Hetaryl-substituted phosphonium-iodonium ylides in synthesis of heterocycles

Article abstract of DOI:10.1021/jo3008836

A series of hitherto unknown hetaryl-substituted (in phosphonium part) phosphonium-iodonium ylides were synthesized. The reaction of these mixed phosphonium-iodonium ylides with acetylenes opens a way to new furyl annelated phosphinolines or unusually substituted phosphininofurans.

Full text of DOI:10.1021/jo3008836

Article
pubs.acs.org/joc
Hetaryl-Substituted Phosphonium-Iodonium Ylides in Synthesis of
Heterocycles
Elena D. Matveeva,*,†,‡ Tatyana A. Podrugina,† Marina A Taranova,† Anastasiya, M. Ivanova,†
Rolf Gleiter,§ and Nikolay S. Zefirov†,‡
†Department of Chemistry, Moscow State Lomonosov University, Russian Federation 119992, Moscow, Lenin Hills 1, Russia
‡Institute of Physiologically Active Compounds, Russian Academy of Sciences, 142432, Chernogolovka, Moscow region, Russia
§Organisch-Chemisches Institut der Universitaet Heidelberg, Im Neuenheimer Feld 270 D-69120 Heidelberg, Germany
S
* Supporting Information
ABSTRACT: A series of hitherto unknown hetaryl-substituted (in
phosphonium part) phosphonium−iodonium ylides were synthe-
sized. The reaction of these mixed phosphonium−iodonium ylides
with acetylenes opens a way to new furyl annelated phosphinolines or
unusually substituted phosphininofurans.
acetonitrile to 1 was studied by steady-state and time-resolved
methods.11 It was found that the formation of the final products
oxazole and phosphonium salt occurs in parallel processes
starting by the heterolytic C−I+−Ph cleavage followed by a 1,3-
dipolar cycloaddition.
The analogous reactions with a CC triple bond proceed
quite differently. In analogy with the CN triple bond one
anticipates the formation of the corresponding furans 3, which
have been found experimentally.12 However, the main pathway
found for this reaction was the formation of phosphinolines 4.
In other words, interaction of acetylenes with ylides 1 using
photochemical conditions led to a mixture of furans 3 and
phosphinolines 4, their ratio being dependent on the nature of
the substituents at the triple bond of acetylenes (Scheme
2).13,14
INTRODUCTION
■
The work of Wittig et al., especially the discovery of carbonyl
olefination by phosphonium ylides,1,2 has spurred the develop-
ment of the chemistry of these species and other ylides.3,4 Some
time ago, we focused our attention on mixed phosphonium−
iodonium ylides, which reveal unusual reactivity. We have
performed our studies mainly using carbonyl-stabilized mixed
ylides 1, Ph3P(IPh)CHR (RCOOC2H5, COAr), which
may be described by resonance structures 1a−d (Scheme 1).5,6
Scheme 1. Resonance Structures (a−d) of Ylide 1
Previously, we proposed a mechanism (Scheme 3) for the
formation λ5-phosphinolines and furans. Upon UV irradiation,
the C−I bond is cleaved with the formation of an electrophilic
intermediate, which interacts with the CC bond to give a
carbocation B. Subsequent intramolecular electrophilic attack to
the benzene ring attached to the phosphorus atom leads to the
formation of six-membered phosphinoline12 (path b, Scheme
3). In other words, this mechanistic scheme includes electro-
philic aromatic substitution as key mechanistic step. This idea
was supported using the corresponding ylide, in which one
phenyl substituent was replaced by a thiophene ring.14 In this
case, the electrophilic substitution prefers the thiophene ring,
known to be more inclined to undergo electrophilic
Our previous research on the chemistry of such phospho-
nium−iodonium ylides revealed several different pathways for
the reactions of these compounds, which crucially depend on
the possibility of the conjugation shown. The resonance
structure 1d clearly reveals the possibility for these ylides to
play a role as nucleophile, having a negatively charged oxygen
center. Indeed, we have shown that ylides 1 can be alkylated,
silylated, or acetylated.7,8 Moreover, we have found that
phosphonium−iodonium ylides enter into photochemical
reaction of 1,3-dipolar cycloaddition (probably via intermediacy
of transient 1.3-dipoles) with a triple CN bond to afford
triphenylphosphonium-substituted oxazoles 2; their formation
is obviously connected with a nucleophilic oxygen center of the
ylides.9,10 The mechanism of the photoinduced cycloaddition of
Received: May 10, 2012
© XXXX American Chemical Society
A
dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 2. Interaction of Acetylenes with Ylides 1
Scheme 3. Formation λ5-Phosphinolines and Furans
ing ylides 8a and 8b because the heterocycle attached to the P
center determines the tendency for electrophilic substitution.
We expect in the case of 5a less and in case of 5b more
tendency to electrophilic substitution as compared to the
phenyl ring. These ylides 8a and 8b were not described
previously in the literature, and Scheme 4 exhibits the synthetic
pathways leading to them. The desired mixed ylides 8a and 8b
were isolated in 80−95% yield as tetrafluoroborates.
