Photochemical synthesis of phosphinolines from phosphonium-iodonium ylides

Article abstract of DOI:10.1021/jo101993a

We describe three different series of experiments which were undertaken to test our hypothesis that during irradiation of phosphonium-iodonium ylides (1a, 1b) an electrophilic carbene is generated. By opposing the assumed intermediate to monosubstituted alkynes, we observed in the case of electron-rich substituents at the triple bond a domination of a 1,3-dipolar cycloaddition of the intermediate with the triple bond to yield furans. In the case of electron poorer substituents, the formation of phosphinolines prevails. A second series of experiments was carried out with mixed ylides in which one phenyl ring at the triarylphosphonium group was replaced by a thienyl group. In this case, we observe only an intramolecular reaction with the thienyl ring to yield the phosphinolines 21-23. In a third test, we replaced in the mixed ylides 1a, 1b the COR group by a CN substituent. This modification leads to phosphinolines only and avoids a 1,3-dipolar cycloaddition.

Full text of DOI:10.1021/jo101993a

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Photochemical Synthesis of Phosphinolines from
Phosphonium-Iodonium Ylides
Elena D. Matveeva,*,§,† Tatyana A. Podrugina,† Marina A. Taranova,†
Anatolyi A. Borisenko,† Andrey V. Mironov,† Rolf Gleiter,‡ and Nikolay S. Zefirov†
†Department of Chemistry, Moscow State Lomonosov University, Moscow, Lenin Hills, 1, Russian
Federation 119992 , and ‡Organisch-Chemisches Institut der Universitaet Heidelberg, Im Neuenheimer Feld
270, D-69120 Heidelberg, Germany
matveeva@org.chem.msu.ru
Received October 13, 2010
We describe three different series of experiments which were undertaken to test our hypothesis that
during irradiation of phosphonium-iodonium ylides (1a, 1b) an electrophilic carbene is generated.
By opposing the assumed intermediate to monosubstituted alkynes, we observed in the case of
electron-rich substituents at the triple bond a domination of a 1,3-dipolar cycloaddition of the
intermediate with the triple bond to yield furans. In the case of electron poorer substituents, the
formation of phosphinolines prevails. A second series of experiments was carried out with mixed
ylides in which one phenyl ring at the triarylphosphonium group was replaced by a thienyl group. In
this case, we observe only an intramolecular reaction with the thienyl ring to yield the phosphinolines
21-23. In a third test, we replaced in the mixed ylides 1a, 1b the COR group by a CN substituent. This
modification leads to phosphinolines only and avoids a 1,3-dipolar cycloaddition.
Introduction
phosphonium-iodonium ylides (1) which are readily avai-
lable.4 Research on these species indicates5 that their electron-
ic ground state may be circumscribed by resonance struc-
tures a-d as shown in Scheme 1 for 1a. The significant
contribution of the highly polar resonance structure d to the
ground state rationalizes very well the observed reactivity of
1a (see Scheme 2). This reagent can be O-alkylated, O-acylated,
and O-silylated.6 The reaction of 1a or 1b with nucleophiles
such as halogen anions or alkyl- or aryl-sulfides replaces the
phenyl-iodonium substituent from 1.6b,7
Highly reactive species, such as carbenes,1 1,3-dipoles,2 or
ylides,3 to name only a few, are of great significance in organ-
ic synthesis. Special interest has arisen lately for the mixed
§Fax: 007 (495) 939 0290
(1) (a) Jones, Jr. M.; Moss, R. A., Carbenes; J. Wiley & Sons: New York,
1973; Vol. 1, p 2. (b) Regitz, M., Ed. Methoden der organischen Chemie
(Houben-Weyl) ; Georg Thieme: Stuttgart, Germany, 1989; p E 19b.
(2) (a) Padwa, A., Ed. 1,3-Dipolar Cycloaddition Chemistry; Wiley:
New York, 1984. (b) Huisgen, R. In Advances in Cycloaddition; Curran,
D. P., Ed.; JAI Press: Greenwich, CT, 1988; Vol. 1, pp 11-31. (c) Cinquini,
M.; Cozzi, F. In Stereoselective Synthesis (Houben-Weyl); Helmchen, G.,
Hoffmann, R. W., Mulzer, J., Schaumann, E., Eds.; Georg Thieme: Stuttgart,
Germany, 1996; Vol. E21, pp 2953-2087.
(3) (a) Wittig, G. Angew. Chem. 1980, 92, 671–675. (b) Johnson, A. W.
Ylides and Imines of Phosphorus; Wiley: New York, 1993. (c) Tallefer, M.;
Cristeau, H.-J. Top. Curr. Chem. 2003, 229, 41–73.
(4) (a) Zefirov, N. S. Pure Appl. Chem. 1996, 68, 881–890. (b) Kasumov,
T. M.; Koz’min, A. S.; Zefirov, N. S. Russ. Chem. Rev. 1997, 66, 936–952.
(c) Pirkuliev, N. S.; Brei, V. K.; Zefirov, N. S. Russ. Chem. Rev. 2000, 69, 118–
133. (d) Zhdankin, V. V.; Stang, P. J. Chem. Rev. 2002, 102, 2523–2584.
(e) Matveeva, E. D.; Proskurina, M. V.; Zefirov, N. S. Heteroat. Chem. 2006,
17, 595–617.
(5) (a) Moriarty, R. M.; Prakash, I.; Prakash, O.; Freeman, W. A. J. Am.
Chem. Soc. 1984, 106, 6082–6084. (b) Zhdankin, V. V.; Maydanovych, O.;
Hushbach, J.; Bruno, J.; Matveeva, E. D.; Zefirov, N. S. Tetrahedron Lett.
2002, 43, 2359–2361. (c) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.;
Takachev, V. V.; Zhdankin, V. V.; Aldoshin, S. M.; Zefirov, N. S. Zh. Org.
Chem. 2003, 39, 536–541.
(6) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Pavlova, A. S.;
Zefirov, N. S. Zh. Org. Chem. 2007, 43, 209–214.
(7) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Zefirov, N. S. Russ. Chem. Bull. Int. Ed. 2008, 57, 400–405.
566 J. Org. Chem. 2011, 76, 566–572
Published on Web 12/22/2010
DOI: 10.1021/jo101993a
r
2010 American Chemical Society

Matveeva et al.
JOCArticle
SCHEME 1. Resonance Structures (a-d) of Ylide 1
SCHEME 2. Generation of 2 by Photolysis of 1
SCHEME 3. Reaction of 2 with Alkyne 3a
of 4. In this paper, we will present our results by reacting
various electron-rich alkynes with 1 and by using a mixed
ylide in which one aryl ring in the triphenylphosphonium
group is replaced by a more nucleophilic thiophen ring.
