Annelated P-containing heterocycles from aryl- and hetaryl-substituted phosphonium iodonium ylides with a methoxycarbonyl-group

Article abstract of DOI:10.1016/j.tet.2013.06.066

Hetaryl-substituted phosphonium-iodonium ylides with a methoxycarbonyl group as acceptor proved to be highly reactive toward various alkynes in comparison with triphenyl-substituted analogue. We were able to isolate annelated P-containing heterocycles - λ

Full text of DOI:10.1016/j.tet.2013.06.066

Tetrahedron 69 (2013) 7395e7402
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Annelated P-containing heterocycles from aryl- and hetaryl-
substituted phosphonium iodonium ylides with a methoxycarbonyl-
group
,
b
,
a
a
Elena D. Matveeva a , Tatyana A. Podrugina , Marina A. Taranova ,
*
Ekaterina Yu. Melikhova a, Rolf Gleiter c, Nikolay S. Zefirov a
,
b
a Moscow State Lomonosov University, Department of Chemistry, Moscow 119992, Russian Federation
b Institute of Physiology Active Compounds, Russian Academy of Sciences, Chernogolovka 142432, Russian Federation
c Organisch-Chemisches Institut der Universitaet Heidelberg, Im Neuenheimer Feld 270, Heidelberg D-69120, Germany
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 29 April 2013
Received in revised form 3 June 2013
Accepted 17 June 2013
Available online 24 June 2013
Hetaryl-substituted phosphoniumeiodonium ylides with a methoxycarbonyl group as acceptor proved
to be highly reactive toward various alkynes in comparison with triphenyl-substituted analogue. We
were able to isolate annelated P-containing heterocyclesd
l l
5-phosphininothiophenes, 5-phosphinino-
furans,
l
5-phosphinolines, and rare polyaryl-substituted phosphonium salts, which can be traced back to
three different rotamers of an intermediate adduct of the alkyne with the cation generated from the
mixed ylide by removal of iodobenzene.
Keywords:
Ylides
Ó 2013 Elsevier Ltd. All rights reserved.
Vinylcations
Phosphinolines
Phosphinino-heterocycles
1. Introduction
Through the study of the properties of mixed ylides, we have
opened new reactions to synthesize annelated P-containing com-
Phosphorus-containing heterocycles are a less numerous and
less accessible class of compounds in comparison with accessible
nitrogen or sulfur heterocycles.1 However, interest in this class of
compound, especially toward the ones with an endocyclic PeC
bond, has increased due to their recent use in wide variety of areas
as model objects in fundamental research,2 as ligands for new
catalysts,3 for modifying properties of materials4 and as important
building blocks for drug discovery5.
poundsdinteresting but virtually unexplored heterocyclic systems.
Recently we investigated the photochemical heterocyclization
of mixed phosphoniumeiodonium ylides of type 1 with a CC-triple
bond7 (Scheme 1). In this paper we summarize our results with the
methoxycarbonyl group (2 in Scheme 1) as acceptor unit. For the
aryl substituent at the phosphorus atom we used phenyl, furyl or
thienyl rings. It will be shown that there are remarkable differences
in the reaction of 1 and 2 with alkynes.
Until recently l
5-phosphinoline (Fig. 1) dthe structural ana-
logue of quinolinedwas virtually inaccessible. There were only two
known approaches to the synthesis of these heterocycles.6
Fig. 1.
l
5-Phosphinoline is a structural analogue of quinoline.
* Corresponding author. Tel.: þ7 495 939 5247; fax: þ7 495 939 0290; e-mail
Scheme 1. Structural representations of mixed ylides 1 and 2.
address: matveeva@org.chem.msu.ru (E.D. Matveeva).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.06.066

7396
E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
The higher reactivity of 2b, c as compared to 2a allows the
The ylide 2a chemoselectively interacted with alkynes 6e9 with
the formation of
5-phosphinoline 12e15 with yields of 45e75%.
The reaction of 2a with alkynes 10e11 led to two heterocyclic
systemsd
5-phosphinoline 17, 19, and phosphonium substituted
generation of cation 3 (Scheme 2) at room temperature without
irradiation. This in turn allowed us to trap various rotamers of 3 by
reacting this species with alkynes.
l
l
furans 16,18. In the case of alkyne 10 the yield of phosphinoline was
higher than the yield of furan, but this was opposite in the case of
alkyne 11. A similar situation was noted with ylide 1a, but the
product ratio was in favor of the furans in both cases.
2.2. Reactions of 2b with alkynes
Scheme 2. Generation of the intermediate 3 from 2.
The reaction of 2b with terminal alkynes, such as phenyl-
acetylene and 3-ethynylthiophene takes place in a few seconds
without irradiation and even in the dark. Similarly, for 1-decyne, no
light was necessary for the reaction with 2b. This behavior contrasts
with that of benzoyl substituted phosphonium ylides where irra-
diation was necessary. The reaction of 2b with diphenylacetylene
requires irradiation with a mercury lamp (366 nm) for 15 min.
These results are summarized in Scheme 6. In all cases the thio-
phene ring and phenyl ring, respectively, are involved in the re-
action, yielding to phosphininothiophenes (20, 22, 24, 26) and
phosphinolines (21, 23, 25, 27).
2. Results and discussion
The preparation of 2a has been described earlier.8 In Scheme 3
we summarize briefly the most important steps in the synthesis
of the starting materials 2.
Scheme 3. Preparation of 2a, b, c from the phosphonium salts 4a, b, c.
The phosphoranes 5 were obtained quantitatively from the
phosphonium salts 4, respectively. The NMR spectroscopic data of 5
showed that there is a 1:1 mixture between the Z- and E-isomers as
shown in Scheme 4.8c
Scheme 6. The reaction products and yields (%) of 2b with alkynes 6e9. In the case of
diphenylacetylene irradiation was required. *Yield according to 31P NMR spectroscopy
of the reaction mixture.
The reaction of ylide 2b with electron rich alkynes, such as 4-
ethynylanisole and 9-ethynylphenanthrene also occurs very rap-
idly and no irradiation was necessary. The products obtained are
summarized in Scheme 7. The main reaction products were the
phosphonium substituted furans 28 and 30. In the case of 4-
ethynylanisole, the corresponding phosphininothiophene 29
could also be isolated as a minor product.
Scheme 4. Equilibrium between E- and Z-isomers of 5 (Y¼H) and 2 (Y¼IþePh).
Scheme 5. The reaction products and yields (%) of 2a with alkynes 6e11.
The phosphoniumeiodonium ylides 2 (Scheme 3) were syn-
thesized in high yields by oxidation of 5 with di(acetoxy)iodo-
benzene at 0 ꢀC with further treatment of HBF4. We found that the
ylide 2b is less stable than 2a, and 2c is less stable than 2b;
therefore 2b has to be stored at 0 ꢀC and 2cdbelow 0 ꢀC. For the
three mixed ylides 2a, 2b, and 2c we also observed an equilibrium
between E- and Z-isomers by means of NMR studies.
Scheme 7. The reaction products and yields (%) of 2b with alkynes 10e11.
2.3. Reactions of 2c with alkynes
In Scheme 8 we have summarized the reaction between 2c and
alkynes 6e11. Again these reactions proceed without irradiation
and are complete within seconds. In the cases of alkynes 6e9 only
phosphininofurans 31e34 were isolated. In the case of 34, 31P NMR
measurements show a yield of 40% in solution, however, due to the
low stability of the resulting phosphininofuran 34, the isolated
yield was only 10%. It is interesting to note that in the case of 2c no
phosphinolines were isolated.
2.1. Reactions of 2a with alkynes
The reaction of ylide 2a with alkynes took more time in com-
parison with ylide 1a, it requires irradiation with a mercury lamp
(366 nm) for 30e90 min.

E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
7397
Scheme 8. The reaction products and yields (%) of 2c with alkyne 6e11.
The reaction of 2c and the electron-rich alkynes 4-
ethynylanisole and 9-ethynylphenanthrene lead to the formation
of two heterocyclic systems: phosphininofurans (36 and 38) and
phosphonium-substituted furans (35 and 37).
In the 31P NMR spectrum the signals of the phosphinolines,
phosphininothiophenes, phosphininofurans were observed as the
superposition of two signals. This fact indicated the presence of
a dynamic equilibrium between two geometric isomers of these
heterocycles (Scheme 9).
Scheme 10. Plausible mechanism of formation of the products B1eB3 from the ro-
tamers A1eA3, which originate from 3aec and an alkyne.
3. Conclusions
Our studies reveal a considerable difference in the reactivity of
the mixed ylides 1 and 2 toward alkynes. The higher reactivity of 2b
and 2c allowed us to carry out reactions with various alkynes
without irradiation. The results gave us evidence for the presence of
three rotamers of the intermediate vinyl cation, which is generated
from 3 and the alkyne. The reaction between 2 and alkynes pro-
Scheme 9. A dynamic equilibrium between two geometric isomers.
All the studied processes were accompanied by the formation of
the phosphonium salts having a signal in the 31P NMR spectra at
vided us with new heterocycles, such as
l
5-phosphininothio-
5-phosphininofurans, 5-phosphinolines, and rare
l
d
14e15 ppm.9
phenes,
l
polyaryl-substituted phosphonium salts.
2.4. Rationalization of products
4. Experimental section
4.1. General information
Our rationale for the various products is shown in Scheme 10.
This scheme is based on our previous preparative studies and on
recent spectroscopic studies, which used steady state and time
resolved methods to find transient species.9b These investigations
suggest that in the first step, a cleaving of the CeI bond in 2a, b, c
occurs to produce the stabilized cations 3a, b, c, respectively (cf.