The study of the photochemical reactions (2 h in CH2Cl2) of
ylide 8a with acetylenes reveals the data given in Scheme 5. In
the photochemical reaction of ylide 8a with phenylacetylene,
we isolated only the corresponding phosphinoline 9 (RPh)
in 10% yield. The isolation of this product demonstrates the
higher activity of benzene as compared the pyrazole ring in the
electrophilic substitution step. In contrast, the photochemical
reaction of the ylide 8a with 9-ethynylphenanthrene afforded
only the corresponding furan 10 (R = C14H9) in 30% yield. The
low yields are mostly due to the poor solubility of starting
material in a CH2Cl2 as well as the enhanced decomposition of
the ylide 8a to give the corresponding phosphonium salt
15
[Ph2PyrP+CH2COPh] BF4 11 (up to 70%).
−
These results have to be compared with our previous
experiments on the thiophene series 8c14 which led only to
phosphininothiophenes.
Our reactions of the ylide 8b with various acetylenes such as
phenylacetylene, 3-ethynylthiophene, 1-ethynyl-4-methoxyben-
zene, and 9-ethynylphenanthrene afforded either the furans 12
and 13 (Scheme 6) (yields 40−50%) or a new heterocyclic
system: the phosphininofurans 14 and 15 (yields 50−65%). It
is interesting to note that the reaction of ylide 8b with
phenylacetylene proceeds in seconds without UV irradiation.
A comparison between the triphenyl-substituted (1),
pyrazolyldiphenyl-substituted (8a), and thienyl-substituted
(8c) ylides with the furyl-substituted ylide 8b shows the higher
reactivity for the latter. The ylide 8b reacts vigorously in
daylight and even in the dark with high yields.
Thus, we found that interaction of benzoyl-substituted ylide
8b,c with acetylenes depends on the aryl moiety at the
acetylene unit and can lead to the selective formation of furans
(12 and 13, daylight; 16, with UV irradiation) or annelated
phosphinines, phosphininothiophene and phosphininofurans
(14 and 15, daylight; 17,14 with UV irradiation).
substitution than the phenyl ring. The present paper concerns
the future development of this idea, using furyl and pyrazolyl
derivatives, which are correspondingly more and less prone to
undergo electrophilic substitution as compared with phenyl.
RESULTS AND DISCUSSION
We chose to use furyldiphenylphosphine 5b and (pyrazolyl)-
diphenylphosphine 5a (Scheme 4) to prepare the correspond-
■
Scheme 4. Preparation of the Ylides 8
p-Methoxyphenylacetylene in reaction with the ylide (8b) in
the dark leads to formation also the furan (12) with the same
yield.
9-Ethynylphenanthrene in reaction with ylide 8b in the dark
affords two heterocyclic systems, furan (13) and phosphinino-
furan (18), with 30% and 40% yields, respectively (see Scheme
7).
All mentioned reactions are accompanied by the formation of
the corresponding phosphonium salts [Ph2HetP+CH2COPh]-
−
BF4 . The isolation of iodobenzene confirms that the C−I
bond in the ylide is cleaved.
B
dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
Scheme 5. Photochemical Reactions of Ylide 8a with Acetylenes
Scheme 6. Reactions of the Ylide 8b with Acetylenes
Scheme 7. Reaction of the Ylide 8b with 9-Ethynylphenanthrene in the Dark
°C. 1H NMR (CDCl3), δ: 3.71 (s, 3H), 6.43 (d, 2H, J = 12.4 Hz); 7.18
(dd, 1H, J = 2.0 Hz, J = 2.3 Hz); 7.43 (dd, 2H, J = 7.8 Hz, J = 7.5 Hz);
7.56 (dd, 1H, J = 7.3 Hz, J = 7.3 Hz); 7.64−7.69 (m, 4H); 7.71 (dd,
1H, J = 2.0 Hz, J = 1.5 Hz); 7.75−7.79 (m, 2H); 7.96 (ddd, 4H, J = 7.3
Hz, J = 14.1 Hz, J = 1.0 Hz); 8.31 (d, 2H, J = 7.3 Hz). 13C NMR
(CDCl3), δ: 39.7 (d, JCP = 63.6 Hz); 40.9; 117.2 (d, JCP = 92.2 Hz);
120.7 (d, JCP = 106.9 Hz); 121.6 (d, JCP = 16.9 Hz); 129.0; 130.0;
The structures of all obtained compounds were confirmed by
1H, 13C, and 31P NMR spectroscopy (see the Supporting
Information).
CONCLUSION
■
Our investigations revealed that the products of the reactions
between benzoyl-substituted phosphonium−iodonium ylides
and arylacetylenes depend on the aryl moiety and the
substituents on the phosphonium group. It can either lead to
the selective formation of furans or to annelated phosphinolines
and phosphininofurans.
