
8c, 80
8d, 84
8e, 86
9c, 69
9d, 62
10c, 65
14c, 90
14d, 86
14e, 88
15c, 95
15d, 82
16c, 87
5-methyl-2-furyl
Scheme 3. Synthesis of mixed phosphonium–iodonium ylides.
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E. D. Matveeva et al.
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Table 2. Reaction of ylides 14c–14e with acetylenes.
Ylide
Z
R1
Phosphininofuran,
yield [%]
“Dimer”,
yield [%]
Furan
yield [%]
Phosphonium salt,
yield [%]
14c
14c
14d
14d
14e
14e
COPh
COPh
COOMe
COOMe
PO(OEt)2
PO(OEt)2
Ph
17c, 25
18c, 15
17d, 22
18d, 20
17e, 15
18e, 12
19c, 10
–
19d, 18
20d, 12
19e, 30
20e, 25
–
22c, 49
22c, 35
22d, 52
22d, 56
22e, 50
22e, 45
4-MeOC6H4
Ph
4-MeOC6H4
Ph
21c, 22 (R2 = Ph)
–
21d, 15 (R2 = OMe)
–
–
4-MeOC6H4
Clearly, the structures of phosphininofurans 17 and 18 structure 25 (Scheme 4), and, surprisingly, in favour of
in Scheme 4 differ from the phosphininofuran structures structure 26.
shown in Scheme 2. However, structural elucidation of the
Direct proof of the structure of the phosphininofuran
phosphininofurans obtained from 2-furyl-substituted ylides synthesized from ylide 14c and (4-methoxyphenyl)acetylene
14 using 1D and 2D NMR spectroscopy led to astonishing was obtained from X-ray diffraction data, which showed
results. All of the phosphininofurans prepared from ylides that structure 23c was incorrect, and that structure 18c was
14 showed, as expected, the presence of the α- and β-pro- correct for this product. Crystals of 18c were obtained by
tons of the furan ring. However, 2D 1H,1H NOESY spectra crystallization from acetonitrile. Pale brown single crystals
showed interactions between the β-proton of the furan ring were chosen for the experiment. The structure was solved
and the o-protons of the phenyl substituents on the P-atom, by direct methods, then refined in isotropic and anisotropic
which is inconsistent with the accepted structures 23 and 24 approximations of atomic displacement parameters (ADP)
(Scheme 4), and, surprisingly, in favour of structures 17 and successively for all non-hydrogen atoms. The position of the
18.
hydrogen atoms was calculated according to the geometry
Analogously, the heterocyclization reaction of 5-meth- of the carbon atoms, and their positions were refined con-
ylfuran-2-yl-substituted mixed ylides 15c and 15d with strained at a distance of 1 Å from the carbon atoms. In the
phenylacetylene led to the formation of separable mixtures isotropic approximation, their atomic displacement param-
of phosphininofuran and the corresponding phosphonium eters were taken as 1.2 times larger than those of the neigh-
salts (i.e., 9c and 9d; Scheme 3) in a ratio of 15:59 for 15c, bouring carbon atom.
and 17:56 for 15d. The structures of these phosphininofur-
When we initially attempted to refine the crystal struc-
ans were also determined by 1D and 2D NMR spec- ture, the oxygen atom (O-2) of the five-membered ring was
troscopy. The 1H NMR spectrum showed that the only ring considered as a carbon atom. The R factor was then 0.063,
proton was at the β-position of the furan ring, and that the and ADP for O-2 was half what it was for the neighbouring
methyl group was in the α-position. The 2D 1H,1H NOESY carbon atoms [Ueq = 0.0305(15) Å2 vs. Ueq = 0.06–
spectrum also showed an interaction between the β-proton 0.074 Å2]. In addition, the difference Fourier synthesis re-
of the furan ring and the o-protons of the phenyl substitu- vealed residual peaks of +0.47/–0.18 eÅ–3. The absorption
ents on the P-atom, which is also inconsistent with accepted correction was done according to the crystal shape, so an
Scheme 4. Proposed and observed structures of phosphininofurans.
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Furyl-Substituted Mixed Phosphonium–Iodonium Ylides
incorrectness in the absorption correction could hardly be ψ2 = 26.2°, σ = 0.8; CP parameters: Q = 0.162, θ = 68.4°,
the reason for the observed difference. Two positive maxima φ = 35.2°), but the non-planarity is not significant.
were significantly higher than all of the others, and were
Finally, the reaction of 3-furyl-substituted ylide 16c with
less than 0.5 Å away from the O-2 atom. The occupancy (4-methoxyphenyl)acetylene under UV irradiation (366 nm)
refinement of the O-2 site as carbon type resulted in g = gave phosphininofuran 18c, which was found to be identical
1.515(14) and a reduction of the R factor down to R = to the sample obtained from 2-furyl-substituted ylide 14c.
0.046, while the occupancy refinement of the neighbouring Moreover, the 1H, 13C, and 31P NMR spectra of phos-
carbon atoms remained equal to 1 within 3σ with almost phininofuran 18c prepared from 2- (14c) and 3-furyl-substi-
the same R factor. Thus, the type of the O-2 atom was tuted (16c) ylides were identical both for the separated sam-
changed from carbon to oxygen. This resulted in a decrease ples and for their equimolar mixture. The other products of
of the R factor (to 0.043). Further occupancy refinement this reaction were phosphinoline 27, phosphonium-substi-
gave g = 1.007(9), and a more reasonable ADP [Ueq
=
tuted furan 28, and phosphonium salt 29 (Scheme 5).
0.0672(10) Å2], similar to the neighbouring carbon atoms.
The ratio of phosphininofuran/phosphinoline (3:2)
The positive and negative residual peaks became lower and indicates the priority of heterocyclization on the
almost equal in magnitude (+0.20/–0.14 eÅ–3). Thus, for electron-rich furan ring. The structures of compounds 27
1
the final refinement, this atom was treated as oxygen. The and 28 were confirmed by H, 31P, and 13C NMR spec-
positions of the hydrogen atoms were also refined with con- troscopy.
strained ADP. The final structure obtained is shown in Fig-
ure 1.
Thus, the main result of the X-ray measurements and the
NMR spectroscopic studies was the identity of the product
According to the X-ray diffraction data and the results (i.e., 18c), obtained from both 2-furyl-substituted ylide 14c
of puckering parameter calculations by the Zefirov– and 3-furyl-substituted ylide 16c. This leads to the assump-
Palyulin (ZP)[6] and Cremer–Pople (CP)[7] methods using tion of a rearrangement. To account for this remarkable
the RICON program,[8] the six-membered phosphinoline result, we propose a rearrangement (2,3-shift) of the substit-
ring in structure 18c was found to have a distorted skew- uents in the furan rings for 2-furyl-containing ylides 14 and
boat conformation (ZP parameters: S = 0.201, θ = 61.6°, 5-methyl-2-furyl-containing ylides 15.
Figure 1. X-ray structure of 18c (C33H25O3P).
Scheme 5. Reaction of ylide 16c with (4-methoxyphenyl)acetylene.
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Scheme 6. Proposed mechanism for the heterocyclization of furyl-containing ylides 14c and 16c.
As was mentioned earlier, the formation of phosphin- 848.2440, 1004.2904) and 20d–20e (m/z
= 908.2648,
olines 2 (Scheme 1) includes an electrophilic aromatic sub- 1064.3111) are double the masses of the corresponding
stitution step, B Ǟ 2. Obviously, in the case of 3-furyl-sub- phosphininofurans (i.e., 17c–17e and 18d–18e). Molecules
stituted ylide 16c (Scheme 6), the electrophilic substitution 19 and 20 contain one α-substituted furan ring (signals at δ
step must preferentially occur at the more reactive α posi- = 5.88–6.07 ppm, due to the β-furyl proton, in the 1H
tion of the electron-rich furan ring via intermediates F and NMR spectrum; and signals at δ = 112–113 ppm, attributed
G to give phosphininofuran 18c (Scheme 6).
to the β-furyl carbon atom, and at δ = 149–154 ppm, attrib-
For the heterocyclization of 2-furyl-substituted ylides 14, uted to α carbon atom, in the 13C NMR spectrum). The 1H
we expected that the cyclization would occur at the unsub- and 13C NMR spectra show the presence of a formyl group
1
stituted β position of the furan ring, with the formation of in 19 and 20 (signal at δ = 8.71–8.75 ppm in the H NMR
phosphinino[2,3-b]furan 4a (Scheme 2).[3] However, as we spectrum and signals at δ = 198–199 ppm in the 13C NMR
have now established, the phosphininofuran structure ob- spectrum). This shows that one of the furan rings opened
tained is the same, namely phosphinino[3,2-b]furan 17 and during the formation of compounds 19 and 20. These data
18 (Schemes 4 and 5). This result can be explained by an confirm the structures shown in Figure 2.
electrophilic ipso attack on the α position of the furan ring
in carbocationic intermediate D (Scheme 6) to give cationic
spiro intermediate E. A subsequent carbocationic 2,3-shift
with migration of the phosphonium group to the β position
of the furan ring and deprotonative aromatization gives the
final phosphininofuran 18c (E Ǟ 18c; Scheme 6). To the
best of our knowledge, a rearrangement of this type in the
furan series has not been described in the literature. The
closest analogy we have found is the so-called Planche re-
arrangement in the indole series.[9] Clearly, this process re-
quires further investigation, maybe using a simpler model
compound in the furan series.