Scheme 2). In the case of 2a irradiation was necessary, however, for
2b, c the generation of the cation 3 occurs at room temperature
without light. In the second step we assume the trapping of the
vinylic cation 3 by the alkyne giving rise to cation A for which
different conformers are likely, such as A1, A2, and A3 (see Scheme
10). In case of ylide 2a the products B1 and B2 are equal.
In the case of ylides 2b and 2c, the rotamers A1 and A2 provide
four ortho positions from the two phenyl rings and only one from
the thiophene or furan ring. Therefore we expect a ratio of the
phosphinolines B2 to the phosphininothiophenes or phosphini-
nofuran (B1), respectively of 1:4. For the reaction of 2b with phe-
nylacetylene the ratio found was 1:1 (see Scheme 6). This indicates
a preference of the thiophene over the phenyl ring for electrophilic
substitution. In line with these arguments are the first ionization
energies of thiophene¼8.9 eV and benzene¼9.3 eV. When we look
at the reaction of 2b with diphenylacetylene in Scheme 6 we find
the anticipated ratio of 4:1. For steric reasons the reaction rate with
diphenylacetylene is slowed down and thus the regioselectivity of
the cations A1 and A2 is increased. The occurrence of products B3
when electron rich substituents at the alkyne units are used (cf.
Schemes 5, 7, and 8) can be traced back to a higher stability of the
vinyl cation in the intermediate A3, which leads to B3.
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 at 161 MHz, and 13C NMR at
100 MHz. Chemical shifts (d) are reported in parts per million
(ppm) and coupling constants (J) in Hertz. The IR spectra were
measured in KBr or CCl4. High resolution mass spectra (HRMS)
were measured on a Bruker maXis instrument using electrospray
ionization (ESI).10 The measurements were done in a positive ion
mode (interface capillary voltaged4500 V); mass range from m/z
50 to m/z 3000 Da; external calibration was done with Electrospray
Calibrant Solution (Fluka). A syringe injection was used for solu-
tions in acetonitrile, methanol, or water (flow rate 3 mL/min). Ni-
trogen was applied as a dry gas; interface temperature was set at
180 ꢀC. The progress of the reactions and the purity after chro-
matographic separation were monitored by TLC on silica gel 60
plates. Chromatographic separation was carried out on columns
with silica gel 60.
4.2. General procedure for the synthesis of phosphonium
salts 4b, 4c
Methyl bromoacetate (4.12 mmol) was added to a solution of
phosphine (3.71 mmol) in dry acetonitrile (5 mL). A reaction mix-
ture was stirred under reflux for 2 h, the precipitate was filtered,

7398
E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
washed with diethyl ether (5 mL), and dried in vacuo to afford the
corresponding product 2a (2c).
(2 mL) at 0e5 ꢀC, then a solution of HBF4 (40%, 1.30 mmol) was
added at 0e5 ꢀC. The mixture was stirred for 1 h, then diethyl ether
(5 mL) was added, and stirred for 1 h. The precipitate was filtered,
washed with diethyl ether (10 mL), and dried in vacuo to give the
corresponding product 4.
4.2.1. (2-Methoxy-2-oxoethyl)(diphenyl)thiophen-2-ylphosphonium
bromide (4b). White solid, 80% yield. [Found: C, 54.18; H, 4.32; S, 7.67.
C
19H18BrO2PS requires C, 54.17; H, 4.31; S, 7.61%]; Mp: 177e179 ꢀC;
nmax (KBr) 1720,1470, 780e700 cmꢁ1
ddd, J 4.8, 1.0 Hz, -H thienyl), 8.03 (1H, ddd, J 8.1, 3.8, 1.0 Hz,
thienyl), 7.95e7.89 (4H, m, arom.), 7.86e7.82(2H, m, arom.), 7.72e7.67
(4H, m, arom.), 7.46 (1H, m, -H thienyl), 5.53 (2H, d, J 13.4 Hz, CH2),
3.67 (3H, s, OCH3); dC (100.6 MHz, CDCl3) 164.9 (s, C]O), 143.4 (d, J
9.5 Hz, -C thienyl), 140.0 (s, -C thienyl), 135.1 (s, arom.), 133.3 (d, J
11.7 Hz, arom.), 130.2 (d, J 16.1 Hz, -C thienyl), 130.0 (d, J 13.9 Hz,
arom.),118.5 (d, J 90.8 Hz, arom.),115.2 (d, J 105.4 Hz, -C thienyl), 53.2
;
dH (400 MHz, CD2Cl2) 8.20 (1H,
-H
4.4.1. [Diphenyl(thiophen-2-yl)phosphonio](methoxycarbonyl)(phen
yliodonio)methanide tetrafluoroborate (2b). White solid, 85% yield.
[Found: C, 47.69; H, 3.42; S, 4.79. C25H21BF4IO2PS requires C, 47.65;
H, 3.36; S, 5.09%]; Mp: 210e212 ꢀC; nmax (KBr) 1610, 1470, 1440,
a
b
b
1300, 1120e1040, 750 cmꢁ1
4.8, 4.5, 0.9 Hz,
(12H, m, arom.), 7.43 (2H, t, J 7.7 Hz, arom.), 7.33 (1H, m,
thienyl), 3.62 (3H, br s, OCH3); dC (100.6 MHz, CD3CN) 168.7 (d, J
14.6 Hz, C]O), 142.4 (d, J 10.3 Hz, -C thienyl), 139.4 (d, J 4.4 Hz, -C
;
dH (400 MHz, CD2Cl2) 8.00 (1H, ddd, J
-H thienyl), 7.77e7.73 (2H, m, arom.), 7.63e7.51
-H
b
a
a
b
b
a
(s, OCH3), 34.0 (d, J 60.7 Hz, CH2); dP (161 MHz, CD2Cl2) 14.93.
b
a
thienyl), 135.5 (s, arom.), 134.7 (d, J 11.0 Hz, arom.), 134.2 (s, arom.),
133.4 (s, arom.), 132.8 (s, arom.), 130.9 (d, J 13.7 Hz, arom.), 130.9 (d,
4.2.2. Furan-2-yl(2-methoxy-2-oxoethyl)diphenylphosphonium bro-
mide (4c). White solid, 84% yield. [Found: C, 56.11; H, 4.47.
J 13.7 Hz,
-C thienyl), 119.2 (s, arom.), 53.6 (s, OCH3); dP (161 MHz, CD2Cl2)
22.39.
b-C thienyl), 125.5 (d, J 98.1 Hz, arom.), 124.7 (d, J 90.0 Hz,
C
19H18BrO3P requires C, 56.32; H, 4.48%]; Mp: 187e189 ꢀC; nmax
(KBr) 1760, 1480, 790e700 cmꢁ1
(1H, m, -H fur), 7.99e7.93 (4H, m, arom.), 7.85e7.79 (3H, m, arom.),
7.71e7.66 (4H, m, arom.), 6.81 (1H, ddd, J 3.8, 3.7,1.8 Hz, -H fur), 5.51
(2H, d, J 13.9 Hz, CH2), 3.65 (3H, s, OCH3); dC (100.6 MHz, CDCl3) 164.5
(s, C]O),152.8 (d, J 7.3 Hz, -C fur),135.4 (s, arom.),133.7 (d, J 11.7 Hz,
arom.),132.7 (d, J 132.5 Hz, -C fur),131.1 (d, J 19.8 Hz, -C fur),130.1
(d, J 13.9 Hz, arom.), 116.6 (d, J 94.4 Hz, arom.), 113.1 (d, J 9.5 Hz, -C
;
dH (400 MHz, CD2Cl2) 8.07e8.06
a
a
b
4.4.2. [Furan-2-yl(diphenyl)phosphonio](methoxycarbonyl)(phenylio
donio)methanide tetrafluoroborate (2c). White solid, 74% yield.
[Found: C, 48.44; H, 3.51. C25H21BF4IO3P requires C, 48.81; H,
3.60%]; Mp: 159e160 ꢀC; nmax (KBr) 1610, 1470, 1450, 1300,
a
a
b
b
1100e1040, 750 cmꢁ1
;
dH (400 MHz, CD3CN) 8.04e8.03 (1H, m,
fur), 7.80e7.75 (2H, m, arom.), 7.67e7.57 (11H, m, arom.), 7.48 (2H,
t, J 7.2 Hz, arom.), 7.12e7.11 (1H, m, -H fur), 6.74e6.73 (1H, m, -H
fur), 3.57 (3H, br s, OCH3); dC (100.6 MHz, CD3CN) 168.4 (d, J 14.6 Hz,
C]O), 153.3 (d, J 7.3 Hz, -C fur), 140.1 (d, J 132.5 Hz, -H fur), 135.6
(s, arom.),134.6 (d, J 11.0 Hz, arom.),134.1 (s, arom.),133.4 (s, arom.),
132.9 (s, arom.), 130.9 (d, J 13.9 Hz, arom.), 129.7 (d, J 19.8 Hz, -C
a-H
fur), 53.4 (s, OCH3), 32.1 (d, J 60.7 Hz, CH2); dP (161 MHz, CDCl3) 8.74.
b
b
4.3. General procedure for the synthesis of phosphoranes 5b,
5c
a
a
A solution of sodium methoxide (3.18 mmol) in dry methanol
(1 mL) was added gradually to a solution of phosphonium salt 4b (4c)
(3.10 mmol) in dry methanol (10 mL), at 0e5 ꢀC. The mixture was
stirred for 2 h, then it was evaporated in vacuo, and the residue was
dissolved in methylene chloride (10 mL). The precipitate of sodium
bromide was separated from the solution of ylide 5b (5c) by filtration,
washed on the filter with methylene chloride (2ꢂ5 mL). The residue
was evaporated in vacuo, and the resulted oil was triturated with
diethyl ether. The precipitatewasseparated byfiltration, washed with
ether (10 mL), and dried in vacuo to give the corresponding product
5b (5c). The ylide 5c was then used without further purification.
b
fur), 124.1 (d, J 100.3 Hz, arom.), 119.0 (s, arom.), 113.6 (d, J 9.5 Hz,
C fur), 53.6 (s, OCH3); dP (161 MHz, CD2Cl2) 16.19.
b-
4.5. General procedure for the reaction of ylides 2a, 2b, and 2c
with alkynes
The alkyne (0.60 mmol) was added to a solution of ylide 2
(0.3 mmol) in anhydrous methylene chloride (2 mL). 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 of CH2Cl2 and chromatographed on silica gel. To elute
the residual alkynes and PhI, benzene was used; the corresponding
phosphinoline was eluted by using a CH2Cl2, and the furans were
eluted by using a CH2Cl2/MeOH mixture in a ratio of 100:1 and
CH2Cl2/CH3CN mixture in a ratio of 5:1.