130.5 (d, JCP = 13.9 Hz); 133.77 (d, JCP = 11.0 Hz); 134.82 (d, JCP
=
5.1 Hz); 135.0; 135.5; 140.0 (d, JCP = 15.4 Hz); 191.9 (d, JCP = 5.9
Hz). 31P NMR (CDCl3), δ: 8.61. IR, ν
770, 1480 (Ar). Anal. Calcd for C24H22BrN2OP: C, 61.95; H, 4.77; N,
̃
/cm−1: 1660 (CO), 730−
6.02. Found: C, 61.77; H, 4.76; N, 6.03.
Furan-2-yl(2-oxo-2-phenylethyl)diphenylphosphonium Bromide
1
(6b). Yield: 3.40 g (80%). Mp: 239−240 °C. H NMR (CDCl3), δ:
EXPERIMENTAL SECTION
■
6.39 (d, 2H, J = 12.4 Hz); 6.77−6.79 (m, 1H); 7.51 (t, 2H, J = 7.4
Hz); 7.60−7.68 (m, 5H); 7.74−7.79 (m, 2H); 7.92 (m, 1H); 7.96−
8.02 (m, 4H); 8.14 (dd, 1H, J = 1.0 Hz, J = 3.8 Hz); 8.39 (d, 2H, J =
7.3 Hz). 13C NMR (CDCl3), δ: 38.5 (d, JCP = 65.1 Hz); 113.1 (d, JCP
= 8.8 Hz); 117.6 (d, JCP = 94.4 Hz); 129.0; 130.0; 130.1 (d, JCP = 13.9
Hz); 130.8 (d, JCP = 19.8 Hz); 133.7 (d, JCP = 130.3 Hz); 133.9 (d, JCP
= 11.7 Hz); 134.9; 135.0 (d, JCP = 1.5 Hz); 152.3 (d, JCP = 8.1 Hz);
General Methods. 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 and 13C NMR
at 100 MHz. The IR spectra were measured in CCl4. The mass spectra
were obtained on a quadrupole mass spectrometer (EI, 70 eV, direct
inlet). The progress of the reactions and the purity after chromato-
graphic separation were monitored by TLC on silica gel 60 plates.
Chromatographic separation was carried out on columns with silica gel
60.
̃
191.8 (d, JCP = 5.9 Hz). 31P NMR (CDCl3), δ: 9.87. IR, ν/cm−1: 1660
(CO), 730−760, 1470 (Ar). Anal. Calcd for C24H20BrO2P: C,
64.18; H, 4.58. Found: C, 63.87; H, 4.47.
General Procedure for Preparation of Phosphonium Salts
(6a,b). Bromoacetophenone 1.57 g (7.9 mmol) was dissolved in 8 mL
of dry acetonitrile, and 7.52 mmol phosphine was added. The mixture
was stirred for 30 min, and the precipitate was filtered, washed with
acetonitrile (3 × 5 mL) and diethyl ether (5 mL), and dried at room
temperature.
General Procedure for Preparation of Phosphoranes (7a,b).
A solution of 118 mg of sodium methylate (2.2 mmol) in 1 mL of dry
methanol was added gradually to a solution of 2.15 mmol
phosphonium salt 8 in 5 mL of dry methanol at 0 to +5 °C. The
mixture was stirred for 1 h and then evaporated in vacuo, and the
residue was dissolved in 10 mL of methylene chloride. The precipitate
of sodium bromide was separated from the solution of ylides 9 by
(1-Methyl-1H-pyrazol-5-yl)(2-oxo-2-phenylethyl)-
diphenylphosphonium Bromide (6a). Yield: 2.70 g (80%). Mp: 219
C
dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
filtration, washed on the filter with methylene chloride (3 × 10 mL).
The residue was evaporated in vacuo.
Hz); 7.17 (d, 1H, J = 33.1 Hz); 7.36 (d, 1H, J = 1.8 Hz); 7.34−7.44
(m, 11H); 7.53−7.57 (m, 3H); 7.62 (dd 1H, J = 2.0 Hz, J = 1.5 Hz);
7.64−7.67 (m, 2H); 7.98 (ddd, 2H, J = 6.9 Hz, J = 13.9 Hz, J = 1.6
Hz). 13C NMR (CDCl3), δ: 30.3 (d, JCP = 120.0 Hz); 39.8; 118.0 (d,
JCP = 16.8 Hz); 124.9 (d, JCP = 11.0 Hz); 126.3 (d, JCP = 8.1 Hz);
126.5; 126.8 (d, JCP = 5.8 Hz); 127.6 (d, JCP = 94.4 Hz); 128.4 (d, JCP
= 85.6 Hz); 128.4; 128.7; 129.0; 129.1; 129.1; 130.2 (d, JCP = 7.3 Hz);
132.4; 132.6; 133.0 (d, JCP = 99.5 Hz); 133.1; 133.4 (d, JCP = 11.7 Hz);
135.0 (d, JCP = 6.5 Hz); 138.5 (d, JCP = 14.6 Hz); 140.1; 190.3. 31P
NMR (CDCl3), δ: −12.03.
1-[(1-Methyl-1H-pyrazol-5-yl)(diphenyl)phosphonio]-2-oxo-2-
phenylethanide (7a). Yield: 0.67 g (80%). Mp: 115−116 °C. 1H
NMR (CDCl3), δ: 3.79 (s, 3H); 4.58 (d, 1H, J = 27.3 Hz); 6.24 (s,
1H); 7.36−7.38 (m, 3H); 7.60−7.75 (m, 11H); 7.90−7.92 (m, 2H).