As pointed out above, the photochemical reactions of
ylides 14 give mixtures of products that contain the struc-
Figure 2. Dimeric products 19c–19e and 20d–20e.
tures named as “dimeric” heterocycles (Table 2). Inspection
of Table 2 shows that the ratio of so-called “dimeric” prod-
The final proof of the structure of compound 19d was
ucts to normal (“monomeric”) phosphininofurans depends obtained from its 2D NMR spectra. 2D 1H,1H COSY spec-
on the Z substituent (Scheme 3) and increases along the tra revealed interactions between the aldehyde proton and
sequence: PO(OEt)2 (2:1) Ͼ COOMe (1:1) Ͼ COPh (1:2.5). the protons of the CH2 group (Figure 3, interaction a). 2D
The dimeric character of these products is evident from 1H,13C HSQC spectra indicate an interaction between the
comparison of their HRMS data with the corresponding aldehyde proton and the carbonyl group (Figure 3, interac-
phosphininofuran counterparts. All the dimeric compounds tion b). 2D 1H,13C HMBC spectra (Figure 3, interactions c)
have two structurally slightly different phosphorus atoms, show interactions between the protons of the CH2 group
which is evident from their 31P NMR spectra. On the basis and the carbon center Ca and interactions between the β-
of HRMS, the masses of products 19c–19e (m/z = 940.2840, proton of the furan ring and carbon atom Cb (see Figure 3).
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Furyl-Substituted Mixed Phosphonium–Iodonium Ylides
(Furan-3-yl)(2-oxo-2-phenylethyl)diphenylphosphonium
Bromide
(10c, X = Br): White solid (2.0 g, 60%), m.p. 234 °C. 1H NMR
(400 MHz, CDCl3): δ = 6.29 (d, J = 12.1 Hz, 2 H), 6.88–6.89 (m,
1 H), 7.48 (t, J = 7.8 Hz, 2 H), 7.58–7.68 (m, 5 H), 7.73–7.78 (m,
3 H), 7.96 (dd, J = 14.1, J = 7.3 Hz, 4 H), 8.27 (br. s, 1 H), 8.36
(d, J = 7.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 39.5
(d, J = 65.1 Hz), 112.8 (d, J = 10.3 Hz), 118.7 (d, J = 93.7 Hz),
126.8 (d, J = 136.9 Hz), 128.9, 129.9, 130.1 (d, J = 13.2 Hz), 133.3
(d, J = 11.0 Hz), 134.7, 134.77, 134.84, 146.2 (d, J = 13.9 Hz), 154.2
(d, J = 22.0 Hz), 192.3 (d, J = 5.9 Hz) ppm. 31P NMR (161 MHz,
Figure 3. 1H,1H and 1H,13C interactions within 19d observed by
2D NMR spectroscopy.
CDCl ): δ = 12.06 ppm. IR: ν = 1658, 1472, 720–745 cm–1.
˜
3
C24H20BrO2P (451.30): calcd. C 63.87, H 4.47; found C 64.09, H
4.68.
(2-Methoxy-2-oxoethyl)(5-methylfuran-2-yl)diphenylphosphonium
Bromide (9d, X = Br): Methyl bromoacetate (4.12 mmol) was added
to a solution of phosphine 6 (3.71 mmol) in dry acetonitrile (5 mL).
The reaction mixture was stirred under reflux for 2 h, then the pre-
cipitate was collected by filtration, washed with diethyl ether
(5 mL), and dried in vacuo to give the corresponding product
(0.9 g, 62%) as a white solid, m.p. 182 °C. 1H NMR (400 MHz,
CDCl3): δ = 2.32 (s, 3 H), 3.50 (s, 3 H), 5.22 (d, J = 12.8 Hz, 2 H),
6.30 (br. s, 1 H), 7.52–7.58 (m, 5 H), 7.68–7.69 (m, 3 H), 7.80–7.85
(m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.0, 31.7 (d, J
= 60.0 Hz), 53.1, 109.7 (d, J = 8.8 Hz), 116.6 (d, J = 92.9 Hz),
129.6 (d, J = 133.9 Hz), 129.9 (d, J = 13.9 Hz), 132.4 (d, J =
19.7 Hz), 132.6 (d, J = 11.0 Hz), 133.4 (d, J = 11.0 Hz), 135.1,
164.2 (d, J = 8.8 Hz) ppm. 31P NMR (161 MHz, CDCl3): δ =
Conclusions
A series of new furyl-substituted mixed phosphonium
ylides were synthesized. Their photochemical heterocycliz-
ation reaction with terminal aromatic acetylenes led to the
formation phosphinino[3,2-b]furans and new polycyclic P-
containing heterocycles. A new rearrangement (2,3-shift) of
the furan ring accompanied by a phosphonium fragment is
described.
Experimental Section
General: The 1H, 31P, and 13C NMR spectra were recorded in
CDCl3, CD2Cl2, and CD3CN, with Me4Si as the internal standard.
1H NMR spectra were measured at 400 MHz, 31P NMR spectra at
161 MHz and 13C NMR spectra at 100 MHz. The IR spectra were
measured in CCl4. High-resolution mass spectra (HRMS) were
measured using electrospray ionization (ESI) and a TOF mass ana-
lyser.[10] The measurements were carried out in positive-ion mode
(interface capillary voltage 4500 V); mass range m/z = 50–3000. Ex-
ternal calibration was carried out with Electrospray Calibrant Solu-
tion. Syringe injection was used for solutions in acetonitrile or
methanol (flow rate 3 μL/min). Nitrogen was applied as a dry gas;
the interface temperature was set at 180 °C. The progress of the
reactions and the purity after chromatographic separation were
monitored by TLC on silica gel 60 plates. Chromatographic separa-
tion was carried out on columns with silica gel 60. Compounds 8c,
11c, 14c, 21c, 8d, 11d, 14d, and 21d were synthesized according to
previously published methods.[3]
7.56 ppm. IR: ν = 1662, 1441, 740 cm–1. C H BrO P (419.25):
˜
20 20
3
calcd. C 57.30, H 4.81; found C 57.26, H 4.66.
{[(Diethoxyphosphoryl)methyl]furan-2-yl}diphenylphosphonium Tri-
fluoromethanesulfonate (8e, X = OTf): A solution of (diethoxyphos-
phoryl)methyl triflate (5.10 mmol) in anhydrous CH2Cl2 (3 mL)
was added dropwise to a stirred solution of phosphine 5
(5.71 mmol) in anhydrous CH2Cl2 (9 mL) at 0 °C under argon. The
mixture was warmed to room temp., and then stirred for 24 h. The
solvent was removed in vacuo to about one third of the volume,
and the remaining oil was triturated with diethyl ether (10 mL). A
white solid was formed and collected by filtration. The solid was
washed with diethyl ether (10 mL) to give 8e (2.57 g, 86%) as a
1
white solid, m.p. 118 °C. H NMR (400 MHz, CDCl3): δ = 1.13 (t,
J = 7.0 Hz, 6 H), 3.96–4.08 (m, 4 H), 4.15 (dd, J = 19.5, J =
16.5 Hz, 2 H), 6.77–6.79 (m, 1 H), 7.65–7.70 (m, 4 H), 7.73–7.74
(m, 1 H), 7.78–7.88 (m, 6 H), 8.00 (m, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 15.7 (d, J = 6.6 Hz), 20.8 (dd, J = 134.7,
J = 54.2 Hz), 63.5 (d, J = 6.6 Hz), 112.9 (d, J = 9.6 Hz), 116.9 (d,
J = 93.7 Hz), 129.9 (d, J = 13.9 Hz), 130.8 (d, J = 20.5 Hz), 131.5
(d, J = 95.9 Hz), 133.6 (d, J = 11.7 Hz), 135.4, 152.9 (d, J = 8.1 Hz)
ppm. 31P NMR (161 MHz, CDCl3): δ = 8.71 (d, J = 10.9 Hz), 13.60
General Procedure for the Synthesis of Phosphonium Salts 4b and
4c: Bromoacetophenone (1.57 g, 7.9 mmol) was dissolved in dry
acetonitrile (8 mL), and phosphine 5–7 (7.52 mmol) was added.