Results and Discussion
Preparation of Starting Materials. The preparation of the
phosphonium-iodonium ylides 1d and 1e commenced with
the synthesis of the phosphonium salts 8d and 8e from
bromoacetophenone (6) and 2-thienyldiphenylphosphane
(7d) and 3-thienyldiphenylphosphane (7e). The synthesis
was carried out in acetonitrile (MeCN) (Scheme 4).
The phosphonium salts 8d and 8e were converted to the
ylides 9d and 9e by treatment with sodium methoxide in dry
methanol between 0 and 5 °C (Scheme 5). By treatment of 9d
and 9e with diacetoxyiodobenzene followed by HBF4, the
desired mixed ylides 1d and 1e were isolated in 80-85% yield
as tetrafluoroborates.
Reaction of 1b with Alkynes. The irradiation of the ylide 1b
with four different acetylenes (10-13) yielded a mixture of
the phosphinolines (14-17) and furans (18-21) as summa-
rized in Scheme 6.
These data show a decrease of the yield of the phosphino-
lines and an increase of the yield of furans with increasing the
π-system of the substituent at the alkyne. To rationalize the
result just discussed, we assume two competing reaction
paths: (a) a 1,3-dipolar cycloaddition of the intermediate 2
and the alkyne 3 as described in the left part of Scheme 3, and
(b) an electrophilic attack of the alkyne to the intermediate
with subsequent cycloaddition as described in the right part
of Scheme 3 by the sequence B-C-4. If the positive charge at
the vinylic carbon of B is strongly localized, the formation of
4 competes successfully with the 1,3-dipolar cycloaddition to
5. However, if the positive charge at the vinylic carbon of B is
delocalized by an extended π-system, the 1,3-dipolar cyclo-
addition prevails.
A second test for the proposed mechanism in Scheme 3 is
the reaction with the ylides 1d and 1e. These ylides provide
two different aryl groups at the positively charged phos-
phorus center: two phenyl rings and only one thienyl ring.
The latter is electron richer than the phenyl ring as shown by
the first ionization energies (thiophene, 8.87 eV;10 benzene,
aPath a yields furan 5. Path b yields the intermediates B and C via the
transition state A to 4.
Recently, we discovered a new reaction path of mixed
ylides by irradiation of 1 in presence of triple bonds. Irradia-
tion of 1a or 1b with nitriles as solvents yielded oxazoles.8
The reaction with a monosubstituted alkyne, 3, is shown in
Schemes 2 and 3 as an example.8 In this sequence, it is assumed
that the irradiation of 1 yields the short-lived intermediate 2.
The highly electrophilic species 2 reacts with the alkyne 3 via
the intermediates B and C to 4.9 As a side product, 2 reacts
via a 1,3-dipolar cycloaddition with 3 to the furan 5. On the
basis of theses schemes, we expect that the stabilization of the
vinylic cation B by electron-rich substituents R2 should favor
the production of 4. Furthermore, the nucleophilicity of the
aryl ring at the phosphorus in B should favor the formation
(8) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Gleiter, R.; Zefirov, N. S. Eur. J. Org. Chem. 2009, 74, 2323–2327.
(9) 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.
(10) Eland, J. H. O. Int. J. Mass Spectrom. Ion Phys. 1969, 2, 471–484.
J. Org. Chem. Vol. 76, No. 2, 2011 567

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SCHEME 4. Preparation of the Thienyl-Phenylphosphonium Salts 8d and 8e
SCHEME 5. Preparation of the Mixed Ylides 1d and 1e via the Ylides 9d and 9e, Respectively
SCHEME 6. Preparation of the Phospholines 14-17 and Furans 18-21 by Irradiation of 1b with the Alkynes 10-13
9.24 eV11). Thus, we can expect for path b a preference of the
reaction with the thiophene ring. In Scheme 7, we have
summarized the experimental results.
When a solution of 1d and phenyl acetylene was irradiated
in CH2Cl2, we obtained 22 in 30% yield. When 1e was treated
in the same way, a mixture of 23 and 24 was isolated as red oil
in 25% yield together. A reaction with the phenyl rings was
not observed.
When the benzoyl substituent in 1b or the carbonylethoxy
substituent in 1a is replaced by a CN group, we expect for the
reaction with alkynes no 1,3-dipolar cycloadditions to furans.
This was indeed the case. By using 1c (Scheme 8) and the
alkynes 3, 10, 11, 25, and 26, we obtained phosphinolines
27-31. The lower yields of cyano-substituted phosphino-
lines as compared to benzoyl-substituted is due to the for-
mation of 32. The reagent 1c acts also as a base to abstract the
hydrogen of the substituted phenyl ring. In the case of 1,1,4-
triphenyl-1λ5-phospholine-2-carbonitrile (27), we were able
to study the molecular structure by means of the X-ray
technique on single crystals. As shown before,9 the 10-
membered ring system is almost planar. Indeed, the calcula-
tion of puckering of 6-membered phosphinoline ring gave
puckering amplitude ‘S’=0.394, polar angle θ=61.62, S(2)=
0.347, ψ =24.82, S(3) =0.18712 with ring conformation in-
termediate between screw-boat and boat. The bond lengths
˚
˚
in the heterocyclic ring are P-C2=1.721 A, C2-C3=1.432 A,
˚
˚
C3-C4 = 1.362 A, and C4-C10 = 1.458 A and these values
are similar to those obtained for related phosphinolines.9
Conclusion
The yields of the phosphinolines 14-17 and the furans
18-21 vary considerably in the light-induced reaction of
1b with monosubstituted alkynes (3-ethynylthiophene (10),
(12) (a) Zefirov, N. S.; Palyulin, V. A.; Dashevskaya, E. E. J. Phys. Org.
Chem. 1990, 3, 147–158. (b) Zotov, A.Yu.; Paljulin, V. A.; Zefirov, N. S.
J. Chem. Inf. Comput. Sci. 1997, 37, 766–773.
(11) Clark, I. D.; Frost, D. C. J. Am. Chem. Soc. 1967, 89, 244–247.