13C NMR (CDCl3), δ: 40.3, 47.7 (d, JCP = 113.4 Hz); 118.3 (d, JCP
=
15.3 Hz); 126.5 (d, JCP = 95.1 Hz); 127.2; 128.3; 128.8 (d, JCP = 104.6
Hz); 129.8 (d, JCP = 13,2 Hz); 130.1; 132.8 (d, JCP = 10.2 Hz); 133.2;
138.9 (d, JCP = 13.1 Hz); 140.8 (d, JCP = 14.6 Hz); 180.2. 31P NMR
(CDCl3), δ: 1.44. IR, ν
Anal. Calcd for C24H21NOP: C, 74.99; H, 5.51; N, 7.29. Found: C,
̃
/cm−1: 1590 (CO), 700−740, 1460 (Ar).
(1-Methyl-1H-pyrazol-5-yl)[5-(phenanthren-9-yl)-2-phenylfuran-
3-yl]diphenylphosphonium Tetrafluoroborate (10). Yield: 60 mg
1
(30%). Colorless oil. H NMR(CD2Cl2), δ: 3.50 (s, 3H); 6.80 (dd,
75.26; H, 5.31; N, 7.05.
1H, J = 2.2 Hz, J = 2.7 Hz); 6.82 (d, 1H, J = 3.9 Hz); 7.13−7.17 (m,
2H); 7.13−7.17 (m, 2H); 7.25−7.32 (m, 3H); 7.57−7.64 (m, 2H);
7.66−7.75 (m, 11H); 7.80−7.85 (m, 2H); 7.92 (dd, 1H, J = 8.0 Hz, J =
7.9 Hz); 8.08 (s, 1H); 8.20 (dd, 1H, J = 7.9 Hz, J = 1.1 Hz); 8.65 (d,
1H, J = 7.9 Hz); 8.74 (ddd, 1H, J = 7.5 Hz, J = 8.3 Hz, J = 1.4 Hz). 13C
NMR (CD2Cl2), δ: 42.3; 98.9 (d, JCP = 114.0 Hz); 114.8 (d, JCP = 12.9
Hz); 118.5 (d, JCP = 96.0 Hz); 122.1 (d, JCP = 112.8 Hz); 123.3 (d, JCP
1-[Furan-2-yl(diphenyl)phosphonio]-2-oxo-2-phenylethanide
1
(7b). Yield: 0,74 g (95%). Mp: 167−168 °C. H NMR (CD2Cl2), δ:
4.40 (d, 1H, J = 23.5 Hz); 6.63−6.64 (m, 1H); 7.21−7.22 (m, 1H);
7.39−7.40 (m, 3H); 7.40 (d, 1H, J = 1.8 Hz) 7.51−7.55 (m, 4H, J =
18.3 Hz); 7.61−7.65 (m, 2H); 7.76−7.83 (m, 5H); 7.92−7.95 (m,
2H). 13C NMR (CDCl3), δ: 47.8 (d, JCP = 117.8 Hz); 111.5 (d, JCP
=
8.0 Hz); 124.8 (d, JCP = 18.3 Hz); 126.3 (d, JCP = 96.6 Hz); 127.0;
= 18.5 Hz); 124.3; 125.1; 125.7; 126.8; 128.6; 129.0; 129.1 (d, JCP
=
127.8; 128.8 (d, JCP = 13.2 Hz); 129.6; 132.2; 132.9 (d, JCP = 11.0 Hz);
31
3.2 Hz); 129.80; 130.0; 130.3; 130.5; 130.9; 131.3; 132.3; 132.4;
132.5; 132.8 (d, JCP = 13.6 Hz); 132.9 (d, JCP = 4.0 Hz); 135.2 (d, JCP
= 11.6 Hz); 138.0 (d, JCP = 2.8 Hz); 142.2 (d, JCP = 16.5 Hz); 158.5
140.7 (d, JCP = 14.6 Hz); 149.0 (d, JCP = 4.9 Hz); 185.5.
NMR
P
(CDCl3), δ: 2.93. IR, ν
̃
/cm−1: 1590 (CO), 700−730, 1450 (Ar).
Anal. Calcd for C24H19O2P: C, 77.83; H, 5.17. Found: C, 77.65; H,
(d, JCP = 15.7 Hz); 164.9 (d, 9JCP = 18.5 Hz). 31P NMR (CD2Cl2), δ:
5.25.
−
2.49. IR, ν
̃
/cm−1: 1070 (BF4 ), 700−760, 1470 (Ar). HRMS: calcd for
General Procedure for Preparation of Phosphonium−
Iodonium Ylides (8a,b). A solution of 1.3 mmol of diacetox-
yiodobenzene in 3 mL of methanol was added to the solution of 1.3
mmol ylide 7 in 2 mL of methanol at 0−5 °C, and then 1.3 mmol of a
solution of HBF4 (40%) was added at 0−5 °C. The mixture was stirred
for 1 h, 10 mL of diethyl ether was added, and the mixture was stirred
for 1 h. The precipitate was filtered and washed with diethyl ether.