The mixture was stirred for 30 min, then the precipitate was col-
lected by filtration, washed with acetonitrile (3ϫ 5 mL) and diethyl
ether (5 mL), and dried at room temperature.
(d, J = 10.9 Hz) ppm. IR: ν = 1470, 1280, 1160, 1040, 700–
˜
780 cm–1. C22H25F3O7P2S (552.44): calcd. C 47.83, H 4.56, S 5.80;
found C 48.13, H 4.62, S 5.70.
(5-Methylfuran-2-yl)(2-oxo-2-phenylethyl)diphenylphosphonium
Bromide (9c, X = Br): White solid (2.62 g, 76%), m.p. 245 °C. H
1
NMR (400 MHz, CDCl3): δ = 2.37 (s, 3 H), 6.23 (d, J = 12.7 Hz,
General Procedure for Preparation of Phosphonium Ylides 12–13: A
2 H), 6.35 (br. s, 1 H), 7.46–7.49 (m, 2 H), 7.56–7.66 (m, 5 H), solution of sodium methylate (118 mg, 2.2 mmol) in dry methanol
7.71–7.75 (m, 2 H), 7.87 (br. s, 1 H), 7.97 (dd, J = 14.2, J = 7.3 Hz, (1 mL) was added gradually to a solution of phosphonium salt 8–
4 H), 8.35–8.36 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 10 (2.15 mmol) in dry methanol (5 mL), at 0–5 °C. The mixture
14.2, 38.3 (d, J = 64.9 Hz), 109.7 (d, J = 8.4 Hz), 118.0 (d, J =
94.7 Hz), 128.8, 129.9 (d, J = 13.7 Hz), 129.9, 130.9 (d, J =
was stirred for 1 h, then it was concentrated in vacuo, and the resi-
due was dissolved in dichloromethane (10 mL). The precipitate of
132.8 Hz), 132.4 (d, J = 19.8 Hz), 133.8 (d, J = 11.4 Hz), 134.76, sodium bromide was separated from the solution of ylides by fil-
134.79, 134.9 (d, J = 5.3 Hz), 163.7 (d, J = 7.6 Hz), 191.8 (d, J = tration, and the precipitate was washed on the filter with dichloro-
6.1 Hz) ppm. 31P NMR (161 MHz, CDCl ): δ = 8.81 ppm. IR: ν = methane (3ϫ 10 mL). The combined filtrate and washings were
˜
3
1662, 1470, 728–755 cm–1. C25H22BrO2P (465.33): calcd. C 64.53,
concentrated in vacuo. Ylides 11e, 12c, 12d, and 13c were then used
H 4.77; found C 64.50, H 4.96.
without further purification.
Eur. J. Org. Chem. 2015, 7324–7333
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7329

E. D. Matveeva et al.
FULL PAPER
1-[(5-Methylfuran-2-yl)diphenylphosphonio]-2-oxo-2-phenylethanide
(12c): Colourless oil (0.72 g, 94%). H NMR (400 MHz, CD2Cl2):
31P NMR (161 MHz, CD CN): δ = 13.45 ppm. IR: ν = 1685, 1470,
˜
3
1040–1100, 745 cm–1. C31H25BF4IO2P (674.22): calcd. C 55.22, H
1
δ = 2.38 (s, 3 H), 4.44 (br. s, 1 H), 6.23 (br. s, 1 H), 7.10 (br. s, 1
H), 7.35–7.40 (m, 3 H), 7.49–7.53 (m, 4 H), 7.59–7.63 (m, 2 H),
7.81 (dd, J = 13.4, J = 7.6 Hz, 4 H), 7.93–7.94 (m, 2 H) ppm. 31P
NMR (161 MHz, CD2Cl2): δ = 2.31 ppm.
3.74; found C 55.39, H 3.99.
(Methoxycarbonyl)[(5-methylfuran-2-yl)diphenylphosphonio](phenyl-
iodonio)methanide Tetrafluoroborate (15d): White solid (1.54 g,
82%), m.p. 174 °C. 1H NMR (400 MHz, CD3CN): δ = 2.36 (s, 3
H), 3.55 (br. s, 3 H), 6.36 (m, 1 H), 6.97–6.98 (m, 1 H), 7.47–7.51
(m, 2 H), 7.57–7.68 (m, 11 H), 7.76–7.79 (m, 2 H) ppm. 13C NMR
(100 MHz, CD3CN): δ = 14.46, 53.5, 110.2 (d, J = 8.7 Hz), 124.3
(d, J = 100.3 Hz), 130.6, 130.9 (d, J = 13.9 Hz), 131.4 (d, J =
19.0 Hz), 132.9, 133.3, 133.9, 134.6 (d, J = 11.7 Hz), 135.5, 137.52
(d, J = 134.6 Hz), 164.4 (d, J = 7.3 Hz), 168.46 (d, J = 14.7 Hz)
Methyl [(5-Methylfuran-2-yl)diphenyl-λ5-phosphoranylidene]acetate
1
(12d): Colourless oil (0.51 g, 70%). H NMR (400 MHz, CD2Cl2):
δ = 2.36 (s, 3 H), 2.45, 2.77 (2d, J = 23.0, J = 23.6 Hz, 1 H), 3.29,
3.51 (two s, 3 H), 6.19–6.20 (m, 1 H), 7.05 (t, J = 2.7 Hz, 1 H),
7.45–7.50 (m, 4 H), 7.54–7.58 (m, 2 H), 7.70–7.75 (m, 4 H) ppm.
31P NMR (161 MHz, CD2Cl2): δ = 2.83, 4.04 ppm.
ppm. 31P NMR (161 MHz, CD CN): δ = 15.76 ppm. IR: ν = 1610,
˜
3
1-[(Furan-3-yl)diphenylphosphonio]-2-oxo-2-phenylethanide (13c):
Colourless oil (0.71 g, 90%). 1H NMR (400 MHz, CD2Cl2): δ =
4.38 (d, J = 18.0 Hz, 1 H), 6.70 (br. s, 1 H), 7.36–7.37 (m, 3 H),
7.49–7.52 (m, 4 H), 7.60–7.63 (m, 3 H), 7.71–7.79 (m, 5 H), 7.90–
7.92 (m, 2 H) ppm. 31P NMR (161 MHz, CD2Cl2): δ = 4.03 ppm.
1470, 1040–1100, 750 cm–1. C26H23BF4IO3P (628.15): calcd. C
49.71, H 3.69; found C 49.88, H 3.93.
1-[(Furan-3-yl)diphenylphosphonio]-2-oxo-2-phenyl-1-(phenyliod-
onio)ethanide Tetrafluoroborate (16c): White solid (1.72 g, 87%),
m.p. 156 °C. 1H NMR (400 MHz, CD3CN): δ = 6.84–6.85 (m, 1
H), 7.44–7.48 (m, 2 H), 7.63–7.76 (m, 13 H), 7.84–7.95 (m, 6 H),
8.14 (br. s, 1 H) ppm. 13C NMR (100 MHz, CD3CN): δ = 114.0
(d, J = 11.0 Hz), 124.3 (d, J = 97.5 Hz), 127.7 (d, J = 98.0 Hz),
128.7, 129.8, 130.9 (d, J = 13.2 Hz), 131.8, 133.0, 133.4, 133.6,
133.7, 134.1, 134.3 (d, J = 11.7 Hz), 147.4 (d, J = 13.9 Hz), 154.4
(d, J = 21.2 Hz), 192.0 ppm. 31P NMR (161 MHz, CD3CN): δ =
Diethyl {[(Furan-2-yl)diphenyl-λ5-phosphoranylidene]methyl} Phos-
phonate (11e): A solution of phosphonium salt 8e (4.00 mmol) in
anhydrous THF (16 mL) was added to a stirred suspension of NaH
(10.0 mmol, washed with hexane) in anhydrous THF (16 mL) at
0 °C under argon. The resulting mixture was stirred at 0 °C for 1 h.
The solvent was then removed in vacuo, and the residue was ex-
tracted with anhydrous CH2Cl2 (20 mL). Concentration of the ex-
tracts gave 11e (0.45 g, 82%) as a colourless oil. Ylide 11e was then
16.01 ppm. IR: ν = 1600, 1475, 1040–1110, 740 cm– 1
.