568 J. Org. Chem. Vol. 76, No. 2, 2011

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SCHEME 7. Light-Induced Reaction of 1d and 1e, Respectively, To Yield 22 and 23 þ 24, Respectively
SCHEME 8. Light-Induced Reaction of lc with the Alkynes 3,10, 11, 25, and 26 To Yield the Phosphinolines 27-31 as well as 32
p-methoxy-phenylacetylene (11), 2-ethinyl-6-methoxynaphth-
alene (12), and 9-ethynylphenanthrene (13)). The more ex-
tended the π-system at the alkyne unit was, the higher was the
yield of the furans and the lower the yields of the phospho-
lines. These trends could be ascribed to the electrophilicity of
the intermediate vinylic cation at the former triple bond. The
results summarized in Schemes 7 and 8 corroborate our
picture of an electrophilic reaction of the aryl rings and that
1,3-dipolar cycloadditions are restricted to carbonyl substit-
uents at the phosphonium-iodonium ylides.
General Procedure for Preparation of Phosphonium Salts (8 d,
8e). Bromoacetophenone 1.48 g (7.43 mmol) was dissolved in 8
mL of dry acetonitrile, and 2.00 g (7.43 mmol) of thienyldiphe-
nylphosphine was added. The mixture was stirred for 30 min, the
precipitate was filtered, washed with acetonitrile (3 ꢀ 5 mL) and
diethyl ether (5 mL), and dried at room temperature.
(2-Oxo-2-phenylethyl)(diphenyl)2-thienylphosphonium Bromide
(8d.. Yield: 2.43 g (70%). Mp: 209-210 °C. 1H NMR (CDCl3), δ:
6.33 (d, 2H, J = 12.3 Hz); 7.36 (ddd, 1H, J = 4.8 Hz, J = 3.9 Hz,
J = 2.2 Hz); 7.55-7.59 (m, 1H); 7.60-7.65 (m, 4H); 7.70-7.75
(m, 2H); 7.91-7.97 (m, 4H); 7.99 (ddd, 1H, J=3.9 Hz, J=1.1 Hz,
J = 8.1 Hz); 8.07 (dt, 1H, J = 4.8 Hz, J = 1.1 Hz); 8.34-8.36
(m, 2H). 13C NMR (CDCl3), δ: 38.7 (d, CH2, 1JCP = 64.9 Hz);
116.0 (d, arom., 1JCP=105.1 Hz); 119.1 (d, arom., 1JCP=92.8 Hz);
128.2 (s, arom.); 129.0 (s, arom.); 129.36 (d, arom., 3JCP=18.2 Hz);
129.39 (d, arom., 3JCP=13.6 Hz); 132.8 (d, arom., 2JCP=11.4 Hz);
134.27 (s, arom.); 134.29 (d, arom., 4JCP=3.0 Hz); 134.4 (d, arom.,
3JCP=5.9 Hz); 139.7 (d, arom., 2JCP =4.7 Hz); 142.9 (d, arom.,
3JCP=11.0Hz);191.8(d,CdO, 2JCP=5.9Hz).31PNMR(CDCl3),
δ: 16.54. IR, ν~/cm-1: 1660 (CdO), 730-760, 1470 (Ar). Anal. Calcd
for C24H20BrOPS: C, 61.68; H, 4.31. Found: 61.48; H, 4.49.
Experimental Section
General. The 1H, 31P, and 13C NMR spectra were recorded in
CDCl3 and CD2Cl2 with Me4Si as the internal standard. The IR
spectra were measured in CCl4. HRMS measurements: The
FAB spectra were recorded in positive ion mode using acetoni-
trile alcohol as matrix. The mass spectra were obtained on a
quadrupole mass spectrometer (EI, 70 eV, direct inlet). The
progress of the reactions and the purity after chromatographic
separation were monitored by TLC on silica gel 60 plates.
Chromatographic separations were carried out on columns with
silica gel 60.
(2-Oxo-2-phenylethyl)(diphenyl)3-thienylphosphonium Bro-
mide (8e). Yield: 2.78 g (80%). Mp: 188-190 °C. 1H NMR
(CDCl3), δ: 6.06 (d, 2H, J = 13.0 Hz); 7.44-7.49 (m, 3H);
J. Org. Chem. Vol. 76, No. 2, 2011 569

Matveeva et al.
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7.61-7.65 (m, 5H); 7.75-7.83 (m, 7H); 8.09 (d, 2H, J = 7.5 Hz);
8.32 (dd, 1H, J = 1.5 Hz, J = 8.1 Hz). 13C NMR (CDCl3), δ:
36.1 (d, CH2, 1JCP = 63.4 Hz); 116.3 (d, arom., 1JCP = 95.2 Hz);
ν~/cm-1: 1600 (CdO), 1150 (BF4-), 730-760, 1470 (Ar). Anal.
Calcd for C30H23BF4IOPS: C, 53.28; H, 3.43; S, 4.74. Found: C,
53.28; H, 3.60; S, 4.57.
1
118.4 (d, arom., JCP = 91.1 Hz); 127.6 (s, arom.); 128.11
(s, arom.); 128.7 (d, arom., JCP = 13.2 Hz); 129.2 (d, arom.,
1-[Diphenyl(3-thienyl)phosphonio]-2-oxo-2-phenyl-1-(phenyl-
iodonio)ethanide Tetrafluoroborate (1e). Yield: 1.49 g (85%). Mp:
145 °C. 1H NMR (CD3CN), δ: 7.23-7.25 (m, 2H); 7.28-7.30 (m,
1H); 7.38-7.42 (m, 2H); 7.48-7.53 (m, 3H); 7.60-7.65 (m, 11H);
7.75-7.76 (m, 3H); 7.97 (d, 1H, J =7.3Hz). 13C NMR (CD3CN),
3
2JCP = 16.5Hz); 129.3 (d, arom., 2JCP=16.1 Hz); 132.2 (d, arom.,
2JCP = 11.1 Hz); 133.5 (s, arom.); 133.5 (d, arom., JCP = 2.0
4
Hz); 134.1 (d, arom., 3JCP=6.0 Hz); 140.2 (d, arom., 3JCP=15.3
Hz); 190.9 (d, CdO, JCP = 5.4 Hz). 31P NMR (CDCl3), δ:
δ: 121.9 (s, arom.); 124.3 (d, arom., JCP = 99.5 Hz); 124.9 (d,
2
1
13.82. IR, ν~/cm-1: 1660 (CdO), 730-760, 1470 (Ar). Anal. Calcd
for C24H20BrOPS: C, 61.68; H, 4.31. Found: C, 61.52; H, 4.25.
General Procedure for Preparation of Phosphoranes (9 d, 9e).
A solution of 240 mg of sodium methylate (44 mmol) in 2 mL
of dry methanol was added gradually to a solution of 43 mmol
phosphonium salt (8) in 10 mL of dry methanol, at 0-5 °C.