1-[(1-Methyl-1H-pyrazol-5-yl)(diphenyl)phosphonio]-2-oxo-2-
phenyl-1-(phenyliodonio)ethanide tTetrafluoroborate (8a). Yield:
0,69 g (80%). Mp: 158 °C. 1H NMR (CD3CN), δ: 3.50 (s, 3H); 6.50
(dd, 1H, J = 2.0 Hz, J = 2.3 Hz); 7.20 (d, 2H, J = 7.8 Hz); 7.43 (dd,
2H, J = 7.9 Hz, J = 8.0 Hz); 7.51−7.57 (m, 3H); 7.61−7.68 (m, 11H);
7.70 (dd, 1H, J = 2.0 Hz, J = 1.5 Hz); 7.78−7.83 (m, 2H). 13C NMR
(CD3CN), δ: 40.3; 120.4 (d, JCP = 17.5 Hz); 122.1 (d, JCP = 96.5 Hz);
125.8 (d, JCP = 108.3 Hz); 127.6; 128.6; 129.9 (d, JCP = 13.2 Hz);
130.8; 131.9; 132.6; 133.2 (d, JCP = 8.0 Hz); 133.2; 134.3; 138.8 (d,
C40H30N2OP (M+) m/z 585.2090, found 585.2077.
General Procedure for the Reaction of Ylides (8b,c14) with
Alkynes. The alkyne was added to a solution of ylide 8b,c (0.3 mmol)
in anhydrous methylene chloride. The mixture was stirred under argon
atmosphere. 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 chromato-
graphed on silica gel. Benzene was used to elute the residual alkynes
and PhI; the corresponding phosphinoline was eluted by using a
CH2Cl2/MeOH mixture in a ratio of 200:1, the furans were eluted by
using a CH2Cl2/CH3CN mixture in a ratio of 5:1.
2,3-Dihydrofuran-2-yl[5-(4-methoxyphenyl)-2-phenylfuran-3-yl]-
diphenylphosphonium Tetrafluoroborate (12). Yield: 70 mg (40%).
Colorless oil. 1H NMR (CDCl3), δ: 3.86 (s, 3H); 6.63 (d, 1H, J = 4.0
Hz); 6.76−6.77 (m, 1H.); 6.98 (d, 2H, J = 8.8 Hz); 7.13−7.17 (m,
2H); 7.22−7.23 (m, 2H); 7.26−7.30 (m, 1H); 7.34−7.35 (m, 1H);
7.68−7.78 (m, 10H); 7.82−7.86 (m, 2H); 8.01−8.02 (m, 1H). 13C
NMR (CD2Cl2), δ: 57.0; 98.8 (d, JCP = 115.7 Hz); 109.0 (d, JCP =12.5
Hz); 114.6 (d, JCP = 9.6 Hz); 116.2; 118.5 (d, JCP = 97.6 Hz); 122.3;
127.8; 128.9; 129.8; 130.2; 132.3 (d, JCP = 13.7 Hz); 132.3; 132.6 (d,
JCP = 20.5 Hz); 135.1 (d, JCP = 135.7 Hz); 135.3 (d, JCP = 11.6 Hz);
137.65 (d, JCP = 3.21 Hz); 155.5 (d, JCP = 8.0 Hz); 158.6 (d, JCP =15.3
JCP = 8.1 Hz); 139.5 (d, JCP = 15.4 Hz); 192.1 (d, JCP = 6.6 Hz). 31P
−
NMR (CD3CN), δ: 12.89. IR, ν
̃
/cm−1: 1600 (CO), 1080 (BF4 ),
740−750, 1470 (Ar). Anal. Calcd for C30H26BF4IN2OP: C, 53.36; H,
3.88; N, 4.15. Found: C, C, 53.29; H, 3.93, N, 3.95.
1-[Furan-2-yl(diphenyl)phosphonio]-2-oxo-2-phenyl-1-
(phenyliodonio)ethanide Tetrafluoroborate (8b). Yield: 0,82 g
(95%). Mp: 155 °C. 1H NMR(CD3CN), δ: 6.84−7.86 (m, 1H);
7.14−7.18 (m, 1H); 7.36−7.40 (m, 6H); 7.46−7.76 (m, 14H); 8.11−
8.14 (m., 1H). 13C NMR (CD3CN), δ: 113.8 (d, 8JCP = 8.8 Hz); 123.5
(d, JCP = 98.1 Hz); 128.9; 129.8; 129.9 (d, JCP = 19.0 Hz); 130.9 (d,
JCP = 13.9 Hz); 131.9; 133.0; 133.4; 134.6 (d, JCP = 11.0 Hz); 135.5;
140.1 (d, JCP = 131.0 Hz); 140.1 (d, JCP = 6.6 Hz); 153.3 (d, JCP = 7.3
Hz); 162.5; 164.0 (d, JCP =19.3 Hz). 31P NMR (CD2Cl2), δ: 3.39. IR,
−
ν
̃
/cm−1: 1030−1100 (BF4 ), 710−740, 1450 (Ar). HRMS: calcd for
C33H26O3P (M+) m/z 501.1614, found 501.1611.
Furan-2-yl[5-(phenanthren-9-yl)-2-phenylfuran-3-yl]-
diphenylphosphonium Tetrafluoroborate (13). Yield: 98 mg (50%).
1
Hz); 192.9. 31P NMR (CD3CN), δ: 14.60. IR, ν
1070−1110 (BF4 ), 740, 1470 (Ar). Anal. Calcd for C30H23BF4IO2P:
C, 54.58; H, 3.51. Found: C, 54.81; H, 3.73.