˜
C30H23BF4IO2P (660.19): calcd. C 54.58, H 3.51; found C 54.60,
H 3.80.
1
used without further purification. H NMR (400 MHz, CD2Cl2): δ
= 1.11 (t, J = 7.0 Hz, 6 H), 3.79–3.86 (m, 4 H), 6.56–6.58 (m, 1
H), 7.45–7.49 (m, 5 H), 7.69–7.76 (m, 6 H), 7.77–7.79 (m, 1 H)
ppm. 31P NMR (161 MHz, CD2Cl2): δ = 7.26 (d, J = 40.1 Hz),
32.88 (d, J = 40.1 Hz) ppm.
General Procedure for the Reaction of Mixed Ylides 14–16 with Alk-
ynes: The alkyne (0.9 mmol) was added to a solution of ylide
(0.3 mmol) in anhydrous dichloromethane (4 mL). The mixture was
irradiated in a quartz flask with a mercury lamp (366 nm) under
argon. The progress of the reaction was monitored by TLC. After
the end of the reaction, the mixture was concentrated in vacuo. The
residue was dissolved in a minimum amount of CH2Cl2, and puri-
fied by chromatography on silica gel. Benzene was used to elute the
residual alkynes and PhI; the phosphininofuran was eluted using
CH2Cl2/MeOH (200:1), polycyclic products were eluted using
CH2Cl2/MeOH (100:1), and phosphonium salts using CH2Cl2/
MeOH (20:1).
General Procedure for the Synthesis of Phosphonium–Iodonium
Ylides 14–16: A solution of diacetoxyiodobenzene (0.87 g, 3 mmol)
in methanol (5 mL) was added to a solution of the appropriate
ylide (3 mmol) in methanol (5 mL) at 0 °C. The mixture was stirred
at 0–5 °C for 1 h, and then an aqueous solution of HBF4 (40%;
3 mmol) was added. The mixture was stirred for 10 min, then di-
ethyl ether (20 mL) was added, and the mixture was stirred for 1 h.
The precipitate was collected by filtration, and washed with diethyl
ether (3ϫ 20 mL).
Phenyl(4,4,7-triphenyl-4λ5-phosphinino[3,2-b]furan-5-yl)methanone
(17c): Yellow oil (28 mg, 20%). H NMR (400 MHz, CDCl3): δ =
1
(Diethoxyphosphoryl)[(furan-2-yl)diphenylphosphonio](phenyl-
iodonio)methanide Tetrafluoroborate (14e): White solid (1.82 g,
6.51 (dd, J = 2.3, J = 2.2 Hz, 1 H), 7.22–7.26 (m, 1 H), 7.42 (d, J
= 34.1 Hz, 1 H), 7.35–7.39 (m, 2 H), 7.42–7.47 (m, 3 H), 7.46 (dd,
J = 2.3, J = 2.2 Hz, 1 H), 7.50–7.57 (m, 8 H), 7.67–7.69 (m, 2 H),
7.86 (dd, J = 13.9, J = 7.6 Hz, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 78.9 (d, J = 103.9 Hz), 91.5 (d, J = 104.7 Hz), 107.0
(d, J = 2.9 Hz), 110.7 (d, J = 7.3 Hz), 125.8, 127.2 (d, J = 98.1 Hz),
127.6, 128.1, 128.3, 128.5 (d, J = 13.2 Hz), 128.7, 129.7, 131.6,
132.9 (d, J = 11.7 Hz), 133.4 (d, J = 8.1 Hz), 138.1, 140.2 (d, J =
8.8 Hz), 141.2 (d, J = 13.2 Hz), 161.4 (d, J = 12.5 Hz), 191.6 (d, J
= 5.9 Hz) ppm. 31P NMR (161 MHz, CDCl3): δ = 2.09 ppm. IR:
1
88%), m.p. 160 °C. H NMR (400 MHz, CD3CN): δ = 1.12 (t, J =
7.0 Hz, 6 H), 3.83–3.91 (m, 4 H), 6.71–6.72 (m, 1 H), 7.11 (dd, J
= 3.4, J = 1.8 Hz, 1 H), 7.44 (m, 2 H), 7.55–7.78 (m, 13 H), 8.03
(m, 1 H) ppm. 13C NMR (CD3CN): δ = 16.43 (d, J = 6.6 Hz),
63.12 (d, J = 6.6 Hz), 112.76 (d, J = 8.8 Hz), 117.45, 123.95 (d, J
= 98.1 Hz), 129.24 (d, J = 19.8 Hz), 129.95 (d, arom., J = 13.9 Hz),
131.77, 132.78, 133.74, 134.1 (d, J = 11.0 Hz), 134.83, 140.54 (d, J
= 132.4 Hz), 152.20 (d, J = 7.3 Hz) ppm. 31P NMR (161 MHz,
CD3CN): δ = 18.43 (d, J = 48.0 Hz), 21.67 (d, J = 48.0 Hz) ppm.
IR: ν = 1470, 1210, 1030–1080, 750 cm–1. HRMS: calcd. for
ν = 1520–1590, 1470, 710–740 cm–1. HRMS: calcd. for C H O P
˜
˜
32 23
2
C27H28IO4P2 [M]+ 605.0502; found 605.0486.
[M]+ 470.1436; found 470.1418.
1-[(5-Methylfuran-2-yl)diphenylphosphonio]-2-oxo-2-phenyl-1-(phen-
yliodonio)ethanide Tetrafluoroborate (15c): White solid (1.92 g,
95%), m.p. 152 °C. 1H NMR (400 MHz, CD3CN): δ = 2.32 (s, 3
H), 6.31 (br. s, 1 H), 6.86 (br. s, 1 H), 7.35–7.48 (m, 9 H), 7.54–
Methyl 4,4,7-Triphenyl-4λ5-phosphinino[3,2-b]furan-5-carboxylate
(17d): Yellow oil (26 mg, 20%). H NMR (400 MHz, CD2Cl2): δ =
1
3.59 (br. s, 3 H), 6.50 (dd, J = 2.3, J = 2.3 Hz, 1 H), 7.20 (tt, J =
7.5, J = 1.3 Hz, 1 H), 7.34–7.39 (m, 2 H), 7.43 (dd, J = 2.4, J =
7.63 (m, 5 H), 7.65–7.76 (m, 6 H) ppm. 13C NMR (100 MHz, 2.3 Hz, 1 H), 7.49–7.61 (m, 8 H), 7.59 (d, J = 34.7 Hz, 1 H), 7.69
CD3CN): δ = 14.4, 110.3 (d, J = 8.8 Hz), 123.5 (d, J = 98.8 Hz), (dd, J = 6.5, J = 12.9 Hz, 4 H) ppm. 13C NMR (CD2Cl2): δ = 50.9,
128.7, 129.7, 130.8 (d, J = 13.9 Hz), 131.6 (d, J = 19.0 Hz), 131.8,
133.0, 133.4, 133.7, 134.6 (d, J = 11.0 Hz), 135.4, 137.3 (d, J =
89.4 (d, J = 110.0 Hz), 105.4 (br. s.), 110.8 (d, J = 8.1 Hz), 125.9,
128.0, 128.7, 129.1 (d, J = 13.0 Hz), 130.2 (d, J = 98.5 Hz), 132.3
132.5 Hz), 140.1 (d, J = 6.6 Hz), 164.4 (d, J = 7.3 Hz), 192.4 ppm. (d, J = 3.1 Hz), 133.2 (d, J = 11.7 Hz), 134.3, 139.0, 141.6 (d, J =
7330
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© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 7324–7333

Furyl-Substituted Mixed Phosphonium–Iodonium Ylides
13.9 Hz), 162.6 (d, J = 13.5 Hz), 169.1 ppm. 31P NMR (161 MHz, [6-Benzoyl-3-(5-benzoyl-4,4,7-triphenyl-4λ5-phosphinino[3,2-b]furan-
CD Cl ): δ = 4.50 ppm. IR: ν = 1643, 1439, 694–760 cm–1. HRMS:
2-yl)-1,1,4-triphenyl-1λ5-phosphinin-2-yl]acetaldehyde (19c): Brown
oil (29 mg, 10%). 1H NMR (400 MHz, CDCl3): δ = 3.22 (d, J =
14.3 Hz, 2 H), 6.07 (d, J = 2.4 Hz, 1 H), 7.03–7.22 (m, 8 H), 7.34–
7.54 (m, 22 H), 7.61–7.70 (m, 8 H), 7.81–7.87 (m, 4 H), 8.75 (s, 1
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 45.1 (d, J = 5.0 Hz),
66.7 (d, J = 131.2 Hz), 73.7 (d, J = 127.8 Hz), 91.9 (d, J =
102.6 Hz), 93.6 (d, J = 94.2 Hz), 109.0 (d, J = 12.2 Hz), 113.6 (d,
J = 6.9 Hz), 115.8 (d, J = 8.4 Hz), 124.6, 125.3, 125.6, 125.7, 127.1
(d, J = 100.7 Hz), 127.57, 127.63, 127.7, 127.9, 128.0, 128.1, 128.4
(d, J = 5.3 Hz), 128.5 (d, J = 5.3 Hz), 128.7, 128.85, 128.93 (d, J
= 93.1 Hz), 129.7, 130.2, 131.5 (d, J = 3.8 Hz), 131.9 (d, J =
3.4 Hz), 132.8 (d, J = 12.2 Hz), 133.4 (d, J = 10.7 Hz), 138.7, 138.8
(d, J = 1.5 Hz), 139.5 (d, J = 4.2 Hz), 143.4, 146.5 (d, J = 8.4 Hz),
154.0 (d, J = 6.1 Hz), 159.4 (d, J = 16.4 Hz), 191.7, 192.5 (d, J =
2.3 Hz), 198.0 (d, J = 2.3 Hz) ppm. 31P NMR (161 MHz, CDCl3):
˜
2
2
calcd. for C27H21O3P [M]+ 424.1223; found 424.1219.