The mixture was stirred for 1 h, then it was evaporated in
vacuum and the residue was dissolved in 20 mL of methylene
chloride. The precipitate of sodium bromide was separated
from the solution of ylides (9) by filtration, washed on the filter
with methylene chloride (3 ꢀ 10 mL.). The residue was evapo-
rated in vacuum.
arom., 1JCP = 95.9 Hz); 128.8 (s, arom.); 128.9 (s, arom.); 130.9
(d, arom., 3JCP = 13.2 Hz); 131.2 (d, arom., 2JCP = 6.1 Hz); 131.8
(s, arom.); 132.0 (d, arom., 2JCP = 5.3 Hz); 133.1 (s, arom.); 133.5
2
(s, arom.); 133.8 (s, arom.); 134.6 (d, arom., JCP = 11.0 Hz);
135.3 (s, arom.); 140.8 (d, arom., 3JCP2 = 7.3 Hz); 141.5 (d, arom.,
3JCP = 14.6 Hz); 193.1 (d, CdO, JCP = 4.4 Hz). 31P NMR
(CD3CN), δ: 18.55. IR, ν~/cm-1: 1600 (CdO), 1150 (BF4-),
730-760, 1470 (Ar). Anal. Calcd for C30H23BF4IOPS: C, 53.28;
H, 3.43. Found: C, 53.61; H, 3.53.
General Procedure for the Reaction of Ylide (1b)5a,b with
Alkynes. The alkyne was added to a solution of ylide (1b) (0.3 mmol)
in anhydrous methylene chloride. The mixture was 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 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/MeOH mixture in a ratio of 200:1,
and the furans were eluted by using a CH2Cl2/MeOH mixture in a
ratio of 100:1.
2-[Diphenyl(2-thienyl)phosphoranylidene]-1-phenylethanone
(9d). Yield: 1.48 g (90%). Mp: 201 °C. 1H NMR (CDCl3), δ: 4.51
(d, 1H, J = 23.8 Hz); 7.15-7.18 (m, 1H); 7.36-7.37 (m, 3H);
7.46-7.51 (m, 5H); 7.56-7.59 (m, 2H); 7.71-7.76 (m, 5H);
7.98-8.00 (m, 1H). 13C NMR (CDCl3), δ: 51.6 (d, CH, 1JCP
=
1
116.1 Hz); 126.9 (s, arom.); 127.5 (d, arom., JCP = 95.4 Hz);
127.70 (s, arom.); 127.73 (d, arom., 1JCP = 101.8 Hz); 127.8 (d,
arom., 3JCP = 14.0 Hz); 128.8 (d, arom., 3JCP = 12.7 Hz); 129.4
(s, arom.); 132.2 (d, arom., 4JCP=2.5 Hz); 132.7 (d, arom., 2JCP
10.6 Hz); 134.6 (d, arom., 2JCP=4.7 Hz); 138.2 (d, arom., 3JCP
10.2 Hz); 140.7 (d, arom., 3JCP = 14.0 Hz); 185.1 (d, CdO,2JCP
=
=
=
[1,1-Diphenyl-4-(3-thienyl)-1λ5-phosphinolin-2-yl](phenyl)-
methanone (14). Yield: 88 mg (60%), red oil. 1H NMR (CD2Cl2),
δ: 7.00 (dd, 1H, J = 5.0 Hz, J=1.3 Hz); 7.05 (dd, 1H, J = 2.9 Hz,
J = 1.5 Hz); 7.09 (d, 1H, J=31.8 Hz); 7.22 (dd, 1H, J=5.0 Hz,
J = 3.1 Hz); 7.28-7.32 (m, 5H); 7.34-7.44 (m, 6H); 7.46-7.48
(m, 2H.); 7.50-7.53 (m, 2H); 7.72-7.78 (m, 4H). 13C NMR
2.1 Hz). 31P NMR (CDCl3), δ: 9.34. IR, ν~/cm-1: 1590 (CdO),
730-760, 1470 (Ar). Anal. Calcd for C24H19OPS: C, 74.59; H,
4.96; S, 8.30. Found: C, 74.41; H, 5.10; S, 7.96.
2-[Diphenyl(3-thienyl)phosphoranylidene]-1-phenylethanone
(9e). Yield: 1.40 g (85%). Mp: 173 °C. 1H NMR (CDCl3), δ: 4.35
(br.s, 1H); 7.25-7.27 (m, 3H); 7.31-7.33 (m, 1H); 7.36-7.40 (m,
5H); 7.45-7.49 (m, 2H); 7.59-7.64 (m, 4H); 7.79 (dd, 1H, J =
8.3 Hz, J=1.7 Hz); 7.87-7.89 (m, 1H). 13CNMR(CDCl3), δ: 50.9
1
(CD2Cl2), δ: 75.5 (d, C1, JCP = 100.8 Hz); 112.4 (d, arom.,
1JCP = 94.0 Hz); 112.8 (d, CH=C, JCP = 9.6 Hz); 123.3 (s,
3
arom.); 125.6 (d, arom., 3JCP = 11.7 Hz); 126.4 (s, arom.); 126.9
(d, arom., 2JCP = 7.6 Hz); 128.7 (d, arom., 1JCP = 93.6 Hz); 129.5
(s, arom.); 130.2 (d, arom., JCP = 13.2 Hz); 130.2 (s, arom.);
(d, CH, 1JCP=114.0 Hz); 127.0 (s, arom.); 127.4 (d, arom., 2JCP
=
3
14.9 Hz); 127.5 (d, arom., 1JCP = 92.8 Hz); 127.8 (s, arom.); 128.1
(d, arom., 1JCP=109.2 Hz); 129.0 (d, arom., 3JCP=12.5 Hz); 129.4
131.1 (s, arom.); 131.3 (s, arom.), 133.2 (d, arom., 4JCP = 2.0 Hz);
4
133.4 (d, arom., JCP = 3.3 Hz); 134.9 (d, CH, JCP = 6.8 Hz);
2
(s, arom.); 131.0 (d, arom., 2JCP=15.2 Hz); 132.2 (d, arom., 4JCP
2.4 Hz); 132.8 (d, arom., 2JCP =10.8 Hz); 136.4 (d, arom., 3JCP
14.4 Hz); 141.2 (d, arom., 3JCP = 14.5 Hz); 185.1 (d, CdO, 2JCP
=
=
=
134.9 (d, arom., JCP = 11.3 Hz); 135.03 (d, arom., 3JCP = 8.4
2
Hz); 142.20 (d, arom., 3JCP = 9.7 Hz); 143.13 (d, arom., 2JCP
=
4.8 Hz); 144.8 (s, arom.); 191.0 (d, CO, 2JCP = 5.6 Hz). 31P NMR
(CD2Cl2), δ: 4.89. IR, ν~/cm-1: 1580 (CdO), 1520 (CdC), 720-
750, 1470 (Ar). MS, m/z: 486 [M]þ, 409 [M - C6H5]þ, 381 [M -
PhCO]þ, 183 [Ph2P - 2H]þ. HRMS calcd for C32H23OPS (Mþ)
m/z 486.1207, found 486.1202.