̃
/cm−1: 1540 (CO),
Colorless oil. H NMR (CD2Cl2), δ: 6.81 (m, 1H); 6.93 (d, 1H, J =
−
4.1 Hz); 7.22−7.26 (m, 2H); 7.37−7.40 (m, 4H); 7.70−7.95 (m,
14H); 8.04 (d, 1H, J = 7.9 Hz); 8.08−8.09 (m, 1H); 8.20 (s, 1H); 8.37
(dd, 1H, J = 8.1 Hz, J = 8.4 Hz); 8.77 (d, 1H, J = 8.4 Hz); 8.85 (d, 1H,
J = 8.1 Hz). 13C NMR (CD2Cl2), δ: 97.8 (d, JCP = 115.6 Hz); 113.6 (d,
JCP = 9.6 Hz); 114.1 (d, JCP = 12.5 Hz); 117.4 (d, JCP = 97.6 Hz);
123.3; 124.0; 124.9; 125.9; 127.8; 127.9; 128.0 (d, JCP = 4.1 Hz);
General Procedure for the Reaction of Ylides (8a) with
Alkynes. The ylide (0.3 mmol) was added gradually to a solution of
alkynes (0.9 mmol) in anhydrous dichloromethane. The reactions
were irradiated in a quartz flask with a mercury lamp (366 nm) source
under argon atmosphere. The progress of the reaction was monitored
by TLC. After the end of the reaction, the mixtures were concentrated
in vacuo. The residue was dissolved in a minimum of CH2Cl2 and
chromatographed on silica gel. Benzene was used to elute phenyl-
acetylene and PhI; the corresponding phosphinoline was eluted by
using a CH2Cl2/MeOH mixture in a ratio of 200:1, the furan was
eluted by using a CH2Cl2/CH3CN mixture in a ratio of 5:1.
128.9; 129.0; 129.3; 129.3; 129.9 (d, JCP = 13.2 Hz); 131.3 (d, JCP
14.0 Hz); 131.4 (d, JCP = 7.7 Hz); 131.5; 131.7; 131.9; 134.1 (d, JCP
=
=
136.1 Hz); 134.3 (d, JCP = 11.6 Hz); 136.7 (d, JCP = 2.8 Hz); 154.5 (d,
JCP = 8.0 Hz); 156.9 (d, JCP = 15.3 Hz); 164.3 (d, JCP = 18.8 Hz). 31
P
−
NMR (CD Cl ), δ: 1.41. IR, ν/cm−1: 1070 (BF ), 730−760, 1470
̃
2
2
4
(Ar). HRMS: calcd for C40H28O2P (M+) m/z 571.1821, found
571.1817.
[1-(1-Methyl-1H-pyrazol-5-yl)-1,4-diphenyl-1λ5-phosphinolin-2-
yl](phenyl)methanone (9). Yield: 15 mg (10%). Red oil. 1H
NMR(CDCl3), δ: 3.86 (s, 3H); 6.69 (dd, 1H, J = 2.0 Hz, J = 2.0
Phenyl(4,7,7-triphenyl-7λ5-phosphinino[2,3-b]furan-6-yl)-
methanone (14). Yield: 71 mg (50%). Red oil. 1H NMR (CDCl3), δ:
6.51 (dd, 1H, J = 2.3 Hz, J = 2.2 Hz); 7.22−7.26 (m, 1H); 7.42 (d, 1H,
D
dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Article
J = 34.1 Hz); 7.35−7.39 (m, 2H); 7.42−7.47 (m, 3H); 7.46 (dd, 1H, J
= 2.2 Hz, J = 2.3 Hz); 7.50−7.57 (m, 8H); 7.67−7.69 (m, 2H); 7.86
ASSOCIATED CONTENT
■
S
* Supporting Information
(dd, 4H, J = 7.6 Hz, J = 13.9 Hz). 13C NMR (CDCl3), δ: 78.9 (d, JCP
=
1H, 31P, and 13C NMR spectra of the new compounds 6−10,
12−16, and 18. This material is available free of charge via the
Internet at http://pubs.acs.org.
103.9 Hz); 91.5 (d, JCP = 104.7 Hz); 107.0 (d, JCP = 2.9 Hz); 110.7 (d,
JCP = 7.3 Hz); 125.8; 127.2 (d, JCP = 98.1 Hz); 127.6; 128.1; 128.3;
2
128.5 (d, JCP = 13.2 Hz); 128.7; 129.7; 131.6; 132.9 (d, arom., JCP
=
11.7 Hz); 133.4 (d, JCP = 8.1 Hz); 138.1; 140.2 (d, JCP = 8.8 Hz);
141.2 (d, JCP = 13.2 Hz); 161.4 (d, JCP = 12.5 Hz); 191.6 (d, JCP = 5.9
AUTHOR INFORMATION
Corresponding Author
*E-mail: matveeva@org.chem.msu.ru.
Notes
■
Hz). 31P NMR (CDCl3), δ: 2.09. IR, ν
̃
/cm−1: 1520−1590 (CO),
710−740, 1470 (Ar). HRMS: calcd for C32H23O2P (M+) m/z
470.1436, found 470.1418.