Diethyl (4,4,7-Triphenyl-4λ5-phosphinino[3,2-b]furan-5-yl) Phos-
phonate (17e): Yellow oil (23 mg, 15 %). 1H NMR (400 MHz,
CD2Cl2): δ = 1.10 (td, J = 7.1, J = 0.4 Hz, 6 H), 3.69–3.79 (m, 4
H), 6.44 (t, J = 2.3 Hz, 1 H), 7.15 (dd, J = 37.3, J = 18.2 Hz, 1 H),
7.15–7.19 (m, 1 H, arom.), 7.31–7.35 (m, 2 H, arom.), 7.41 (t, J =
2.5 Hz, 1 H), 7.48–7.55 (m, 8 H), 7.73–7.79 (m, 4 H) ppm. 13C
NMR (100 MHz, CD2Cl2): δ = 16.6 (d, J = 7.2 Hz), 48.9 (dd, J =
204.4, J = 102.2 Hz), 61.3 (d, J = 5.8 Hz), 87.6 (dd, J = 111.6, J =
12.2 Hz), 105.2 (dd, J = 15.1, J = 5.8 Hz), 110.4 (dd, J = 8.6, J =
3.6 Hz), 125.7, 127.7, 128.7, 128.9 (d, J = 12.3 Hz), 131.4 (dd, J =
95.0, J = 2.2 Hz), 132.2 (d, J = 2.9 Hz), 133.3 (d, J = 11.5 Hz),
136.7 (d, J = 2.9 Hz), 139.0, 141.3 (d, J = 14.4 Hz), 162.2 (d, J =
11.5 Hz) ppm. 31P NMR (161 MHz, CD2Cl2): δ = 8.66 (d, J =
δ = 0.95, 8.91 ppm. IR: ν = 1720, 1581, 1438, 694–742 cm–1
.
˜
55.0 Hz), 25.57 (d, J = 55.0 Hz) ppm. IR: ν = 1581, 1262, 742–
HRMS: calcd. for C64H46O4P2 [M]+ 940.2866; found 940.2840.
˜
800 cm–1. HRMS: calcd. for C29H28O4P2 [M]+ 502.1463; found
502.1457.
Methyl 2-[6-(Methoxycarbonyl)-4-(4-methoxyphenyl)-2-(2-oxo-
ethyl)-1,1-diphenyl-1λ5-phosphinin-3-yl]-7-(4-methoxyphenyl)-4,4-di-
phenyl-4λ5-phosphinino[3,2-b]furan-5-carboxylate (19d): Brown oil
(33 mg, 12 %). 1H NMR (400 MHz, CDCl3): δ = 3.17 (d, J =
14.5 Hz, 2 H), 3.55 (s, 3 H), 3.59 (br. s, 3 H), 3.78 (s, 3 H), 3.85 (s,
3 H), 6.01 (d, J = 2.5 Hz, 1 H), 6.74 (d, J = 8.7 Hz), 6.88 (d, J =
8.7 Hz, 2 H), 7.01 (d, J = 8.7 Hz, 2 H), 7.22 (d, J = 8.7 Hz, 2 H),
7.45–7.49 (m, 5 H), 7.51–7.61 (m, 14 H), 7.66–7.73 (m, 5 H), 8.72
(s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 44.7 (d, J =
8.1 Hz), 50.4, 50.7, 55.1, 55.2, 67.4 (d, J = 150.8 Hz), 81.7 (d, J =
166.9 Hz), 87.5 (d, J = 89.3 Hz), 90.2 (d, J = 106.1 Hz), 100.5 (d,
J = 14.6 Hz), 112.7 (d, J = 5.1 Hz), 113.0, 113.4, 115.3 (d, J =
11.0 Hz), 126.7 (d, J = 92.2 Hz), 128.0, 128.3 (d, J = 15.4 Hz),
128.6 (d, J = 11.7 Hz), 129.6, 130.0 (d, J = 125.9 Hz), 131.5, 131.8,
132.5 (d, J = 11.7 Hz), 133.2 (d, J = 11.7 Hz), 134.7, 136.1, 138.2
(d, J = 7.3 Hz), 140.6, 144.4 (d, J = 9.5 Hz), 149.0 (d, J = 14.6 Hz),
157.1, 157.5, 161.1 (d, J = 11.0 Hz), 167.6, 168.0, 198.5 ppm. 31P
[7-(4-Methoxyphenyl)-4,4-diphenyl-4λ5-phosphinino[3,2-b]furan-5-yl-
](phenyl)methanone (18c): Brown solid (23 mg, 15%). m.p. 201 °C.
1H NMR (400 MHz, CDCl3): δ = 3.83 (s, 3 H), 6.46 (br. s, 1 H),
6.91 (d, J = 8.7 Hz, 2 H), 7.36–7.52 (m, 13 H), 7.65–7.66 (m, 2 H),
7.84 (dd, J = 14.1, J = 6.8 Hz, 4 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 55.2, 78.5 (d, J = 104.1 Hz), 91.5 (d, J = 103.8 Hz),
106.7 (d, J = 4.6 Hz), 110.6 (d, J = 6.9 Hz), 113.7, 127.3 (d, J =
98.0 Hz), 128.0, 128.3, 128.5 (d, J = 8.4 Hz), 128.7, 129.6, 130.2,
130.7 (d, J = 1.1 Hz), 131.5 (d, J = 3.1 Hz), 132.3 (d, J = 8.4 Hz),
132.8 (d, J = 11.8 Hz), 141.1 (d, J = 13.4 Hz), 157.9, 161.5 (d, J =
12.6 Hz), 191.2 (d, J = 6.1 Hz) ppm. 31P NMR (161 MHz, CDCl3):
δ = 1.62 ppm. IR: ν = 1671, 1467, 694–725 cm–1. HRMS: calcd.
˜
for C33H25O3P [M]+ 500.1536; found 500.1529.
Methyl 7-(4-Methoxyphenyl)-4,4-diphenyl-4λ5-phosphinino[3,2-b]-
furan-5-carboxylate (18d): Yellow oil (27 mg, 20 %). 1H NMR
(400 MHz, CD2Cl2): δ = 3.58 (br. s), 3.82 (s), 6.49 (dd, J = 2.2, J
= 2.2 Hz, 1 H), 6.91 (d, J = 8.7 Hz, 2 H), 7.42 (dd, J = 2.5, J =
2.5 Hz, 1 H), 7.50 (d, J = 8.7 Hz, 2 H), 7.49–7.56 (m, 6 H), 7.57
(d, J = 32.2 Hz, 1 H), 7.68 (dd, J = 13.4, J = 7.2 Hz, 4 H) ppm.
13C NMR (100 MHz, CD2Cl2): δ = 50.9, 55.8, 89.4 (d, J =
118.5 Hz), 105.2, 110.8 (d, J = 7.6 Hz), 114.1, 129.0 (d, J =
13.5 Hz), 129.2, 131.5, 132.2 (d, J = 2.7 Hz), 133.2 (d, J = 11.2 Hz),
133.2, 141.6 (d, J = 13.9 Hz), 158.4, 162.8 (d, J = 13.5 Hz),
NMR (161 MHz, CDCl ): δ = 3.79, 11.51 ppm. IR: ν = 1722, 1673,
˜
3
1438, 694–744 cm–1. HRMS: calcd. for C56H46O8P2 [M]+ 908.2662;
found 908.2648.