4.3.1. Methyl [diphenyl(thiophen-2-yl)-
(5b). White solid, 74% yield. [Found: C, 66.82; H, 5.14; S, 9.15.
19H17O2PSrequires C, 67.04; H, 5.03; S, 9.42%]; Mp: 157e179 ꢀC; nmax
(KBr) 1620,1470,1440, 770e710 cmꢁ1
dH (400 MHz, CDCl3) 7.72 (1H,
dd, J 4.2 Hz, -H thienyl), 7.67 (4H, dd, J 13.0, 7.7 Hz, arom.), 7.56e7.53
l
5-phosphanylidene]acetate
C
;
a
(2H, m, arom.), 7.47e7.43 (5H, m, arom.), 7.16e7.15 (1H, m, arom.),
3.56 (3H, br s, OCH3), 2.99 (1H, br s, CH); dC (100.6 MHz, CDCl3) 171.3
4.5.1. Methyl 1,1,4-triphenyl-1l
5-phosphinoline-2-carboxylate
(br s, C]O), 137.7 (d, J 6.6 Hz,
thienyl),132.3 (d, J 11.0 Hz, arom.),132.0 (s, arom.),128.5 (d, J 12.4 Hz,
arom.),128.0 (d, J 13.9 Hz, -C thienyl),128.0 (d, J 98.8 Hz, arom.), 49.5
(s, OCH3), 30.8 (d, J 131.7 Hz, CH); dP (161 MHz, CD2Cl2) 10.44, 9.28.
b-C thienyl), 134.2 (d, J 2.9 Hz, a-C
(12). Yellow oil, 75% yield (reaction with UV irradiation with
a mercury lamp (366 nm) for 30 min). nmax (liquid film) 1635, 1577,
1436, 767e692 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.06 (4H, dd, J 8.2,
b
11.7 Hz, arom.), 7.61e7.51 (6H, m, arom.), 7.49e7.28 (9H, m, arom.),
7.06 (1H, dd, J 7.1, 7.1 Hz, arom.), 3.60 (3H, br s, OCH3); dC
(100.6 MHz, CD2Cl2) 168.7 (d, J 10.2 Hz, C]O),143.4 (s, arom.),142.2
(d, J 4.7 Hz, arom.), 133.7 (d, J 10.9 Hz, arom.), 133.7 (d, J 7.8 Hz,
arom.), 133.4 (br s, arom.), 132.3 (d, J 3.1 Hz, arom.), 131.8 (d, J 1.6 Hz,
arom.), 130.6 (s, arom.), 129.1 (d, J 13.2 Hz, arom.), 128.8 (s, arom.),
126.3 (s, arom.), 125.6 (d, J 7.8 Hz, arom.), 123.8 (d, J 11.7 Hz, arom.),
50.8 (br s, OCH3); dP (161 MHz, CD2Cl2) 5.47; HRMS (EI): Mþ, found
434.1420. C29H23O2P requires 434.1430.
4.3.2. Methyl
[furan-2-yl(diphenyl)-
l
5-phosphanylidene]acetate
(5c). White solid, 70% yield. dH (400 MHz, CD2Cl2) 7.79 (1H, br s,
H fur), 7.75e7.68 (4H, m, arom.), 7.60e7.57 (2H, m, arom.), 7.51e7.47
(4H, m, arom.), 7.19 (1H, br s, -H fur), 6.60e6.59 (1H, m, -H fur),
a
-
b
b
3.51, 3.30 (3H, 2 br s, OCH3), 2.78, 2.47 (1H, 2 d, J 23.2 Hz, CH); dP
(161 MHz, CD2Cl2) 4.70, 3.51.
4.4. General procedure for the synthesis of phospho-
niumeiodonium ylides 2b, 2c
4.5.2. Methyl 1,1-diphenyl-4-thiophen-3-yl-1l
5-phosphinoline-2-
carboxylate (13). Yellow oil, 50% yield (reaction with UV irradia-
tion with a mercury lamp (366 nm) for 30 min). nmax (liquid film)
A solution of diacetoxyiodobenzene (1.30 mmol) in methanol
(3 mL) was added to the solution of ylide 3 (1.30 mmol) in methanol
1637, 1575, 1437, 788e744 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.73 (4H, dd,

E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
7399
J 7.8, 12.5 Hz, arom.), 7.60e7.41 (9H, m, arom.), 7.38e7.34 (2H, m,
arom.), 7.20 (1H, dd, J 3.1, 1.2 Hz, arom.), 7.16 (1H, dd, J 4.7, 1.2 Hz,
arom.), 7.08e7.04 (1H, m, arom.), 3.57 (3H, br s, OCH3); dC
(100.6 MHz, CD2Cl2) 168.6 (br s, C]O), 143.8, 142.3 (two s, arom.),
133.7 (d, J 10.2 Hz, arom.), 132.3, 131.9, 130.4 (all s, arom.), 129.1 (d, J
12.5 Hz, arom.), 125.5 (d, J 8.1 Hz, arom.), 125.1 (s, arom.), 123.8 (d, J
12.4 Hz, arom.), 122.1 (s, arom.), 50.7 (br s, OCH3); dP (161 MHz,
CD2Cl2) 5.53; HRMS (EI): Mþ, found 440.0989. C27H21O2PS requires
440.0994.
arom.), 133.7 (d, J 7.8 Hz, arom.), 132.3 (d, J 2.6 Hz, arom.), 131.7 (s,
arom.),129.1 (d, J 12.9 Hz, arom.),125.7 (d, J 7.8 Hz, arom.),123.7 (d, J
12.9 Hz, arom.), 114.2 (s, arom.), 55.8 (s, Ph-OCH3), 50.6 (br s, C(O)
OCH3); dP (161 MHz, CD2Cl2) 5.63; HRMS (EI): Mþ, found 464.1543.
C30H25O3P requires 464.1536.
4.5.7. (2-Methoxy-5-phenanthren-9-ylfuran-3-yl)(triphenyl)-phos-
phonium tetrafluoroborate (18). Colorless oil, 65% yield (reaction
with UV irradiation with a mercury lamp (366 nm) for 60 min). nmax
(liquid film) 1590, 1470,1070, 750e720 cmꢁ1
; dH (400 MHz, CD2Cl2)
4.5.3. Methyl 1,1,3,4-tetraphenyl-1
l
5-phosphinoline-2-carboxylate
8.80 (1H, d, J 7.8 Hz, arom.), 8.72 (1H, d, J 8.4 Hz, arom.), 8.23 (1H,
dd, J 8.2, 1.4 Hz, arom.), 8.03 (1H, s, arom.), 7.98 (1H, d, J 8.0 Hz,
arom.), 7.94e7.90 (3H, m, arom.), 7.81e7.64 (16H, m, arom.), 6.61
(1H, d, J 2.6 Hz, CH), 4.14 (3H, s, OCH3); dC (100.6 MHz, CD2Cl2) 166.1
(d, J 13.2 Hz, OeCePhntr), 147.8 (d, J 13.9 Hz, MeOeCeO), 136.0 (s,
arom.), 134.4 (d, J 11.0 Hz, arom.), 131.35, 131.23 (two s, arom.), 130.9
(d, J 13.9 Hz, arom.), 129.6, 129.4, 129.2, 129.0, 128.5, 127.9, 127.7,
125.9, 124.9, 123.9, 123.1 (all s, arom.), 119.1 (d, J 94.4 Hz, arom.),
112.3 (d, J 10.2 Hz, Ph3PþCeCH), 73.9 (d, J 121.5 Hz, Ph3PþC), 59.8 (s,
OCH3); dP (161 MHz, CD2Cl2) 12.50; HRMS (EI): Mþ, found 535.1824.