[7,7-Diphenyl-4-(thiophene-3-yl)-7λ5-phosphinino[2,3-b]furan-6-
1
The authors declare no competing financial interest.
yl](phenyl)methanone (15). Yield: 93 mg (65%). Red oil. H NMR
(CD2Cl2), δ: 6.42 (dd, 1H, J = 2.0 Hz, J = 2.6 Hz); 7.15−7.19 (m,
2H); 7.42 (d, 1H, J = 36.2 Hz); 7.32−7.36 (m, 3H); 7.40 (dd, 1H, J =
3.43 Hz, J = 1.87 Hz); 7.41−7.49 (m, 7H); 7.51−7.54 (m, 2H); 7.72
(dddd, 4H, J = 6.7 Hz, J = 14.0 Hz, J = 1.4 Hz, J = 1.7 Hz). 13C NMR
(CD2Cl2), δ: 80.1 (d, JCP = 104.0 Hz); 93.0 (d, JCP = 104.0 Hz); 103.8
(d, JCP = 4.4 Hz); 112.2 (d, JCP = 7.3 Hz); 119.9; 126.2; 128.3; 128.9
(d, JCP = 97.6 Hz); 129.7; 130.1; 130.1 (d, JCP = 13.0 Hz); 131.3; 133.3
(d, JCP = 3.2 Hz); 133.8 (d, JCP = 8.8 Hz); 134.45 (d, JCP = 11.6 Hz);
139.8; 141.9 (d, JCP = 8.8 Hz); 143.1 (d, JCP = 13.2 Hz); 162.9 (d, JCP
ACKNOWLEDGMENTS
■
We are grateful to the Russian Foundation for Basic Research
(Project No. 11-03-00641) and the Division of Chemistry and
Materials Science of the Russian Academy of Sciences
(OChNM-1, and OChNM-9).
REFERENCES
■
(1) (a) Wittig, G. Acc. Chem. Res. 1974, 7, 6−14. (b) Maryanoff, B.
E.; Reitz, A. B. Chem. Rev. 1989, 89, 863−927.
(2) Taillefer, M.; Cristau, H. J. Top. Curr. Chem. 2003, 229, 41−73.
(3) Neiland, O.; Vanag, G. Dokl. Acad. Nauk SSSR. 1964, 159, 373−
376.
(4) Moriarty, R. M.; Prakash, I.; Prakash, O.; Freeman, W. A. J. Am.
Chem. Soc. 1984, 106, 6082−6084.
(5) Zhdankin, V. V.; Maydanovych, O.; Herschbach, J.; Bruno, J.;
Matveeva, E. D.; Zefirov, N. S. J. Org. Chem. 2003, 68, 1018−1023.
(6) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Takachev, V.
V.; Zhdankin, V. V.; Aldoshin, S. M.; Zefirov, N. S. Russ. J. Org. Chem.
2003, 39, 536−541.
(7) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Pavlova, A. S.;
Zefirov, N. S. Russ. J. Org. Chem. 2007, 43, 201−206.
(8) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Zefirov, N. S. Russ. Chem. Bull. 2008, 57, 400−405.
(9) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Zefirov, N. S. Russ. Chem. Bull. 2008, 57, 2237−2239.
(10) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A.
V.; Gleiter, R.; Zefirov, N. S. Eur. J. Org. Chem. 2009, 14, 2323−2327.
(11) Nekipelova, T. D.; Kuzmin, V. A.; Matveeva, E. D.; Gleiter, R.;
Zefirov, N. S. J. Phys. Org. Chem. 2012, DOI: 10.1002/poc.2972.
(12) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A.
V.; Borisenko, A. A.; Gleiter, R.; Zefirov, N. S. J. Org. Chem. 2009, 74,
9428−9432.
(13) Matveeva, E. D.; Gleiter, R.; Zefirov, N. S. Russ. Chem. Bull.
2010, 59, 488.
(14) Matveeva, E. D.; Podrugina, T. A.; Taranova, M. A.; Borisenko,
A. A.; Mironov, A. V.; Gleiter, R.; Zefirov, N. S. J. Org. Chem. 2011, 76,
566−572.
= 12.9 Hz); 192.7 (d, JCP = 5.6 Hz) 31P NMR (CDCl3), δ: 1.54. IR, ν
̃
/
cm−1: 1520−1580 (CO), 710−760, 1470 (Ar). HRMS: calcd for
C30H21O2PS (M+) m/z 476.0999, found 476.0985.
[5-(Phenanthren-9-yl)-2-phenylfuran-3-yl](diphenyl)thiophene-
2-ylphosphonium Tetrafluoroborate (16). Yield: 142 mg (70%).