Diethyl 2-{6-[Ethoxy(propyl)phosphoryl]-2-(2-oxoethyl)-1,1,4-tri-
phenyl-1λ5-phosphinin-3-yl}-4,4,7-triphenyl-4λ5-phosphinino[3,2-b]-
furan-5-yl Phosphonate (19e): Brown oil (90 mg, 30%). 1H NMR
(400 MHz, CDCl3): δ = 1.04 (t, J = 7.0 Hz, 6 H), 1.09 (t, J =
7.0 Hz, 6 H), 3.13 (d, J = 14.9 Hz, 2 H), 3.64–3.78 (m, 8 H), 5.88
(d, J = 2.4 Hz, 1 H), 7.02–7.05 (m, 3 H), 7.07–7.13 (m, 4 H), 7.21–
7.29 (m, 6 H), 7.34–7.51 (m, 6 H), 7.55–7.61 (m, 5 H), 7.72–7.78
(m, 5 H), 8.73 (t, J = 1.6 Hz, 1 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 16.1 (d, J = 7.2 Hz), 16.2 (d, J = 7.2 Hz), 44.6 (dd, J
= 9.4, J = 2.9 Hz), 49.0 (dd, J = 201.5, J = 101.5 Hz), 57.1 (dd, J
169.06 ppm. 31P NMR (161 MHz, CD Cl ): δ = 4.47 ppm. IR: ν
˜
2
2
= 1645, 1450, 730–800 cm–1. HRMS: calcd. for C28H23O4P [M]+
454.1328; found 454.1324.
Diethyl [7-(4-Methoxyphenyl)-4,4-diphenyl-4λ5-phosphinino[3,2-b]-
furan-5-yl] Phosphonate (18e): Yellow oil (19 mg, 12%). 1H NMR
(400 MHz, CD2Cl2): δ = 1.11 (t, J = 7.0 Hz, 6 H), 3.70–3.78 (m, 4 = 200.1, J = 94.3 Hz), 60.8 (d, J = 5.1 Hz), 61.0 (d, J = 5.0 Hz),
H), 3.81 (s, 3 H), 6.44 (t, J = 2.2 Hz, 1 H), 6.90 (d, J = 8.8 Hz, 2 83.6 (dd, J = 90.7, J = 7.9 Hz), 88.20 (dd, J = 110.1, J = 11.5 Hz),
H), 7.05 (dd, J = 37.3, J = 18.0 Hz, 1 H), 7.41 (t, J = 2.5 Hz, 1 H), 104.45 (dd, J = 15.1, J = 5.8 Hz, arom.), 112.7 (dd, J = 7.9, J =
7.45 (d, J = 8.8 Hz, 2 H), 7.49–7.55 (m, 6 H), 7.73–7.79 (m, 4 H) 3.6 Hz), 115.7 (dd, J = 14.4, J = 14.3 Hz), 124.8, 125.0, 127.2,
ppm. 13C NMR (100 MHz, CD2Cl2): δ = 16.6 (d, J = 6.9 Hz), 35.9
(dd, J = 206.0, J = 110.6 Hz), 55.8, 61.3 (d, J = 5.3 Hz), 88.5 (d, J
= 98.4 Hz), 92.9 (d, J = 16.8 Hz), 110.49 (dd, J = 7.6, J = 3.0 Hz),
114.1, 128.9 (d, J = 13.0 Hz), 128.9, 131.6 (dd, J = 94.6, J =
127.6, 128.0, 128.3 (d, J = 13.7 Hz), 128.6 (d, J = 13.0 Hz), 128.7
(dd, J = 100.8, J = 2.2 Hz), 130.5 (dd, J = 95.0, J = 1.4 Hz), 131.4
(d, J = 2.9 Hz), 131.9 (d, J = 3.6 Hz), 132.6 (d, J = 11.5 Hz), 133.4
(d, J = 10.8 Hz), 136.7 (dd, J = 5.0, J = 1.4 Hz), 138.1, 141.2 (d, J
2.9 Hz), 132.1 (d, J = 3.0 Hz), 133.3 (d, J = 11.4 Hz), 135.8 (dd, J = 3.6 Hz), 143.5, 144.1 (dd, J = 7.9, J = 2.2 Hz), 149.1 (dd, J =
= 4.6, J = 1.5 Hz), 138.5, 141.3 (d, J = 14.5 Hz), 158.2, 165.01 (d, 15.1, J = 14.4 Hz), 160.7 (dd, J = 12.2, J = 2.2 Hz), 198.8 (d, J =
J = 6.1 Hz) ppm. 31P NMR (161 MHz, CD2Cl2): δ = 8.6 (d, J =
2.9 Hz) ppm. 31P NMR (161 MHz, CDCl3): δ = 7.90 (d, J =
54.8 Hz), 25.87 (d, J = 54.8 Hz) ppm. IR: ν = 1579, 1242, 692– 55.4 Hz), 14.52 (d, J = 46.0 Hz), 23.55 (d, J = 46.0 Hz), 26.11 (d,
˜
790 cm–1. HRMS: calcd. for C30H30O5P2 [M]+ 532.1568; found J = 55.4 Hz) ppm. IR: ν = 1720, 1572, 1230, 692–777 cm–1. HRMS:
˜
532.1556.
calcd. for C58H56O8P4 [M]+ 1004.2920; found 1004.2904.
Eur. J. Org. Chem. 2015, 7324–7333
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7331

E. D. Matveeva et al.
FULL PAPER
Methyl 2-[6-(Methoxycarbonyl)-2-(2-oxoethyl)-1,1,4-triphenyl-1λ5- ppm. 13C NMR (100 MHz, CDCl3): δ = 32.1 (d, J = 60.7 Hz), 53.4,
phosphinin-3-yl]-4,4,7-triphenyl-4λ5-phosphinino[3,2-b]furan-5-carb- 113.1 (d, J = 9.5 Hz), 116.6 (d, J = 94.4 Hz), 130.12 (d, J =
oxylate (20d): Brown oil (46 mg, 18 %). 1H NMR (400 MHz,
CDCl3): δ = 3.16 (dd, J = 14.4, J = 1.1 Hz, 2 H), 3.53 (s, 3 H),
13.9 Hz), 131.13 (d, J = 19.8 Hz), 132.7 (d, J = 132.5 Hz), 133.7
(d, J = 11.7 Hz), 152.8 (d, J = 7.3 Hz), 164.5 ppm. 31P NMR
3.56 (br. s., 3 H), 6.03 (d, J = 2.6 Hz, 1 H), 7.10 (t, J = 5.1 Hz, 2 (161 MHz, CDCl ): δ = 8.74 ppm. IR: ν = 1670, 1480, 1030–1100,
˜
3
H), 7.16–7.22 (m, 4 H), 7.27–7.31 (m, 2 H), 7.43–7.72 (m, 23 H),
8.71 (s, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 44.8 (d, J =
8.8 Hz), 50.6, 50.8, 67.5 (d, J = 154.4 Hz), 81.1 (d, J = 156.6 Hz),
87.7 (d, J = 120.0 Hz), 90.8 (d, J = 98.1 Hz), 105.0 (d, J = 6.6 Hz),
112.9 (d, J = 6.6 Hz), 115.8 (d, J = 8.8 Hz), 125.0, 125.3, 126.7 (d,
J = 91.5 Hz), 127.5, 127.6, 128.0, 128.4 (d, J = 13.2 Hz), 128.6,
128.7 (d, J = 13.1 Hz), 130.0 (d, J = 96.6 Hz), 131.5, 131.9, 132.5
(d, J = 11.7 Hz), 133.3 (d, J = 11.0 Hz), 134.6 (d, J = 2.9 Hz),
137.9, 138.7 (d, J = 4.4 Hz), 143.5, 145.1 (d, J = 8.1 Hz), 149.2 (d,
J = 11.7 Hz), 161.1 (d, J = 18.3 Hz), 167.9, 168.0, 198.5 ppm. 31P
700–790 cm–1.