3.2 Hz). 31P NMR (CDCl3), δ: 8.35. IR, ν~/cm-1: 1590 (CdO),
730-760, 1470 (Ar). Anal. Calcd for C24H19OPS: C, 74.59; H,
4.96. Found: C, 74.63; H, 4.90.
General Procedure for Preparation of Phosphonium-Iodonium
Ylides (1d, 1e). A solution of 3 mmol of diacetoxyiodobenzene in
8 mL of methanol was added to the solution of 3 mmol ylides (9)
in 5 mL of methanol at 0-5 °C, then 3 mmol of a solution of
HBF4 (40%) was added at 0-5 °C. The mixture was stirred for
1 h, then 10 mL of diethyl ether was added and stirred for 1 h. The
precipitate was filtered and washed with diethyl ether.
[4-(6-Methoxy-2-naphthyl)-1,1-diphenyl-1λ5-phosphinolin-2-yl]-
1
(phenyl)methanone (16). Yield: 16 mg (10%), red oil. H NMR
(CD2Cl2), δ: 3.92 (s, 3H); 7.13 (dd, 2H., J = 8.7 Hz, J = 2.5 Hz);
7.18 (d, 1H, J = 2.3 Hz); 7.22 (d, 1H, J = 31.6 Hz); 7.34-7.47 (m,
7H); 7.52-7.62 (m, 6H); 7.64-7.67 (m, 2H); 7.70-7.74 (m, 3H);
7.87-7.93 (m, 4H). 13C NMR (CD2Cl2), δ: 55.9 (s, OCH3); 74.6
1-[Diphenyl(2-thienyl)phosphonio]-2-oxo-2-phenyl-1-(phenyl-
iodonio)ethanide Tetrafluoroborate (1d). Yield: 1.40 g (80%).
(d, C1, 1JCP = 100.8 Hz); 106.3 (s, arom.); 111.5 (d, arom., 1JCP
=
3
85.9 Hz); 117.4 (d, CH=C, JCP = 10.0 Hz); 119.2 (s, arom.);
1
Mp: 157 °C. H NMR (CD3CN), δ: 7.24 (d, 2H, J = 7.6 Hz);
124.6 (d, arom., 3JCP = 11.7 Hz); 126.2 (d, arom., 2JCP = 7.6 Hz);
1
7.34-7.41 (m, 3H); 7.49-7.61 (m, 15H); 7.76-7.77(m, 2H);8.09-
8.11 (m, 3H). 13C NMR (CD3CN), δ: 124.0 (s, arom.); 124.4 (d,
arom., 1JCP=109.0 Hz); 125.0 (d, arom., 1JCP = 97.3 Hz); 128.8
127.0 (s, arom.); 127.8 (d, arom., JCP = 93.6 Hz); 128.4 (s,
arom.); 128.5 (s, arom.); 129.2 (d, arom., 3JCP = 12.9 Hz); 129.3
(s, arom.); 129.7 (s, arom.); 129.9 (s, arom.); 130.0(s, arom.); 132.1
(d, arom., 4JCP = 1.6 Hz); 132.4 (d, arom., 4JCP = 3.2 Hz); 133.8
(s, arom.); 133.95 (d, arom., 2JCP = 11.2 Hz); 134.04 (d, arom.,
3
(s, arom.); 129.9 (s, arom.); 130.6 (d, arom., JCP = 15.4) Hz;
131.0 (d, arom., JCP = 13.9 Hz); 132.0 (s, arom.); 133.1 (s,
3
arom.); 133.6 (s, arom.); 134.0 (s, arom.); 134.7 (d, arom., 2JCP
=
3JCP = 7.6 Hz); 134.1 (d, CH, JCP = 7.6 Hz); 138.7 (s, arom.);
2
10.3 Hz); 135.5 (s, arom.); 139.6 (d, arom., 2JCP = 4.4 Hz); 140.7
(d, arom., 3JCP=7.3 Hz); 141.9 (d, arom., 3JCP=11.0 Hz); 193.3
141.2 (d, arom., 3JCP = 10.0 Hz); 142.3 (d, arom., 2JCP = 4.8 Hz);
158.1 (s, arom.); 190.0 (d, CO, JCP = 6.0 Hz). 31P NMR
2
(d, CdO, JCP = 5.9 Hz). 31P NMR (CD3CN), δ: 20.07. IR,
(CD2Cl2), δ: 5.01. IR, ν~/cm-1: 1580 (CdO), 1520 (CdC),
2
570 J. Org. Chem. Vol. 76, No. 2, 2011

Matveeva et al.
JOCArticle
730-750, 1460 (Ar). MS, m/z: 560 [M]þ, 545 [M - Me]þ, 183
[Ph2P - 2H]þ, 105 [PhC(O)]þ, 77 [Ph]þ. HRMS calcd for C39H29-
O2P (Mþ) m/z 560.1905, found 560.1900.
127.8 (s, arom.); 127.95 (s, arom.); 128.01 (s, arom.); 128.8 (s,
arom.); 129.2 (s, arom.); 129.3 (s, arom.); 129.8(s, arom.); 130.0 (s,
arom.); 131.2 (s, arom., 3JCP = 13.3 Hz); 131.30 (s, arom.); 131.32
(s, arom.); 131.4(s, arom.); 134.7(d, arom., 2JCP=10.8 Hz); 136.3
[4-(9-Phenanthryl)-1,1-diphenyl-1λ5-phosphinolin-2-yl](phenyl)-
methanone (17). Yield: 8 mg (5%), red oil. 1H NMR (CD2Cl2), δ:
6.84 (dd, 1H, J = 8.1 Hz, J = 5.3 Hz); 7.05-7.10 (m, 1H); 7.16-
7.20 (m, 1H); 7.26 (d, 1H, J = 31.9 Hz); 7.28-7.30 (m, 2H); 7.44-
7.50 (m, 2H); 7.57-7.68 (m, 12H); 7.76 (s, 1H); 7.80 (dd, 1H, J =
8.3 Hz, J = 1.0 Hz); 7.89 (dd, 1H, J = 7.8 Hz, 4JHH = 1.2 Hz);
(d, arom., JCP = 2.8 Hz); 156.8 (d, C-Phntr, 3JCP = 13.4 Hz);
4
163.4 (d, Ph-C-O, 2JCP = 16.9 Hz). 31P NMR (CD2Cl2), δ: 16.32.