(14). Yellow oil, 45% yield (reaction with UV irradiation with
a mercury lamp (366 nm) for 90 min). nmax (liquid film) 1627, 1427,
784e759 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.82 (4H, ddd, J 13.0, 8.3, 1.6,
arom.), 7.63e7.54 (6H, m, arom.), 7.36 (1H, ddd, J 12.9, 7.8, 1.3,
arom.), 7.27e7.24 (1H, m, arom.), 7.14e6.94 (11H, m, arom.), 6.91
(1H, dd, J 8.2, 5.3, arom.), 2.97 (3H, s, OCH3); dC (100.6 MHz, CD2Cl2)
167.6 (d, J 12.4, C]O), 144.5 (d, J 10.2, arom.), 143.7 (d, J 2.9, arom.),
142.8 (d, J 5.1, arom.), 141.9, 133.66 (two s, arom.), 133.6 (d, J 11.0,
arom.), 132.8 (d, J 7.3, arom.), 132.1, 131.7, 130.4 (all s, arom.), 129.8
(d, J 92.2, arom.), 129.1 (d, J 12.4, arom.), 120.0 (s, arom.), 126.9 (d, J
8.1, arom.), 126.8, 125.9, 125.4 (all s, arom.), 124.0 (d, J 11.7, arom.),
118.3 (d, J 8.1, arom.), 110.6 (d, J 88.6, arom.), 55.8 (d, J 109.0, C-
COOMe), 49.7 (s, OCH3); dP (161 MHz, CD2Cl2) 9.35; HRMS (EI): Mþ,
found 510.1728. C35H27O2P requires 510.1743.
C37H28O2P requires 535.1821.
4.5.8. Methyl 4-(phenanthren-9-yl)-1,1-diphenyl-1
l
5-phosphinoline-
2-carboxylate (19). Yellow oil, 10% yield (reaction with UV irradia-
tion with a mercury lamp (366 nm) for 90 min). nmax (liquid film)
1666, 1637, 1573, 1436, 786e763 cmꢁ1
; dH (400 MHz, CD2Cl2) 8.77
4.5.4. Methyl 4-octyl-1,1-diphenyl-1
l
5-phosphinoline-2-carboxylate
(2H, t, J 9.0, arom.), 7.92e7.78 (7H, m, arom.), 7.70e7.44 (12H, m,
arom.), 7.16e7.12 (1H, m, arom.), 7.03e6.99 (1H, m, arom.), 6.83
(1H, dd, J 8.1, 5.7, arom.), 3.53 (3H, br s, OCH3); dC (100.6 MHz,
CD2Cl2) 168.8 (d, J 13.2, C]O), 143.1 (d, J 3.7, arom.), 139.7 (s, arom.),
134.0 (d, J 11.0, arom.), 133.7 (d, J 11.0, arom.), 133.5 (d, J 9.5, arom.),
133.0, 132.4, 131.8, 131.1, 130.5, 129.4 (all s, arom.), 129.3 (d, J 13.2,
arom.), 129.1 (d, J 12.4, arom.), 129.0, 128.0, 127.2, 127.0, 126.8 (all s,
arom.), 126.4 (d, J 7.3, arom.), 123.7 (d, J 12.4, arom.), 123.4, 123.0
(two s, arom.), 50.70 (br s, OCH3); dP (161 MHz, CD2Cl2) 8.01; HRMS
(EI): Mþ, found 534.1728. C37H27O2P requires 534.1743.
(15). Yellow oil, 55% yield (reaction with UV irradiation with
a mercury lamp (366 nm) for 60 min). nmax (liquid film) 2925, 1666,
1635, 1579, 1434, 786e744 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.69e7.64
(4H, m, arom.), 7.56e7.37 (9H, m, arom.), 7.24 (1H, d, J 29.4, CH),
7.06e7.02 (1H, m, arom.), 3.60, 3.39 (3H, two br s, OCH3), 2.57 (2H, t,
J 7.5, CH2), 1.64e1.55 (2H, m, CH2), 1.41e1.30 (10H, m, 5CH2), 0.90
(3H, t, J 7.1, CH3); dC (100.6 MHz, CD2Cl2) 168.7 (d, J 13.9, C]O),142.5
(d, J 4.4, arom.), 133.9 (d, J 8.1, arom.), 133.7 (d, J 11.0, arom.), 132.1
(d, J 2.2, arom.), 132.0 (s, arom.), 130.4 (br s, CH), 129.0 (d, J 13.2,
arom.), 123.6 (d, J 8.1, arom.), 123.3 (d, J 12.4, arom.), 111.7 (br s,
arom.), 103.5 (d, J 101.7, arom.), 50.63, 50.14 (two br.s, OCH3), 34.8,
32.5, 30.6, 30.3, 30.2, 30.0, 23.3 (all s, 7CH2), 14.5 (s, CH3); dP
(161 MHz, CD2Cl2) 6.50, 6.01; HRMS (EI): Mþ, found 470.2356.
4.5.9. Methyl 4,7,7-triphenyl-7
carboxylate (20). Yellow oil, 20% yield. nmax (liquid film) 1641,
1479, 1437, 797e758 cmꢁ1
dH (400 MHz, CD2Cl2) 7.69 (4H, dd, J
l
5-phosphinino[2,3-b]thiophene-6-
;
C
31H35O2P requires 470.2369.
13.4, 7.0 Hz, arom.), 7.58e7.48 (8H, m, arom.), 7.44 (1H, d, J 32.1 Hz,
CH), 7.38 (2H, m, arom.), 7.26 (1H, tt, J 7.3, 1.3 Hz, arom.), 7.03e6.98
4.5.5. [2-Methoxy-5-(4-methoxyphenyl)furan-3-yl](triphenyl)phos-
phonium tetrafluoroborate (16). Colorless oil, 20% yield (reaction
with UV irradiation with a mercury lamp (366 nm) for 30 min). nmax
(2H, m, a,b-H thienyl), 3.56 (3H, br s, OCH3); dC (100.6 MHz, CD2Cl2)
169.1 (d, J 15.3 Hz, C]O), 154.6 (d, J 8.5 Hz, arom.), 142.9 (s, arom.),
133.4 (d, J 11.7 Hz, arom.), 132.4 (br s, CH]CePh), 132.3 (d, J 2.7 Hz,
arom.), 129.1 (d, J 13.0 Hz, arom.), 129.0 (s, arom.), 128.7 (s, arom.),
(liquid film) 1470, 1070, 730 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.91e7.87
(3H, m, arom.), 7.77e7.72 (6H, m, arom.), 7.66 (6H, dd, J 7.3, 13.5 Hz,
arom.), 7.53 (2H, d, J 9.0 Hz, arom.), 6.96 (2H, d, J 9.0 Hz, arom.), 6.33
(1H, d, J 2.6 Hz, CH), 4.05 (3H, s, OCH3), 3.83 (3H, s, OCH3); dC
(100.6 MHz, CD2Cl2) 165.4 (d, J 13.7 Hz, CePheOMe), 160.6 (s,
arom.), 148.5 (d, J 13.7 Hz, MeOeCeO), 135.9 (d, J 2.9 Hz, arom.),
134.4 (d, J 10.8 Hz, arom.), 130.9 (d, J 13.7 Hz, arom.), 125.5 (s,
arom.), 121.4 (s, arom.), 119.2 (d, J 94.3 Hz, arom.), 115.0 (s, arom.),
105.6 (d, J 10.1 Hz, Ph3PþCeCH), 73.9 (d, J 121.6 Hz, Ph3PþC), 59.6 (s,
OCH3), 55.9 (s, OCH3); dP (161 MHz, CD2Cl2) 12.25; HRMS (EI): Mþ,
found 465.1623. C30H26O3P requires 465.1614.
128.6 (d, J 13.0 Hz,
arom.), 121.3 (d, J 17.1 Hz,
b
-C thienyl), 128.1 (d, J 99.2 Hz, arom.), 126.7 (s,
-C thienyl), 111.9 (br s, CH]CePh), 104.5
a
(d, J 100.1 Hz, arom.), 61.7 (d, J 110.4 Hz, C1), 50.9 (d, J 2.7 Hz, OCH3);
dP (161 MHz, CD2Cl2) 2.94; HRMS (EI): Mþ, found 440.0995.
C27H21O2PS requires 440.0994.
4.5.10. Methyl 1,4-diphenyl-1-thiophen-2-yl-1
carboxylate (21). Yellow oil, 20% yield. nmax (liquid film) 1664,
1458, 1435, 767e705 cmꢁ1
dH (400 MHz, CD2Cl2) 7.84 (1H, ddd, J
5.0, 5.0, 1.1 Hz, -H thienyl), 7.79 (2H, dd, J 14.0, 7.0 Hz, arom.),
7.58e7.47 (5H, m, arom.), 7.41e7.25 (8H, m, arom.), 7.22 (1H, ddd, J
5.0, 3.6, 1.7 Hz, -H thienyl), 7.09e7.04 (1H, m, arom.), 3.55 (3H, br s,
OCH3); dC (100.6 MHz, CD2Cl2) 168.7 (d, J 14.8 Hz, C]O), 143.3 (s,
arom.), 142.1 (d, J 5.8 Hz, arom.), 138.4 (d, J 19.3 Hz, -C thienyl),
135.7 (d, J 4.9 Hz, -C thienyl), 133.9 (d, J 8.1 Hz, -C thienyl), 133.3
l
5-phosphinoline-2-
;
b
4.5.6. Methyl 4-(4-methoxyphenyl)-1,1-diphenyl-1
l
5-phosphinoline-
b
2-carboxylate (17). Yellow oil, 50% yield (reaction with UV irradi-
ation with a mercury lamp (366 nm) for 30 min). nmax (liquid film)
b
1640, 1580, 1470, 750e730 cmꢁ1
;
dH (400 MHz, CD2Cl2) 7.76e7.71
b
a
(4H, m, arom.), 7.59e7.50 (6H, m, arom.), 7.46e7.29 (4H, m, arom.),
7.30 (2H, d, J 8.7 Hz, arom.), 7.04 (1H, dd, J 7.5, 7.5 Hz, arom.), 6.94
(2H, d, J 8.7 Hz, arom.), 3.84 (3H, s, PhOCH3), 3.56 (3H, br s, C(O)
OCH3); dC (100.6 MHz, CD2Cl2) 168.7 (d, J 12.9 Hz, C]O), 158.6 (s,
arom.), 142.6 (d, J 5.2 Hz, arom.), 135.8 (s, arom.), 133.7 (d, J 10.4 Hz,
(d, J 11.2 Hz, arom.), 133.0 (br s, CH]CePh), 132.5 (d, J 3.1 Hz,
arom.), 132.0 (d, J 1.8 Hz, arom.), 130.7 (s, arom.), 129.1 (d, J 13.5 Hz,
arom.),128.8 (s, arom.),128.8 (d, J 13.9 Hz, arom.),128.1 (d, J 95.1 Hz,
arom.), 127.9 (d, J 87.1 Hz, arom.), 126.4 (s, arom.), 125.8 (d, J 8.5 Hz,
arom.), 123.8 (d, J 12.6 Hz, arom.), 115.8 (br s, CH]CePh), 109.8 (d, J

7400
E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
91.6 Hz, arom.), 50.7 (br s, OCH3); dP (161 MHz, CD2Cl2) ꢁ1.36;
8.5 Hz, arom.), 126.8 (s, arom.), 126.0 (s, arom.), 125.5 (s, arom.),
123.9 (d, J 12.6 Hz, arom.),118.1 (d, J 8.5 Hz, CePh),110.6 (d, J 91.1 Hz,
arom.), 58.3 (d, J 112.2 Hz, C1), 49.9 (s, OCH3); dP (161 MHz, CD2Cl2)
0.62; HRMS (EI): Mþ, found 516.1299. C33H25O2PS requires
516.1307.