[(Diethoxyphosphoryl)methyl](furan-2-yl)diphenylphosphonium
Tetrafluoroborate (22e): Yellow oil (for yield, see Scheme 4). H
1
NMR (400 MHz, CDCl3): δ = 1.13 (t, J = 7.0 Hz, 6 H), 3.96–4.08
(m, 4 H), 4.15 (dd, J = 19.5, J = 16.5 Hz, 2 H), 6.77–6.79 (m, 1
H), 7.65–7.70 (m, 4 H), 7.73–7.74 (m, 1 H), 7.78–7.88 (m, 6 H),
8.00 (m, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 15.7 (d, J
= 6.6 Hz), 20.8 (dd, J = 134.7, J = 54.2 Hz), 63.5 (d, J = 6.6 Hz),
112.9 (d, J = 9.6 Hz), 116.9 (d, J = 93.7 Hz), 129.9 (d, J = 13.9 Hz),
130.8 (d, J = 20.5 Hz), 131.5 (d, J = 95.9 Hz), 133.6 (d, J =
11.7 Hz), 135.4, 152.9 (d, J = 8.1 Hz) ppm. 31P NMR (161 MHz,
CDCl3): δ = 8.71 (d, J = 10.9 Hz), 13.60 (d, J = 10.9 Hz) ppm. IR:
NMR (161 MHz, CDCl ): δ = 3.79, 11.51 ppm. IR: ν = 1720, 1648,
˜
3
1434, 696–748 cm–1. HRMS: calcd. for C54H42O6P2 [M]+ 848.2451;
found 848.2440.
ν = 1470, 1280, 1040–1100, 700–780 cm–1.
˜
(2-Methyl-4,4,7-triphenyl-4λ5-phosphinino[3,2-b]furan-5-yl)(phenyl)-
methanone (26c): Yellow oil (22 mg, 15%). 1H NMR (400 MHz,
CDCl3): δ = 2.32 (s, 3 H), 6.07 (br. s, 1 H, HC), 7.20 (t, J = 7.4 Hz,
1 H), 7.31–7.40 (m, 6 H), 7.46–7.54 (m, 8 H), 7.64–7.65 (m, 2 H),
7.83 (dd, J = 13.8, J = 7.7 Hz, 4 H, HB) ppm. 13C NMR (100 MHz,
CDCl3): δ = 13.7, 78.7 (d, J = 104.1 Hz), 92.1 (d, J = 104.0 Hz),
106.2 (d, J = 6.1 Hz), 107.1 (d, J = 3.5 Hz), 125.6, 127.4 (d, J =
98.0 Hz), 127.6, 128.0, 128.2, 128.32, 128.34, 128.5 (d, J = 14.7 Hz),
129.6, 130.9, 131.5 (d, J = 3.5 Hz), 132.2 (d, J = 8.7 Hz), 132.9 (d,
J = 11.3 Hz), 140.3 (d, J = 9.5 Hz), 151.5 (d, J = 13.9 Hz), 191.4
(d, J = 5.2 Hz) ppm. 31P NMR (161 MHz, CDCl3): δ = 1.06 ppm.
Diethyl 5-[5-(Diethoxyphosphoryl)-7-(4-methoxyphenyl)-4,4-di-
phenyl-4λ5-phosphinino[3,2-b]furan-2-yl]-4-(4-methoxyphenyl)-6-(2-
oxoethyl)-1,1-diphenyl-1λ5-phosphinin-2-yl Phosphonate (20e):
Brown oil (80 mg, 25%). 1H NMR (400 MHz, CDCl3): δ = 1.06 (t,
J = 7.0 Hz, 6 H), 1.10 (t, J = 7.0 Hz, 6 H), 3.13 (d, J = 14.5 Hz, 2
H), 3.65–3.78 (m, 8 H), 3.75 (s, 3 H), 3.82 (s, 3 H), 5.95 (d, J =
2.4 Hz, 1 H), 6.71 (d, J = 8.7 Hz, 2 H), 6.85 (d, J = 8.6 Hz, 2 H),
6.96 (dd, J = 37.2, J = 18.4 Hz, 1 H), 6.96 (d, J = 8.7 Hz, 2 H),
7.15 (dd, J = 32.3, J = 19.1 Hz, 1 H), 7.15 (d, J = 8.7 Hz, 2 H),
7.44–7.62 (m, 16 H), 7.73–7.78 (m, 4 H), 8.72 (br. s, 1 H) ppm. 13
C
NMR (100 MHz, CDCl3): δ = 15.9 (d, J = 7.6 Hz), 16.0 (d, J =
7.6 Hz), 44.5 (dd, J = 8.4, J = 2.6 Hz), 48.2 (dd, J = 200.7, J =
102.2 Hz), 55.0, 55.2, 57.7 (dd, J = 198.0, J = 87.2 Hz), 60.7 (d, J
= 4.6 Hz), 60.9 (d, J = 5.3 Hz), 83.6 (dd, J = 90.8, J = 8.4 Hz),
88.1 (dd, J = 107.6, J = 11.5 Hz), 104.0 (dd, J = 15.3, J = 3.1 Hz),
112.6 (dd, J = 7.6, J = 2.6 Hz), 113.1, 113.4, 115.2 (dd, J = 13.7,
J = 14.5 Hz), 128.2 (d, J = 13.0 Hz), 128.3, 128.5 (d, J = 13.0 Hz),
129.5, 131.3 (dd, J = 110.6, J = 1.6 Hz), 130.8 (dd, J = 94.6, J =
2.3 Hz), 131.4 (d, J = 3.0 Hz), 131.8 (d, J = 3.0 Hz), 132.5 (d, J =
11.4 Hz), 133.4 (d, J = 11.4 Hz), 135.6 (dd, J = 4.6, J = 2.3 Hz),
136.2, 140.6 (d, J = 3.8 Hz), 140.6, 143.5, 144.0 (d, J = 6.9 Hz),
149.3 (dd, J = 15.3, J = 15.2 Hz), 157.2, 157.5, 160.7 (d, J =
10.7 Hz), 198.3 (d, J = 3.0 Hz) ppm. 31P NMR (161 MHz, CDCl3):
δ = 7.74 (d, J = 55.4 Hz), 14.42 (d, J = 46.2 Hz), 23.05 (d, J =
IR: ν = 1670, 1434, 700–740 cm–1. HRMS: calcd. for C H O P
˜
33 25
2
[M]+ 484.1587; found 484.1576.
Methyl 2-Methyl-4,4,7-triphenyl-4λ5-phosphinino[3,2-b]furan-5-
carboxylate (26d): Yellow oil (22 mg, 17%). 1H NMR (400 MHz,
CDCl3): δ = 2.32 (s, 3 H), 3.64 (br. s, 3 H), 6.06 (br. s, 1 H), 7.21–
7.23 (m, 1 H), 7.38 (t, J = 6.7 Hz, 2 H), 7.48–7.55 (m, 6 H), 7.64–
7.75 (m, 7 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 13.5, 53.3,
74.8 (d, J = 119.3 Hz), 90.6 (d, J = 101.7 Hz), 105.7 (d, J = 5.1 Hz),
108.0 (d, J = 6.6 Hz), 125.1, 127.4, 128.0 (d, J = 98.1 Hz), 128.1,
128.2, 128.4 (d, J = 12.4 Hz), 131.4, 132.4 (d, J = 8.8 Hz), 132.6
(d, J = 11.7 Hz), 138.8 (d, J = 8.8 Hz), 151.1 (d, J = 13.9 Hz),
168.0 ppm. 31P NMR (161 MHz, CDCl ): δ = 3.63 ppm. IR: ν =
˜
3
1695, 1441, 690–760 cm–1. HRMS: calcd. for C28H23O3P [M]+
46.2 Hz), 25.74 (d, J = 55.4 Hz) ppm. IR: ν = 1718, 1572, 1242,
˜
438.1384; found 438.1379.
692–833 cm–1. HRMS: calcd. for C60H60O10P4 [M]+ 1064.3131;
found 1064.3111.