IR, ν~/cm-1: 1070 (BF4-), 730-760, 1470 (Ar). MS, m/z: 581 [M -
BF4]þ, 504 [M - BF4-C6H5]þ. HRMS calcd for C42H30OP
(Mþ) m/z 581.2029, found 581.2029.
7.93-8.00 (m, 4H); 8.74 (dd, 2H, J = 8.1 Hz, J = 10.4 Hz). 13
C
General Procedure for the Reaction of Ylides (1e, 1d) with Phe-
nylacetylene. The ylides (0.3 mmol) were added gradually to a
solution of phenylacetylene 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. To elute phenylacetylene and PhI, benzene was used;
the corresponding phosphininothiophene was eluted by using a
CH2Cl2/MeOH mixture in a ratio of 200:1.
NMR (CD2Cl2), δ: 74.6 (d, C1, 1JCP = 100.3 Hz); 111.1 (d, arom.,
1JCP = 84.8 Hz); 114.8 (d, CHdC, JCP = 10.4 Hz); 123.1 (s,
3
arom.); 123.4 (s, arom.); 124.5 (d, arom., 3JCP = 11.6 Hz); 126.7
(d, arom., 2JCP = 7.6 Hz); 126.92 (s, arom.); 126.94 (s, arom.);
1
127.0 (s, arom.); 127.3 (s, arom.); 127.6 (d, arom., JCP = 94.8
Hz); 127.9 (s, arom.); 128.0 (d, arom., 1JCP = 93.6 Hz); 129.5 (s,
arom.); 128.4 (s, arom.); 129.1 (d, arom., 3JCP = 12.5 Hz); 129.2
(s, arom.); 129.25 (s, arom.); 129.29 (s, arom.); 129.31 (d, arom.,
3JCP = 12.5Hz); 131.2(s, arom.); 132.1(d, arom., 4JCP = 1.6Hz);
132.4 (d, arom., 4JCP = 3.3 Hz); 132.5 (d, arom., 4JCP = 2.8 Hz);
132.9 (s, arom.); 133.4 (s, arom.); 133.9 (s, CH, 2JCP = 7.2 Hz);
133.98 (d, arom., 2JCP = 10.9 Hz); 134.02 (d, arom., 2JCP = 10.9
Hz); 134.3 (d, arom., 3JCP = 7.6 Hz); 139.6 (s, arom.); 141.1 (d,
arom., 3JCP = 10.0 Hz); 142.9 (d, arom., 2JCP = 4.8 Hz); 190.0 (s,
CO). 31P NMR (CD2Cl2), δ: 5.42. IR, ν~/cm-1: 1580 (CdO), 1510
(CdC), 720-750, 1460 (Ar). MS, m/z: 580 [M]þ, 490 [M -
PhC(O) þ H]þ, 183 [Ph2P - 2H]þ, 105 [PhC(O)]þ, 77 [Ph]þ.
HRMS calcd for C42H29OP (Mþ) m/z 580.1956, found 580.1951.
Triphenyl[2-phenyl-5-(3-thienyl)-3-furyl]phosphonium Tetra-
fluoroborate (18). Yield: 12 mg (7%), colorless oil. 1H NMR
(CDCl3), δ: 6.60 (d, 1H, J = 3.8 Hz); 7.08 (t, 2H, arom., J = 7.4
Hz); 7.18 (d, 2H, J = 7.2Hz); 7.23 (t, 1H, J = 7.4Hz);7.40 (d, 2H,
J = 2.1 Hz); 7.67-7.75 (m, 13H); 7.78-7.83 (m, 3H). 13C NMR
Phenyl(4,7,7-triphenyl-7λ5-phosphinino[2,3-b]thiophen-6-yl)-
methanone (22). Yield: 44 mg (30%), red oil. 1H NMR (CD2Cl2),
δ: 7.04 (dd, 1H, J = 5.3 Hz, J = 3.6Hz); 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, C1,
1JCP = 103.4 Hz); 107.0 (d, arom., JCP = 90.8 Hz); 113.5 (d,
1
CHdC, 3JCP = 8.1 Hz); 122.1 (d, R-Thio-arom., 3JCP = 16.5 Hz);
127.1 (s, arom.); 128.1 (d, arom., 1JCP=98.8 Hz); 128.6(s, arom.);
128.8 (s, arom.); 129.05 (s, arom.); 129.06 (d, arom., JCP =
3
13.3 Hz); 129.09 (s, arom.); 129.2 (d, β-Thio-arom., 3JCP = 11.1
Hz); 130.2 (s, arom.); 132.2 (d, CH, JCP = 7.6 Hz); 132.3 (d,
2
arom., 4JCP = 3.2 Hz); 133.6 (d, arom., 2JCP = 11.2 Hz); 141.2 (d,
(CDCl3),δ: 98.4 (d, Ph3PþC, 1JCP=109.8 Hz); 109.2 (d, CH, 2JCP
=
arom., 3JCP = 9.3 Hz); 142.8 (s, arom.); 154.2 (d, arom., 2JCP
=
11.9 Hz); 117.6 (d, arom., 1JCP=92.8 Hz); 122.7 (s, arom.); 124.8
(s, arom.); 127.4 (s, arom.); 128.1 (s, arom.); 128.5 (s, arom.); 129.5
(s, arom.); 130.5 (s, arom.); 130.7 (s, arom., 3JCP = 13.6 Hz); 134.1
(d, arom., 2JCP=11.1 Hz); 135.6 (d, arom., 4JCP = 3.0 Hz); 153.4
(d, C-The, 3JCP = 14.9 Hz); 161.3 (d, Ph-C-O, 2JCP = 17.0 Hz).
31P NMR (CDCl3), δ: 14.20. IR, ν~/cm-1: 1120 (BF4-), 730-760,
1470 (Ar). MS, m/z: 486 [M - BF4 - 1]þ, 410 [M - BF4-C6H5]þ.
HRMScalcdfor C32H24OPS(Mþ) m/z 487.1280, found 487.1280.