HRMS (EI): Mþ, found 440.0988. C27H21O2PS requires 440.0994.
4.5.11. Methyl 7,7-diphenyl-4-thiophen-3-yl-7
thiophene-6-carboxylate (22). Yellow oil, 20% yield. nmax (liquid
film) 1655, 1477, 1427, 784e707 cmꢁ1
dH (400 MHz, CD2Cl2) 7.68
(4H, dd, J 13.6, 7.0 Hz, arom.), 7.60e7.49 (8H, m, arom.), 7.38e7.33
(2H, m, arom.), 7.07 (1H, dd, J 5.5, 3.1 Hz, -H thienyl), 7.01 (1H, dd, J
5.5, 3.7 Hz, -H thienyl), 3.57 (3H, br s, OCH3); dC (100.6 MHz,
l
5-phosphinino[2,3-b]
;
4.5.15. Methyl 4-octyl-1-phenyl-1-thiophen-2-yl-1
2-carboxylate (27). Yellow oil, 25% yield. nmax (liquid film) 2926,
2854, 1635, 1462, 1433, 787e692 cmꢁ1
dH (400 MHz, CD2Cl2) 7.81
(1H, ddd, J 4.7, 4.7, 0.8 Hz, -H thienyl), 7.73 (2H, dd, J 13.9, 7.5 Hz,
arom.), 7.57e7.45 (7H, m, arom.), 7.20 (1H, d, J 30.8 Hz, CH), 7.19
(1H, ddd, J 5.1, 3.7, 1.9 Hz, -H thienyl), 7.09e7.04 (1H, m, arom.),
l
5-phosphinoline-
a
b
;
CD2Cl2) 169.0 (d, J 9.9 Hz, C]O), 154.4 (d, J 8.5 Hz, arom.), 143.3 (s,
arom.), 133.4 (d, J 11.7 Hz, arom.), 132.3 (d, J 3.1 Hz, arom.), 132.2 (br
s, CH]C thienyl), 129.1 (d, J 103.7 Hz, arom.), 129.1 (d, J 13.0 Hz,
b
b
arom.), 128.6 (d, J 13.0 Hz,
arom.), 121.5 (d, J 17.5 Hz,
b
-C thienyl), 128.6 (s, arom.), 125.6 (s,
3.59 (3H, br s, OCH3), 2.59e2.54 (2H, m, CH2), 1.63e1.55 (2H, m,
CH2), 1.41e1.30 (10H, m, 5CH2), 0.90 (3H, t, J 6.7 Hz, CH3); dC
(100.6 MHz, CD2Cl2) 168.6 (br s, C]O), 142.3 (d, J 5.4 Hz, arom.),
a
-C thienyl), 120.0 (s, arom.), 106.8 (br s,
CH]C thienyl), 104.4 (d, J 97.4 Hz, arom.), 50.9 (d, J 4.0 Hz, OCH3); dP
(161 MHz, CD2Cl2) 4.85; HRMS (EI): Mþ, found 446.0550.
138.0 (d, J 10.3 Hz,
b-C thienyl), 135.4 (d, J 4.5 Hz, b-C thienyl), 134.1
C
25H19O2PS2 requires 446.0559.
(d, J 8.1 Hz, -C thienyl), 133.3 (d, J 11.2 Hz, arom.), 132.4 (d, J 2.7 Hz,
a
arom.), 132.2 (d, J 1.3 Hz, arom.), 131.4 (d, J 109.1 Hz, arom.), 130.3
(br s, CH]CeC8H17), 129.6 (d, J 98.3 Hz, arom.), 129.0 (d, J 13.5 Hz,
arom.), 128.7 (d, J 14.4 Hz, arom.), 124.0 (d, J 8.5 Hz, arom.), 123.3 (d,
J 13.0 Hz, arom.), 112.1 (br s, CH]CeC8H17), 110.6 (d, J 88.9 Hz,
arom.), 64.0 (d, J 124.3 Hz, C1), 50.6 (d, J 8.5 Hz, OCH3), 34.7, 32.5,
30.7, 30.3, 30.2, 30.0, 23.3 (all s, 5CH2), 14.5 (s, CH3); dP (161 MHz,
CD2Cl2) ꢁ0.46, ꢁ1.32; HRMS (EI): Mþ, found 476.1928. C29H33O2PS
requires 476.1933.
4.5.12. Methyl 1-phenyl-1-thiophen-2-yl-4-thiophen-3-yl-1
phinoline-2-carboxylate (23). Yellow oil, 20% yield. nmax (liquid film)
1664, 1458, 1435, 779e717 cmꢁ1
dH (400 MHz, CD2Cl2) 7.83 (1H,
ddd, J 5.0, 5.0, 0.9 Hz, -H thienyl), 7.77 (2H, dd, J 14.2, 7.2 Hz, arom.),
7.59e7.43 (6H, m, arom.), 7.38 (1H, d, J 30.5 Hz, CH), 7.39e7.34 (2H,
m, arom.), 7.21 (1H, ddd, J 5.1, 3.7, 1.9 Hz, -H thienyl), 7.18 (1H, dd, J
2.9, 1.3 Hz, arom.), 7.13 (1H, dd, J 4.8, 1.3 Hz, arom.), 7.10e7.05 (1H,
m, arom.), 3.55 (3H, br s, OCH3); dC (100.6 MHz, CD2Cl2) 168.6 (br s,
C]O), 143.8 (s, arom.), 142.2 (d, J 5.4 Hz, arom.), 138.5 (d, J 10.3 Hz,
l
5-phos-
;
b
b
4.5.16. [2-Methoxy-5-(4-methoxyphenyl)furan-3-yl](diphenyl)thio-
b
-C thienyl), 135.7 (d, J 4.5 Hz,
b
-C thienyl), 133.9 (d, J 8.1 Hz,
a
-C
phen-2-ylphosphonium tetrafluoroborate (28). Colorless oil, 35%
thienyl), 133.3 (d, J 11.7 Hz, arom.), 133.2 (br s, CH]C thienyl), 132.6
(d, J 3.1 Hz, arom.), 132.2 (d, J 1.8 Hz, arom.), 130.5 (s, arom.), 129.1
(d, J 13.5 Hz, arom.), 128.8 (d, J 14.4 Hz, arom.), 128.0 (d, J 98.3 Hz,
arom.), 127.8 (d, J 87.5 Hz, arom.), 125.7 (d, J 8.1 Hz, arom.), 125.2 (s,
arom.), 123.8 (d, J 12.6 Hz, arom.), 122.3 (s, arom.), 110.2 (br s, CH]C
thienyl), 108.7 (d, J 91.1 Hz, arom.), 50.8 (d, J 4.1 Hz, OCH3); dP
(161 MHz, CD2Cl2) 0.58; HRMS (EI): Mþ, found 446.0554.
yield. nmax (liquid film) 1441, 1057, 795e708 cmꢁ1
;
dH (400 MHz,
-H thienyl), 7.92e7.87 (2H,
m, arom.), 7.77e7.67 (9H, m, arom.), 7.54e7.50 (1H, m, -H thienyl),
7.52 (2H, d, J 8.3 Hz, arom.), 6.96 (2H, d, J 9.0 Hz, arom.), 6.35 (1H,d, J
3.0 Hz, -H fur), 4.08 (3H, s, OCH3), 3.83 (3H, s, OCH3); dC
(100.6 MHz, CD2Cl2) 165.4 (d, J 14.4 Hz, -C fur), 160.7 (s, arom.),
148.6 (d, J 14.4 Hz, -C fur),142.8 (d, J 11.2 Hz, -C thienyl),140.4 (d, J
5.1 Hz, -C thienyl), 136.2 (d, J 3.1 Hz, arom.), 133.9 (d, J 12.1 Hz,
arom.), 131.1 (d, J 16.0 Hz, -C thienyl), 130.9 (d, J 13.9 Hz, arom.),
125.6 (s, arom.),121.4 (s, arom.),120.0 (d, J 97.8 Hz, arom.),118.2 (d, J
110.9 Hz, -C thienyl), 115.0 (s, arom.), 105.3 (d, J 10.8 Hz, -C fur),
74.6 (d, J 126.1 Hz, -C fur), 59.7 (s, OCH3), 56.0 (s, OCH3); dP
(161 MHz, CD2Cl2) 5.49; HRMS (EI): Mþ, found 471.1172.