Colorless oil (reaction with UV irradiation with a mercury lamp (366
nm)). 1H NMR (CD2Cl2), δ: 6.82 (d, 1H, J = 4.0 Hz); 7.18 (dd, 2H, J
= 7.3 Hz, J = 8.1 Hz); 7.32−7.35 (m, 3H); 7.43−7.45 (m, 1H);7.66−
7.90 (m, 15H); 8.00 (d, 1H, J = 7.8 Hz); 8.15 (s, 1H); 8.22 (dt, 1H, J
= 4.8 Hz, J = 1.3 Hz); 8.31 (dd, 1H, J = 8.1 Hz, J = 1.5 Hz); 8.74 (d,
1H, J = 8.3 Hz); 8.83 (d, 1H, J = 8.3 Hz). 13C NMR (CD2Cl2), δ: 99.1
(d, JCP = 114.1 Hz); 113.8 (d, JCP = 12.5 Hz); 116.6 (d, JCP = 98.8
Hz); 118.6 (d, JCP = 96.6 Hz); 122.7; 123.4; 124.3; 125.3; 127.3;
127.5; 128.3; 128.7; 129.3; 130.0; 130.7 (d, JCP = 13.9 Hz); 130.7 (d,
JCP = 16.1 Hz); 130.9; 133.7 (d, JCP = 11.0 Hz); 136.0; 140.5 (d, JCP
=
5.1 Hz); 143.0 (d, JCP = 11.0 Hz); 156.1 (d, JCP = 16.1 Hz); 163.1 (d,
−
̃
JCP = 17.6 Hz). 31P NMR (CD2Cl2), δ: 7.95. IR, ν/cm−1: 1070 (BF4 ),
730−760, 1470 (Ar). HRMS: calcd for C40H28OPS (M+) m/z
587.1593, found 587.1593.
Phenyl(4,7,7-triphenyl-7λ5-phosphinino[2,3-b]thiophene-6-yl)-
methanone (17). Yield: 44 mg (30%). Red oil (reaction with UV
1
irradiation with a mercury lamp (366 nm)). H NMR (CD2Cl2), δ:
7.04 (dd, 1H, J = 5.3 Hz, J = 3.6 Hz); 7.10 (dd, 1H, J = 5.3 Hz, J = 2.8
Hz); 7.17 (d, 1H, J = 34.0 Hz); 7.24−7.28 (m, 1H); 7.34−7.38 (m,
2H); 7.40−7.43 (m, 3H); 7.50−7.60 (m, 8H); 7.62−7.64 (m, 2H);
7.82−7.87 (m, 4H). 13C NMR (CD2Cl2), δ: 78.5 (d, JCP = 103.4 Hz);
107.0 (d, JCP = 90.8 Hz); 113.5 (d, JCP = 8.1 Hz); 122.1 (d, JCP = 16.5
Hz); 127.1; 128.1 (d, JCP = 98.8 Hz); 128.6; 128.8; 129.1; 129.1 (d, JCP
= 13.3 Hz); 129.1; 129.2 (d, JCP = 11.1 Hz); 130.2; 132.2 (d, JCP = 7.6
Hz); 132.3 (d, JCP = 3.2 Hz); 133.6 (d, JCP = 11.2 Hz); 141.2 (d, JCP
=
(15) The decomposition of ylides to give the corresponding
phosphonium salt is the common phenomenon, which we have
observed in many different related photochemical processes. This
reaction is under careful investigation, using deuterium labeling,
because the source of two hydrogens is not absolutely clear yet.
9.3 Hz); 142.8; 154.2 (d, JCP = 8.0 Hz); 191.5 (d, JCP = 5.6 Hz) 31P
NMR (CD2Cl2), δ: 1.97. MS, m/z: 486 [M]+, 409 [M − C6H5]+, 381
[M − PhCO]+, 183 [Ph2P − 2H]+.
[4-(Phenanthren-9-yl)-7,7-diphenyl-7λ5-phosphinino[2,3-b]-
furan-6-yl](phenyl)methanone (18). Yield: 68 mg (40%). Red oil. 1H
NMR (CD2Cl2), δ: 6.45 (dd, 1H, J = 2.2 Hz, J = 2.3 Hz); 7.23 (d, 1H,
J = 36.4 Hz); 7.21 (dd, 1H, J = 2.4 Hz, J = 2.1 Hz); 7.22−7.25 (m,
3H); 7.42−7.58 (m, 12H); 7.66 (s, 1H); 7.76−7.87 (m, 6H); 8.61 (d,
1H, J = 8.3 Hz); 8.66 (d, 1H, J = 8.3 Hz). 13C NMR (CD2Cl2), δ: 80.1
(d, JCP = 104.0 Hz); 92.6 (d, JCP = 104.0 Hz); 107.2 (d, JCP = 1.6 Hz);
112.2 (d, JCP = 6.8 Hz); 124.1; 124.4; 127.9; 128.0; 128.; 128.7; 129.6;
129.7; 130.0; 130.2 (d, JCP = 13.6 Hz); 131.2 (d, JCP = 92.4 Hz); 131.2;
131.6; 133.4 (d, JCP = 3.3 Hz); 133.5; 133.9; 134.6 (d, JCP = 11.6 Hz);
135.7 (d, JCP = 8.1 Hz); 136.5; 139.6 (d, JCP = 7.7 Hz); 141.6 (d, JCP
=
8.8 Hz); 143.5 (d, JCP = 13.7 Hz); 163.8; 192.4. 31P NMR (CD2Cl2),
δ: 4.37. IR, ν
̃
/cm−1: 1520−1580 (CO), 700−800, 1470 (Ar).
HRMS: calcd for C40H27O2P (M+) m/z 570.1743, found 570.1722.
E
dx.doi.org/10.1021/jo3008836 | J. Org. Chem. XXXX, XXX, XXX−XXX