[5-(6-Methoxy-2-naphthyl)-2-phenyl-3-furyl](triphenyl)phos-
phonium Tetrafluoroborate (20). Yield: 116 mg (60%), colorless
oil. 1H NMR (CDCl3), δ: 3.93 (s, 3H); 6.76 (d, 1H, J = 3.9 Hz);
7.09-7.14 (m, 3H); 7.16 (dd, 1H, J = 8.9 Hz, J = 2.5 Hz); 7.23 (s,
1H); 7.24 (d, 2H, J = 8.1 Hz); 7.68-7.78 (m, 14H); 7.79-7.84 (m,
4H); 8.19 (s, 1H). 13C NMR (CDCl3), δ: 55.4 (s, OCH3); 98.6 (d,
8.0 Hz); 191.5 (d, CO, 2JCP = 5.6 Hz) 31P NMR(CD2Cl2), δ: 1.97.
MS, m/z: 486 [M]þ, 409 [M - C6H5]þ, 381 [M - PhCO]þ, 183
[Ph2P - 2H]þ. HRMS calcd for C32H23OPS (Mþ) m/z 486.1207,
found 486.1202.
Phenyl(4,4,7-triphenyl-4λ5-phosphinino[3,2-b]thiophen-5-yl)-
methanone (23) and Phenyl(1,1,4-triphenyl-1λ5-phosphinino[2,3-c]-
thiophen-2-yl)methanone (24). Yield: 36 mg (25%), red oil. H
1
NMR (CD2Cl2), δ: 7.03 (dd, 1H, arom., 3JHH = 5.3 Hz, 3JHP
=
3.6 Hz); 7.10 (dd, 1H, arom., 3JHH = 5.3 Hz, 4JHP = 2.7 Hz); 7.15
(d, 1H, CH, 3JPH = 33.9 Hz); 7.17 (d, 1H, CH, 3JPH = 34.7 Hz);
7.22 (dd, 1H, arom., 4JHH = 5.1 Hz, 3JHP = 4.3 Hz); 7.23-7.26
(m, 2H, arom.); 7.33-7.41 (m, 12H, arom.); 7.50-7.54 (m, 10H,
arom.); 7.56-7.59 (m, 4H, arom); 7.60-7.64 (m, 4H, arom); 7.68
4
4
(dd, 1H, arom., JHH = 5.1, JHP = 2.7); 7.81-7.86 (m, 8H,
Ph3PþC, 1JCP = 109.4 Hz); 106.0 (s, arom.); 109.1 (d, CH, 2JCP
=
arom.). 13C NMR (CD2Cl2), δ: 75.5 (d, C1, JCP = 103.9 Hz);
1
11.9 Hz); 117.6 (d, arom., 1JCP = 92.4 Hz); 119.8 (s, arom.); 122.6
(s, arom.); 123.1 (s, arom.); 123.9 (s, arom.); 127.5 (s, arom.); 127.8
(s, arom.); 128.1 (s, arom.); 128.57 (s, arom.); 128.64 (s, arom.);
130.1 (s, arom.); 130.5 (s, arom.); 130.7 (d, arom., 3JCP = 13.1 Hz);
134.1 (d, arom., 2JCP = 10.6 Hz); 135.0 (s, arom.); 135.7 (d, arom.,
78.5 (d, C1, 1JCP = 103.1 Hz); 115.6 (d, CHdC, 3JCP = 7.5 Hz);
122.1 (d, Thio-arom., 3JCP = 16.6 Hz); 126.4 (s, arom.); 126.95 (d,
Thio-arom., 2JCP = 9.7 Hz); 127.03 (s, arom.); 127.5 (d, arom.,
1JCP = 99.5 Hz); 128.0 (d, arom., JCP = 95.6 Hz); 128.6 (s,
1
arom.); 128.8 (s, arom.); 128.9 (d, arom., 3JCP = 13.8 Hz); 128.97
(s, arom.); 129.04 (d, arom., 3JCP = 13.3 Hz); 129.06 (s, arom.);
129.14 (d, Thio-arom., 2JCP = 10.8 Hz); 129.3 (s, arom.); 130.1 (s,
arom.); 130.2 (s, arom.); 132.2 (d, CH, 2JCP = 7.7 Hz); 132.26 (d,
arom., 4JCP2 = 3.0 Hz); 132.32 (d, arom., 4JCP = 3.3 Hz); 133.60
4JCP = 3.0 Hz); 156.9 (d, C-Naph, JCP = 14.4 Hz); 158.7 (s,
3
arom.); 161.7 (d, Ph-C-O, 2JCP = 17.4 Hz). 31P NMR (CDCl3),
δ: 14.25. IR, ν~/cm-1: 1070 (BF4-), 730-760, 1470 (Ar). MS, m/z:
561 [M - BF4]þ, 484 [M - BF4-C6H5]þ. HRMS calcd for
C39H30O2P (Mþ) m/z 561.1978, found 561.1978.
2
(d, arom., JCP2= 11.3 Hz); 133.61 (d, arom., JCP = 11.9 Hz);
3
[5-(9-Phenanthryl)-2-phenyl-3-furyl](triphenyl)phosphonium
Tetrafluoroborate (21). Yield: 160 mg (80%), colorless oil. H
133.8 (d, CH, JCP = 6.6 Hz); 141.0 (d, arom., JCP = 9.4 Hz);
141.1 (d, arom., 3JCP =9.1 Hz); 143.2 (d, arom., 4JCP =1.4 Hz);
142.8 (d, arom., 4JCP =1.1 Hz); 150.7 (d, arom., 2JCP = 5.5 Hz);
191.6 (s, CO); 192.9 (s, CO). 31P NMR (CD2Cl2), δ: -0.08 (23),
0.42 (24). MS, m/z: 486 [M]þ, 409 [M - C6H5]þ, 381 [M -
PhCO]þ, 183 [Ph2P - 2H]þ. HRMS calcd for C32H23OPS (Mþ)
m/z 486.1207, found 486.1202.
1
NMR (CD2Cl2), δ: 6.82 (d, 1H, J=3.7 Hz); 7.16 (t, 2H, J=8.1
Hz); 7.29-7.34 (m, 2H); 7.66-7.91 (m, 20H); 8.02 (dd, 1H, J =
7.8 Hz, J = 1.3 Hz); 8.17 (s, 1H); 8.33 (dd, 1H, J = 7.9 Hz, J =
1.4Hz); 8.73 (d, 1H, J =8.1 Hz);8.82 (dd, 1H, J= 8.1Hz, J= 1.4
Hz). 13C NMR (CD2Cl2), δ: 98.8 (d, Ph3PþC, 1JCP = 109.6 Hz);
114.6 (d, CH, 2JCP = 11.7 Hz); 118.2 (d, arom., 1JCP = 92.8 Hz);
123.2 (s, arom.); 123.9(s, arom.); 124.9 (s, arom.); 125.9 (s, arom.);
General Procedure for the Reaction of Ylide 1c with Alkynes.