28H24O3PS requires 471.1178.
CD2Cl2) 8.23 (1H, ddd, J 4.8, 4.8, 1.1 Hz,
a
b
b
a
a
a
C
25H19O2PS2 requires 446.0559.
b
b
4.5.13. Methyl 4,5,7,7-tetraphenyl-7
l
5-phosphinino[2,3-b]thiophene-
6-carboxylate (24). Yellow oil, 40% yield (reaction with UV irradi-
ation with a mercury lamp (366 nm)). nmax (liquid film) 1682, 1466,
a
b
b
1427, 760e700 cmꢁ1
; dH (400 MHz, CD2Cl2) 7.80 (4H, ddd, J 13.6, 7.3,
1.7 Hz, arom.), 7.59e7.53 (6H, m, arom.), 7.14e6.97 (12H, m, arom.),
3.07 (3H, s, OCH3); dC (100.6 MHz, CD2Cl2) 169.3 (d, J 12.6 Hz, C]O),
157.7 (d, J 9.4 Hz, arom.), 144.4 (d, J 12.1 Hz, arom.), 143.7 (d, J 7.6 Hz,
CePh), 143.2 (s, arom.), 134.3 (d, J 11.2 Hz, arom.), 133.6 (s, arom.),
133.0 (d, J 2.7 Hz, arom.), 131.6 (d, J 94.7 Hz, arom.), 131.5 (s, arom.),
130.0 (d, J 13.0 Hz, arom.), 129.5 (d, J 11.7 Hz,
arom.), 128.0 (s, arom.), 127.6 (s, arom.), 126.9 (s, arom.), 123.5 (d, J
16.6 Hz, -C thienyl), 114.8 (d, J 6.7 Hz, CePh), 106.1 (d, J 94.2 Hz,
C
4.5.17. Methyl 4-(4-methoxyphenyl)-7,7-diphenyl-7
[2,3-b]thiophene-6-carboxylate (29). Red oil, 15% yield. nmax (liquid
film) 1639, 1479, 1436, 761e708 cmꢁ1
dH (400 MHz, CD2Cl2) 7.69
(4H, dd, 13.2, 6.9 Hz, arom.), 7.57e7.48 (6H, m, arom.),
7.48e7.44 (2H, m, arom.), 7.36 (1H, d, J 31.8 Hz, CH), 7.03e6.99
(2H, m, -H thienyl), 6.94e6.91 (2H, m, arom.), 3.84 (3H, s,
l
5-phosphinino
;
b
-C thienyl), 129.2 (s,
J
a
a,b
arom.), 61.2 (d, J 112.2 Hz, C1), 51.0 (s, OCH3); dP (161 MHz, CD2Cl2)
OCH3), 3.56 (3H, br s, COOCH3); dC (100.6 MHz, CD2Cl2) 169.1 (br
s, C]O), 158.7 (s, arom.), 155.2 (d, J 8.1 Hz, arom.), 135.4 (s,
arom.), 133.4 (br s, CH]CeC6H14epOMe), 133.4 (d, J 11.2 Hz,
arom.), 132.2 (d, J 102.3 Hz, arom.), 132.2 (d, J 2.7 Hz, arom.),
4.79; HRMS (EI): Mþ, found 516.1301. C33H25O2PS requires 516.1307.
4.5.14. Methyl 1,3,4-triphenyl-1-thiophen-2-yl-1l
5-phosphinoline-2-
carboxylate (25). Yellow oil, 10% yield (reaction with UV irradia-
tion with a mercury lamp (366 nm)). nmax (liquid film) 1674, 1456,
129.9 (s, arom.), 129.0 (d, J 13.0 Hz, arom.), 128.7 (d, J 12.1 Hz,
b-C
thienyl), 121.3 (d, J 17.1 Hz, -C thienyl), 114.3 (s, arom.), 111.6 (br
a
1427, 758e700 cmꢁ1
;
dH (400 MHz, CD2Cl2) 7.90e7.84 (3H, m,
s, CH]CeC6H4epOMe), 104.5 (d, J 95.6 Hz, arom.), 55.8 (s, OCH3),
50.8 (br s, COOCH3); dP (161 MHz, CD2Cl2) 2.91; HRMS (EI): Mþ,
found 470.1092. C28H23O3PS requires 470.1100.
arom.), 7.60e7.53 (3H, m, arom.), 7.50 (1H, ddd, J 7.6, 3.6, 0.9 Hz,
arom.), 7.42 (1H, ddd, J 13.6, 7.8, 0.9 Hz, arom.), 7.29e7.25 (2H, m,
arom.), 7.13e6.95 (11H, m, arom.), 6.90e6.87 (1H, m, arom.), 3.04
(3H, s, OCH3); dC (100.6 MHz, CD2Cl2) 167.6 (d, J 11.2 Hz, C]O),144.3
(d, J 11.7 Hz, arom.), 143.6 (d, J 8.5 Hz, CePh), 142.8 (d, J 5.8 Hz,
4.5.18. (2-Methoxy-5-phenanthren-9-ylfuran-3-yl)(diphenyl)thio-
phen-2-ylphosphonium tetrafluoroborate (30). Colorless oil, 60%
arom.), 141.9 (s, arom.), 138.3 (d, J 9.9 Hz,
b-C thienyl), 135.5 (d, J
yield. nmax (liquid film) 1439, 1057, 750e691 cmꢁ1
;
dH (400 MHz,
CD2Cl2) 8.80e8.78 (1H, m, arom.), 8.71 (1H, d, J 8.4 Hz, arom.), 8.28
(1H, ddd, J 5.0, 5.0, 1.1 Hz, -H thienyl), 8.26e8.24 (1H, m, arom.),
4.0 Hz, -C thienyl), 133.7 (s, arom.), 133.1 (d, J 7.6 Hz,
b
a
-C thienyl),
133.0 (d, J 11.2 Hz, arom.), 132.3 (d, J 2.2 Hz, arom.), 132.0 (d, J
97.8 Hz, arom.), 131.9 (s, arom.), 131.2 (d, J 96.0 Hz, arom.), 129.1 (d, J
13.5 Hz, arom.), 128.7 (d, J 14.4 Hz, arom.), 128.0 (s, arom.), 127.1 (d, J
a
8.05 (1H, s, arom.), 7.99 (1H, dd, J 7.8, 1.3 Hz, arom.), 7.95e7.90 (2H,
m, arom.), 7.82e7.77 (10H, m, arom.), 7.76e7.70 (3H, m, arom.),

E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
7401
7.68e7.64 (1H, m, arom.), 7.55 (1H, ddd, J 4.8, 3.7, 2.2 Hz,
thienyl), 6.64 (1H,d, J 2.8 Hz, -H fur), 4.16 (3H, s, OCH3); dC
(100.6 MHz, CD2Cl2) 166.1 (d, J 13.9 Hz, -C fur), 147.8 (d, J 14.4 Hz,
-C fur), 142.9 (d, J 11.2 Hz, -C thienyl), 140.5 (d, J 5.8 Hz, -C
thienyl), 136.2 (d, J 3.1 Hz, arom.), 134.0 (d, J 11.7 Hz, arom.), 131.4 (s,
arom.), 131.2 (d, J 15.7 Hz, -C thienyl), 131.0 (d, J 13.9 Hz, arom.),
129.7 (s, arom.), 129.4 (s, arom.), 129.2 (s, arom.), 128.5 (s, arom.),
127.9 (s, arom.), 127.9 (s, arom.), 127.7 (s, arom.), 125.9 (s, arom.),
124.9 (s, arom.), 123.9 (s, arom.), 123.1 (s, arom.), 120.0 (d, J 97.8 Hz,
b
-H
7.2 Hz, CH3); dC (100.6 MHz, CD2Cl2) 169.0 (br s, C]O), 164.5 (d, J
13.5 Hz, CH]CeC8H17), 141.6 (d, J 13.9 Hz, -C fur), 133.1 (d, J
11.2 Hz, arom.), 132.0 (d, J 2.2 Hz, arom.), 131.1 (br s, CH]CeC8H17),
129.9 (d, J 124.3 Hz, arom.), 128.9 (d, J 13.0 Hz, arom.), 110.8 (d, J
b
a
a
a
a
b
7.6 Hz, b-C fur), 104.5 (br s, arom.), 88.6 (d, J 115.3 Hz, arom.), 50.6
b
(br s, OCH3), 32.5, 31.0, 30.9, 30.1, 30.1, 29.9, 23.3 (all s, 5CH2),14.5 (s,
CH3); dP (161 MHz, CD2Cl2) 6.88; HRMS (EI): Mþ, found 460.2152.
C29H33O3P requires 460.2162.
arom.), 118.1 (d, J 110.9 Hz,
74.6 (d, J 125.7 Hz,
a
-C thienyl), 112.0 (d, J 10.3 Hz,
b
-C fur),
4.5.23. Furan-2-yl[2-methoxy-5-(4-methoxyphenyl)furan-3-yl]di-
b
-C fur), 59.9 (s, OCH3); dP (161 MHz, CD2Cl2)
phenylphosphonium tetrafluoroborate (35). Colorless oil, 15% yield.