[1-(Furan-3-yl)-1,4-diphenyl-1λ5-phosphinolin-2-yl](phenyl)methan-
1
one (27): Brown oil (15 mg, 10%). H NMR (400 MHz, CDCl3): δ
(Furan-2-yl)(2-oxo-2-phenylethyl)diphenylphosphonium Tetrafluoro-
borate (22c): Yellow oil (for yield, see Scheme 4). 1H NMR
(400 MHz, CDCl3): δ = 6.39 (d, J = 12.4 Hz, 2 H), 6.77–6.79 (m),
7.51 (t, J = 7.4 Hz, 2 H), 7.60–7.68 (m, 5 H), 7.74–7.79 (m, 2 H),
7.92 (m, 1 H), 7.96–8.02 (m, 4 H), 8.14 (dd, J = 3.8, J = 1.0 Hz, 1
H), 8.39 (d, J = 7.3 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 38.5 (d, J = 65.1 Hz), 113.1 (d, J = 8.8 Hz), 117.6 (d, J =
94.4 Hz), 129.0, 130.0, 130.1 (d, J = 13.9 Hz), 130.8 (d, J =
19.8 Hz), 133.7 (d, J = 130.3 Hz), 133.9 (d, J = 11.7 Hz), 134.9,
135.0 (d, J = 1.5 Hz), 152.3 (d, J = 8.1 Hz), 191.8 (d, J = 5.9 Hz)
= 3.84 (s, 3 H), 6.83 (t, J = 2.3 Hz, 1 H), 6.92 (d, J = 8.6 Hz, 2 H),
7.12 (d, J = 33.4 Hz, 2 H), 7.27 (d, J = 8.6 Hz, 2 H), 7.35–7.39 (m,
5 H), 7.47–7.53 (m, 5 H), 7.57–7.58 (m, 1 H), 7.66 (dd, J = 7.1, J
= 3.5 Hz, 1 H), 7.82–7.88 (m, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 55.3, 73.8 (d, J = 116.4 Hz), 97.0 (d, J = 97.3 Hz),
106.1 (d, J = 8.8 Hz), 107.2 (d, J = 13.9 Hz), 110.2 (d, J = 92.9 Hz),
122.6, 124.6 (d, J = 11.7 Hz), 126.0 (d, J = 8.1 Hz), 127.0, 128.0
(d, J = 114.9 Hz), 128.1, 128.4, 128.8, 129.9, 132.2 (d, J = 22.0 Hz),
132.3 (d, J = 7.3 Hz), 133.1 (d, J = 12.4 Hz), 133.2 (d, J = 8.05 Hz),
134.0 (d, J = 5.9 Hz), 140.1 (d, J = 6.6 Hz), 140.9, 143.4 (d, J
= 13.2 Hz), 152.8 (d, J = 13.9 Hz), 159.9, 190.0 ppm. 31P NMR
ppm. 31P NMR (161 MHz, CDCl ): δ = 9.87 ppm. IR: ν = 1660,
˜
3
1470, 1035–1105, 730–760 cm–1.
(161 MHz, CDCl ): δ = –9.35 ppm. IR: ν = 1658, 1482, 692–
˜
3
731 cm–1. HRMS: calcd. for C33H25O3P [M]+ 500.1536; found
(Furan-2-yl)(2-methoxy-2-oxoethyl)diphenylphosphonium Tetra-
fluoroborate (22d): Yellow oil (for yield, see Scheme 4). 1H NMR
(400 MHz, CDCl3): δ = 3.65 (s, 3 H), 5.51 (d, J = 13.9 Hz, 2 H),
6.81 (ddd, J = 3.8, J = 3.1 Hz, J = 1.8 Hz, 1 H), 7.66–7.71 (m, 4
500.1534.
(Furan-3-yl)[5-(4-methoxyphenyl)-2-phenylfuran-3-yl]diphenylphos-
phonium Tetrafluoroborate (28): Colourless oil (38 mg, 25%). 1H
H), 7.79–7.85 (m, 3 H), 7.93–7.99 (m, 4 H), 8.06–8.07 (m, 1 H) NMR (400 MHz, CDCl3): δ = 3.84 (s, 3 H), 6.59 (d, J = 4.2 Hz, 1
7332
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© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2015, 7324–7333

Furyl-Substituted Mixed Phosphonium–Iodonium Ylides
H), 6.76–6.77 (m, 1 H), 6.96 (d, J = 9.0 Hz, 2 H), 7.15 (t, J =
1.263 g/cm3]. Absorption correction by crystal shape was applied
7.5 Hz, 2 H), 7.21–7.23 (m, 2 H), 7.26–7.30 (m, 1 H), 7.66–7.76 (m, to the set of experimental data. The structure was solved by direct
12 H), 7.78–7.82 (m, 3 H), 7.88–7.89 (m, 1 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 55.4, 98.6 (d, J = 113.4 Hz), 103.2, 107.6
methods (SIR2002 program package),[11] then refined with iso-
tropic and anisotropic approximations of atomic displacement pa-
(d, J = 12.4 Hz), 111.8 (d, J = 11.0 Hz), 114.6, 117.9 (d, J = rameters (ADP) successively for all non-hydrogen atoms by the
95.9 Hz), 120.69, 126.87 (d, J = 114.9 Hz), 126.4, 128.2, 128.6,
JANA2000 program package (Table 3).[12] CCDC-1062276 con-
130.6, 130.8 (d, J = 13.90 Hz), 133.4 (d, J = 11.7 Hz), 135.8, 147.7 tains the supplementary crystallographic data for this paper. These
(d, J = 13.9 Hz), 153.6 (d, J = 22.7 Hz), 156.7 (d, J = 14.6 Hz),
data can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.cam.ac.uk/data_request/cif
160.7, 161.3 (d, J = 9.5 Hz) ppm. 31P NMR (161 MHz, CDCl3): δ
= 3.64 ppm. IR: ν = 1438, 1024–1101, 692–750 cm–1. HRMS:
˜
calcd. for C33H26O3P [M]+ 501.1614; found 501.1612.
Acknowledgments
(Furan-3-yl)(2-oxo-2-phenylethyl)diphenylphosphonium Tetrafluoro
borate (29): Yellow oil (48 mg, 35%). 1H NMR (400 MHz, CDCl3):
δ = 6.29 (d, J = 12.1 Hz, 2 H), 6.88–6.89 (m, 1 H), 7.48 (t, J =
7.8 Hz, 2 H), 7.58–7.68 (m, 5 H), 7.73–7.78 (m, 3 H), 7.96 (dd, J
= 14.1, J = 7.3 Hz, 4 H), 8.27 (br. s, 1 H), 8.36 (d, J = 7.3 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 9.5 (d, J = 65.1 Hz,
CH2), 112.8 (d, J = 10.3 Hz), 118.7 (d, J = 93.7 Hz), 126.8 (d, J =
136.9 Hz), 128.9, 129.9, 130.1 (d, J = 13.2 Hz), 133.3 (d, J =
11.0 Hz), 134.7, 134.77, 134.84, 146.2 (d, J = 13.9 Hz), 154.2 (d, J
= 22.0 Hz), 192.3 (d, J = 5.9 Hz) ppm. 31P NMR (CDCl3): δ =
We thank the Russian Foundation of Basic Research (Project 11-
03-00795), the Grant of the President of the Russian Federation
(NSh-5130.2014.3), and the Division of Chemistry and Materials
Science of the Russian Academy of Sciences (OKhNM-1 and
OKhNM-9) for financial support.
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12.06 ppm. IR: ν = 1658, 1472, 1024–1100, 720–745 cm–1.
˜
X-ray Diffraction Analysis of 18c: Crystallographic data were col-
lected with an Enraf–Nonius CAD-4 diffractometer at 293 K (Cu-
Kα radiation, λ = 1.54178 Å). Cell parameters were determined
from a set of 23 reflections [P21/c; a = 12.261(7) Å, b = 12.123(5) Å,
c = 17.787(5) Å, β = 95.65(3)°, V = 2631(2) Å3, Z = 4, Dcalcd.
=
Table 3. Crystal data and details of the refinement procedure for
18c.
Empirical formula
Molecular mass
Crystal system
Space group
a [Å]
b [Å]
C33H25O3P
500.5
monoclinic
P21/c
12.261(7)
12.123(5)
17.787(5)
95.65(3)
c [Å]
β [°]
V [Å3]
2631(2)
Z
4
Dcalcd. [gcm–3]
Radiation, wavelenghth [Å]
Temperature [K]
Crystal shape
Crystal size [mm]
Diffractometer
Data collection method
Absorption correction
No. of measured reflections
1.263
Cu-Kα, 1.54178
293
prism
0.22ϫ0.13ϫ0.15
CAD-4
ω scan
analytical (crystal shape)
5580
No. of observed independent reflec- 2147
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[12] V. Petricek, M. Dusek, L. Platinus, Structure Determination
Software Programs, Institute of Physics, Prague, Czech Repub-
lic, 2000.
tions [I Ͼ 3(I)]
θ limits [°]
4.42–60.0
Range of h, k, l
0ՅhՅ12, –4ՅkՅ13,
–19ՅlՅ19
Rint
0.058
0.043/0.056
R/Rw [I Ͼ 3(I)]
Goodness of fit
1.26
407
No. of refined parameters
Weighting scheme
Positive/negative Δrmax [eÅ–3]
w = [σ2(F) + (0.01225F)2]–1
Received: July 7, 2015
Published Online: October 21, 2015
+0.10/–0.12
Eur. J. Org. Chem. 2015, 7324–7333
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
7333