5.56; HRMS (EI): Mþ, found 541.1380. C35H26O2PS requires
541.1386.
nmax (liquid film) 1440, 1070, 750e700 cmꢁ1
;
dH (400 MHz, CD2Cl2)
-H fur), 7.90e7.88 (2H, m, arom.),
7.76e7.74 (5H, m, arom.), 7.72e7.69 (3H, m, arom.), 7.53 (2H, d, J
8.13 (1H, ddd, J 2.7, 1.7, 0.8 Hz,
a
4.5.19. Methyl 4,7,7-triphenyl-7
carboxylate (31). Yellow oil, 45% yield. nmax (liquid film) 1643,
1483, 1439, 760e694 cmꢁ1
dH (400 MHz, CD2Cl2) 7.69 (4H, dd, J
12.9, 6.5 Hz, arom.), 7.59 (1H, d, J 34.7 Hz, CH), 7.61e7.49 (8H, m,
arom.), 7.43 (1H, dd, J 2.3, 2.3 Hz, -H fur), 7.39e7.34 (2H, m, arom.),
7.20 (1H, tt, J 7.5, 1.3 Hz, arom.), 6.50 (1H, dd, J 2.3, 2.3 Hz, -H fur),
3.59 (3H, br s, OCH3); dC (100.6 MHz, CD2Cl2) 169.1 (br s, C]O),
162.6 (d, J 13.5 Hz, CH]C-Ph), 141.6 (d, J 13.9 Hz, -C fur), 139.0 (s,
l
5-phosphinino[2,3-b]furan-6-
9.0 Hz, arom.), 7.29 (1H, ddd, J 3.7, 2.0, 0.6 Hz,
9.0 Hz, arom.), 6.84 (1H, ddd, J 3.7, 1.9, 1.9 Hz,
b
b
-H fur), 6.96 (2H, d, J
-H fur), 6.38 (1H,d, J
;
3.1 Hz,
(100.6 MHz, CD2Cl2) 165.9 (d, J 14.8 Hz,
154.1 (d, J 8.1 Hz, -C fur), 148.8 (d, J 14.4 Hz,
3.1 Hz, arom.), 134.9 (d, J 136.9 Hz, -C fur), 134.0 (d, J 12.1 Hz,
arom.), 131.0 (d, J 13.9 Hz, arom.), 130.7 (d, J 21.1 Hz, -C fur), 125.6
(s, arom.),121.4 (s, arom.),118.3 (d, J 98.7 Hz, arom.),115.0 (s, arom.),
113.4 (d, J 9.4 Hz, -C fur), 104.8 (d, J 10.8 Hz, -C fur), 72.0 (d, J
127.9 Hz,
b
-H fur), 4.05 (3H, s, OCH3), 3.83 (3H, s, OCH3); dC
-C fur), 160.7 (s, arom.),
-C fur), 136.3 (d, J
a
a
a
a
b
a
b
a
arom.), 134.3 (br s, CH]CePh), 133.2 (d, J 11.7 Hz, arom.), 132.3 (d, J
3.1 Hz, arom.), 130.2 (d, J 98.5 Hz, arom.), 129.1 (d, J 13.0 Hz, arom.),
128.7 (s, arom.),128.0 (s, arom.),125.9 (s, arom.),110.8 (d, J 8.1 Hz,
b
b
b
-C fur), 59.7 (s, OCH3), 56.0 (s, OCH3); dP (161 MHz,
b
-
CD2Cl2) ꢁ1.11; HRMS (EI): Mþ, found 455.1411. C28H24O4P requires
C fur), 105.4 (br s, arom.), 89.4 (d, J 110.0 Hz, arom.), 50.9 (s, OCH3);
455.1407.
dP (161 MHz, CD2Cl2) 4.50; HRMS (EI): Mþ, found 424.1219.
C
27H21O3P requires 424.1223.
4.5.24. Methyl 4-(4-methoxyphenyl)-7,7-diphenyl-7
[2,3-b]furan-6-carboxylate (36). Yellow oil, 30% yield. nmax (liquid
film) 1645, 1470, 1450, 800e730 cmꢁ1
dH (400 MHz, CD2Cl2) 7.68
l
5-phosphinino
4.5.20. Methyl 7,7-diphenyl-4-thiophen-3-yl-7
furan-6-carboxylate (32). Yellow oil, 40% yield. nmax (liquid film)
1645, 1485, 1440, 800e710 cmꢁ1
dH (400 MHz, CD2Cl2) 7.84 (1H, d,
J 34.1 Hz, CH), 7.67 (4H, dd, J 13.7, 7.2 Hz, arom.), 7.57e7.47 (8H, m,
arom.), 7.44 (1H, dd, J 5.1, 1.4 Hz, -H thienyl), 7.32 (1H, dd, J 5.0,
3.0 Hz, -H thienyl), 6.49 (1H, dd, J 2.3, 2.3 Hz, -H fur), 3.60 (3H, br
s, OCH3); dC (100.6 MHz, CD2Cl2) 168.9 (d, J 12.6 Hz, C]O),162.4 (d, J
13.0 Hz, CH]C thienyl), 141.7 (d, J 13.9 Hz, -C fur), 138.9 (s, arom.),
l
5-phosphinino[2,3-b]
;
(4H, dd, J 13.4, 7.2 Hz, arom.), 7.57 (1H, d, J 32.2 Hz, CH),
7.56e7.49 (6H, m, arom.), 7.50 (2H, d, J 8.7 Hz, arom.), 7.42 (1H,
;
dd, J 2.5, 2.5 Hz,
dd, J 2.2, 2.2 Hz,
a
-H fur), 6.91 (2H, d, J 8.7 Hz, arom.), 6.49 (1H,
-H fur), 3.82 (3H, s, OCH3), 3.58 (3H, br s,
a
b
b
b
COOCH3); dC (100.6 MHz, CD2Cl2) 169.1 (br s, C]O), 162.8 (d, J
13.5 Hz, CH]CeC6H4epOMe), 158.4 (s, arom.), 141.6 (d, J 13.9 Hz,
a
a
-C fur), 133.2 (br s, CH]CeC6H4epOMe), 133.2 (d, J 11.2 Hz,
arom.), 132.2 (d, J 2.7 Hz, arom.), 131.5 (s, arom.), 129.2 (s, arom.),
129.0 (d, J 13.5 Hz, arom.), 114.1 (s, arom.), 110.8 (d, J 7.6 Hz, -C
133.3 (br s, CH]C thienyl), 133.2 (d, J 11.7 Hz, arom.), 132.3 (d, J
2.7 Hz, arom.), 129.9 (d, J 113.1 Hz, arom.), 129.1 (d, J 13.0 Hz, arom.),
b
127.3 (s, arom.), 124.9 (s, arom.), 117.9 (s, arom.), 110.8 (d, J 7.6 Hz,
b
-
fur), 105.2 (br s, arom.), 89.4 (d, J 118.5 Hz, arom.), 55.8 (s, OCH3),
50.9 (s, COOCH3); dP (161 MHz, CD2Cl2) 4.47; HRMS (EI): Mþ,
found 454.1324. C28H23O4P requires 454.1328.
C fur), 100.9 (d, J 2.2 Hz, arom.), 89.5 (d, J 109.9 Hz, arom.), 62.0 (d, J
116.2 Hz, C1), 51.0 (s, OCH3); dP (161 MHz, CD2Cl2) 4.08; HRMS (EI):
Mþ, found 430.0787. C25H19O3PS requires 430.0787.
4.5.25. Furan-2-yl(2-methoxy-5-phenanthren-9-ylfuran-3-yl)diphe-
nylphosphonium tetrafluoroborate (37). Colorless oil, 20% yield. nmax
4.5.21. Methyl 4,5,7,7-tetraphenyl-7
carboxylate (33). Yellow oil, 40% yield. nmax (liquid film) 1695,
1600, 760e690 cmꢁ1
dH (400 MHz, CD2Cl2) 7.78 (4H, ddd, J 13.7,
7.5, 1.6 Hz, arom.), 7.58e7.52 (6H, m, arom.), 7.30 (1H, dd, J 2.2,
2.2 Hz, -H fur), 7.11e7.01 (10H, m, arom.), 6.45 (1H, dd, J 2.2, 2.2 Hz,
-H fur), 3.07 (3H, s, OCH3); dC (100.6 MHz, CD2Cl2) 168.3 (d, J
12.6 Hz, C]O), 162.6 (d, J 14.8 Hz, CePh), 145.2 (d, J 9.4 Hz, CePh),
143.0 (d, J 13.0 Hz, arom.), 141.9 (d, J 13.5 Hz, -C fur), 138.0 (s,
l
5-phosphinino[2,3-b]furan-6-
(liquid film) 1439, 1084, 750e690 cmꢁ1
;
dH (400 MHz, CD2Cl2) 8.81
(1H, dd, J 8.1, 0.8 Hz, arom.), 8.73 (1H, d, J 8.3 Hz, arom.), 8.23 (1H,
dd, J 8.1, 1.4 Hz, arom.), 8.17e8.16 (1H, m, -H fur), 8.04 (1H, s,
arom.), 7.98 (1H, dd, J 7.6, 0.8 Hz, arom.), 7.95e7.90 (2H, m, arom.),
7.83e7.65 (12H, m, arom.), 7.37e7.36 (1H, m, -H fur), 6.88 (1H,
ddd, J 3.4, 1.7, 1.7 Hz, -H fur), 6.66 (1H,d, J 3.0 Hz, -H fur), 4.13 (3H,
s, OCH3); dC (100.6 MHz, CD2Cl2) 166.6 (d, J 14.4 Hz, -C fur), 154.2
(d, J 8.1 Hz, -C fur), 148.1 (d, J 14.8 Hz, -C fur), 136.4 (d, J 2.7 Hz,
arom.), 134.9 (d, J 136.9 Hz, -C fur), 134.1 (d, J 12.1 Hz, arom.), 131.4
(d, J 8.5 Hz, -C fur), 131.1 (d, J 13.9 Hz, arom.), 130.8 (s, arom.), 129.7
;
a
a
b
b
b
b
a
a
arom.), 133.2 (d, J 11.2 Hz, arom.), 132.9 (s, arom.), 132.0 (d, J 2.2 Hz,
arom.),130.7 (d, J 97.4 Hz, arom.),130.6 (s, arom.),129.0 (d, J 13.0 Hz,
arom.), 127.7 (s, arom.), 127.0 (s, arom.), 126.0 (s, arom.), 110.7 (d, J
a
a
a
b
7.2 Hz,
b
-C fur), 108.0 (d, J 1.8 Hz, arom.), 90.2 (d, J 107.7 Hz, arom.),
(s, arom.), 129.4 (s, arom.), 129.3 (s, arom.), 128.6 (s, arom.), 128.0 (s,
arom.), 127.8 (s, arom.), 125.9 (s, arom.), 124.9 (s, arom.), 124.0 (s,
arom.), 123.2 (s, arom.), 118.3 (d, J 98.7 Hz, arom.), 113.5 (d, J 9.4 Hz,
60.3 (d, J 113.1 Hz, C1), 50.1 (s, OCH3); dP (161 MHz, CD2Cl2) 7.06;
HRMS (EI): Mþ, found 500.1522. C35H26O3P requires 500.1536.
b
-C fur), 111.7 (d, J 10.8 Hz, b-C fur), 72.1 (d, J 127.9 Hz, b-C fur), 60.0
4.5.22. Methyl 4-octyl-7,7-diphenyl-7
carboxylate (34). Yellow oil, 10% yield. nmax (liquid film) 2925,
2854, 1635, 1497, 1437, 789e692 cmꢁ1
dH (400 MHz, CD2Cl2) 7.62
(4H, dd, J 12.3, 7.0 Hz, arom.), 7.55e7.45 (6H, m, arom.), 7.40 (1H, dd,
J 2.3, 2.3 Hz, -H fur), 7.20 (1H, d, J 33.9 Hz, CH), 6.42 (1H, dd, J 2.2,
2.2 Hz, -H fur), 3.55 (3H, br s, OCH3), 2.46 (2H, t, J 7.3 Hz, CH2),
1.62e1.54 (2H, m, CH2), 1.34e1.29 (10H, m, 5CH2), 0.89 (3H, t, J
l
5-phosphinino[2,3-b]furan-6-
(s, OCH3); dP (161 MHz, CD2Cl2) ꢁ1.01; HRMS (EI): Mþ, found
525.1611. C35H26O3P requires 525.1614.
;
4.5.26. Methyl
[2,3-b]furan-6-carboxylate (38). Yellow oil, 30% yield. nmax (liquid
film) 1643, 1477, 1433, 766e690 cmꢁ1
dH (400 MHz, CD2Cl2) 8.77
(1H, d, J 8.3 Hz, arom.), 8.73 (1H, d, J 8.1 Hz, arom.), 7.90 (1H, dd, J
4-phenanthren-9-yl-7,7-diphenyl-7l
5-phosphinino
a
b
;

7402
E.D. Matveeva et al. / Tetrahedron 69 (2013) 7395e7402
7.8, 1.6 Hz, arom.), 7.87 (1H, dd, J 8.3, 1.1 Hz, arom.), 7.80e7.51 (16H,
m, arom.), 7.26 (1H, dd, J 2.3, 2.3 Hz, -H fur), 6.52 (1H, dd, J 2.4,
2.2 Hz, -H fur), 3.58 (3H, br s, OCH3); dC (100.6 MHz, CD2Cl2) 169.0
(br s, C]O), 163.3 (d, J 13.9 Hz, CH]CePhenantryl), 142.0 (d, J
13.9 Hz, -C fur), 135.7 (s, arom.), 135.4 (br s, CH]CePhenantryl),
133.3 (d, J 11.2 Hz, arom.),133.0 (s, arom.),132.7 (s, arom.),132.3 (d, J
3.1 Hz, arom.), 131.6 (d, J 95.6 Hz, arom.), 131.1 (s, arom.), 130.5 (s,
arom.), 129.1 (d, J 13.5 Hz, arom.), 129.0 (s, arom.), 128.7 (s, arom.),
127.8 (s, arom.), 127.2 (s, arom.), 126.8 (s, arom.), 126.8 (s, arom.),
References and notes
a
1. (a) Quin, L. The Heterocyclic Chemistry of Phosphorus System Based on the
Phosphorusecarbon Bond; Wiley: New York, NY; (b) Mader, M.; Bartlett, P. Chem.
Rev. 1997, 97, 1281e1301; (c) Nyulszi, L. Chem. Rev. 2001, 101, 1229e1246; (d)
Wang, Z.-X.; Schleyer, P. Helv. Chim. Acta 2001, 84, 1578e1600.
2. (a) Toshimitsu, A.; Saeki, T.; Tamao, K. J. Am. Chem. Soc. 2001, 123, 9210e9211;
(b) Heinike, J.; Gupta, N.; Surana, A.; Peulecke, N.; Witt, B.; Steinhauser, K.;
Bansal, R. K.; Jones, P. G. Tetrahedron 2001, 57, 9963e9972.
3. (a) Herwig, J.; Bohnen, H.; Scutta, P.; Sturn, S.; Van Leeuwen, P. W. N. M.;
Bronger, R. WO 0,268,434, 2002; Chem. Abstr. 2002, 627, 1571e1581. (b) Kenten,
J. H.; Von Borstel, R.; Casadei, J. M.; Kamireddy, B.; Martin, M. T.; Massey, R. J.;
Napper, A. D.; Simpson, D. M.; Smith, R. G.; Titmas, R. C.; Williams, R. O. U.S.
Patent 740,501, 1993; Chem. Abstr. 1993, 119, 210716.
b
a
123.3 (s, arom.), 123.1 (s, arom.), 110.8 (d, J 7.6 Hz, b-C fur), 103.6 (d, J
4.5 Hz, arom.), 88.8 (d, J 116.7 Hz, arom.), 61.5 (d, J 122.1 Hz, C1),
50.9 (br s, OCH3); dP (161 MHz, CD2Cl2) 5.19; HRMS (EI): Mþ, found
524.1531. C35H25O3P requires 524.1536.
4. Krebs, F. C.; Larsen, P. S.; Larsen, J.; Jacobsen, C. S.; Boutton, C.; Thorup, N. J. Am.
Chem. Soc. 1997, 119, 1208e1216.
ꢀ
€
€€
€ €
5. (a) Martinek, T.; Forro, E.; Gunther, G.; Sillanpaa, R.; Fulop, F. J. Org. Chem. 2000,
65, 316e321; (b) Bujard, M.; Gouverneur, V.; Mioskowski, C. J. Org. Chem. 1999,
65, 2119e2123.
Acknowledgements
€
6. (a) Markl, G. Angew. Chem. 1963, 75, 168; (b) Heim, U.; Pritzkow, H.; Fleischer,
€
U.; Grutzmacher, H.; Sanchez, M.; Reau, R.; Bertrand, G. Chem.dEur. J. 1996, 2,
We are grateful to the Russian Foundation for Basic Research
(Project No. 11-03-00641/12) and the Division of Chemistry and
Material Science of the Russian Academy of Science (OChNM-1 and
OChNM-9) for financial support. High resolution mass spectra were
recorded in the Department of Structural Studies of Zelinsky In-
stitute of Organic Chemistry, Moscow. R.G. is grateful to Petra
68e74.
7. (a) Matveeva, E.; Podrugina, T.; Pavlova, A.; Mironov, A.; Borisenko, A.; Gleiter,
R.; Zefirov, N. J. Org. Chem. 2009, 74, 9428e9432; (b) Matveeva, E.; Podrugina,
T.; Taranova, M.; Borisenko, A.; Mironov, A.; Gleiter, R.; Zefirov, N. J. Org. Chem.
2011, 76, 566e572; (c) Matveeva, E.; Podrugina, T.; Taranova, M.; Ivanova, A.;
Gleiter, R.; Zefirov, N. J. Org. Chem. 2012, 77, 5770e5774.
8. (a) Neiland, O.; Vanag, G. Dokl. Akad. Nauk SSSR 1964, 159, 373e376; (b) Mor-
iarty, R.; Prakash, I.; Prakash, O.; Freeman, W. A. J. Am. Chem. Soc. 1984, 106,
6082e6084; (c) Matveeva, E.; Podrugina, T.; Grishin, Y.; Pavlova, A.; Zeforiv, N.
Russ. J. Org. Chem. 2007, 43, 201e206.
€
Kramer for putting part of the draft into a readable form.
9. (a) Nekipelova, T.; Taranova, M.; Matveeva, E.; Podrugina, T.; Kuzmin, V.; Ze-
firov, N. Dokl. Chem. 2012, 447, 262e265; (b) Nekipelova, T.; Kuzmin, V.; Mat-
veeva, E.; Gleiter, R.; Zefirov, N. J. Phys. Org. Chem. 2013, 26, 137e143.
10. Belyakov, P. A.; Kadentsev, V. I.; Chizhov, A. O.; Kolotyrkina, N. G.; Shashkov, A.
S.; Ananikov, V. P. Mendeleev Commun. 2010, 20, 125e131.
Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.tet.2013.06.066.