The alkyne was added to a solution of the ylide 1c (0.3 mmol) in
J. Org. Chem. Vol. 76, No. 2, 2011 571

Matveeva et al.
JOCArticle
anhydrous methylene chloride. The solution was irradiated in a
quartz flask with a mercury lamp (366 nm) under argon atmo-
sphere. The course of the reaction was monitored by TLC. After
the end of the reaction, the solvent was removed in vacuum. The
residue was resolved in a minimum of CH2Cl2 and chromato-
graphed on silica gel. To elute the residual alkynes and PhI,
benzene was used. The corresponding phosphinoline was eluted
by using CH2Cl2/MeOH mixture in a ratio of 200:1.
(d, CH, 2JCP = 5.4 Hz); 134.39 (d, arom., 4JCP = 3.2 Hz); 136.0 (s,
arom.); 142.7 (d, arom., JCP = 5.7 Hz); 159.8 (s, arom.). 31P
2
NMR (CD2Cl2), δ: 11.49. IR, ν~/cm-1: 2175 (CN), 1570 (CdC),
720-750, 1460 (Ar). MS, m/z: 431 [M]þ, 416 [M - CH3]þ, 354
[M - C6H5]þ, 183 [Ph2P - 2H]þ. HRMS calcd for C29H22NOP
(Mþ) m/z 431.1439, found 431.1434.
4-Hex-5-yn-1-yl-1,1-diphenyl-1λ5-phosphinoline-2-carboni-
trile (30). Yield: 24 mg (20%), yellow oil. 1H NMR (CDCl3), δ:
1.45-1.53 (m, 2H); 1.55-1.62 (m, 2H); 1.85 (t, 1H, J = 2.8 Hz);
2.12 (dt, 2H, J= 6.9 Hz, J=2.8Hz);2.47(t, 2H, J=7.6Hz);6.69
(d, 1H, J = 26.0 Hz); 7.03-7.07 (m, 1H); 7.30-7.35 (m, 1H);
7.40-7.47 (m, 6H); 7.49-7.50 (m, 1H); 7.51-7.57 (m, 5H). 13C
NMR (CDCl3), δ: 18.4, 28.3, 28.8, 33.4 (all s, CH2); 29.9 (d, C1,
1JCP = 119.2 Hz); 68.4 (s, CtCH); 84.6 (s, CtCH); 105.6 (d,
arom., 1JCP = 93.1 Hz); 112.3 (d, CN, 2JCP = 9.3 Hz); 123.4 (d,
arom., 3JCP = 12.8 Hz); 123.6 (d, arom., 3JCP = 8.9 Hz); 124.8 (d,
CHdC, 3JCP =11.6 Hz); 127.9 (d, arom., 1JCP = 89.2 Hz); 129.2
(d, arom., 3JCP = 12.5 Hz); 130.9 (d, CH, 2JCP = 4.0 Hz); 131.9 (d,
arom., 4JCP = 2.0 Hz); 132.0 (d, arom., 2JCP = 8.8 Hz); 132.6 (d,
arom., 4JCP = 3.3 Hz); 132.8 (d, arom., 2JCP = 10.4 Hz); 140.7 (d,
1,1,4-Triphenyl-1λ5-phosphinoline-2-carbonitrile (27). Yield:
42 mg (35%), yellow oil. This oil was dissolved in a minimum
of CH2Cl2 and subsequent addition of diethyl ether to this
solution resulted in crystallization of phosphinoline 27 as red
crystal, mp 263-264 °C. 1H NMR (CDCl3), δ: 6.85 (d, 1H, J =
26.0 Hz); 7.02-7.08 (m, 1H); 7.15-7.21 (m, 1H); 7.23-7.38 (m,
7H); 7.43-7.55 (m, 6H); 7.56-7.65 (m, 4H). 13C NMR (CDCl3),
δ: 31.9 (d, C1, 1JCP = 119.1 Hz); 104.8 (d, arom., 1JCP = 93.4
Hz); 116.9 (d, CN, 2JCP = 9.4 Hz); 123.9 (d, arom., 3JCP = 12.7
Hz); 124.3 (d, CHCPh,, 3JCP=12.2 Hz); 125.7 (d, arom., 3JCP
=
8.3 Hz); 126.1 (s, arom.); 127.5 (d, arom., 1JCP = 89.6 Hz); 128.5
(s, arom.); 129.3(d, arom., 3JCP=12.7Hz); 130.0 (s, arom.); 131.7
(d, arom., 2JCP = 5.3 Hz); 131.8 (d, arom., 4JCP = 1.7 Hz); 132.8
(d, arom., 4JCP = 3.1 Hz); 132.9 (d, arom., 2JCP = 10.7 Hz); 133.3
(d, CH, 2JCP = 4.2 Hz); 140.8 (d, arom., 2JCP = 5.5 Hz); 141.9 (d,
arom., 2JCP = 5.6 Hz). 31P NMR (CDCl3), δ: 10.31. IR, ν~/cm-1
:
2170 (CN), 1580 (CdC), 730-750, 1470 (Ar), 3260 (tC-H). MS,
m/z: 405 [M]þ, 338 [M - (CH2)3CtCH]þ, 183 [Ph2P - 2H]þ.
HRMS calcd for C28H24NP (Mþ) m/z 405.1646, found 405.1641.
4-Octyl-1,1-diphenyl-1λ5-phosphinoline-2-carbonitrile (31).
Yield: 20 mg (15%), yellow oil. 1H NMR (CDCl3), δ: 0.80 (t,
3H); 1.12-1.22 (m, 12H); 1.43-1.47 (m, 2H); 6.68 (d, 1H, J =
26.0 Hz); 7.03-7.06 (m, 1H); 7.29-7.35 (m, 1H); 7.42-7.46
(m, 6H); 7.49-7.57 (m, 6H). 13C NMR (CDCl3), δ: 14.2 (s,
CH3), 22.8, 29.4, 29.60, 29.62, 29.8, 32.0, 33.9 (all s, CH2);
arom., 4JCP = 1.1 Hz) 31P NMR (CDCl3), δ: 9.39. IR, ν~/cm-1
:
2170 (CN), 1560 (CdC), 720-750, 1470 (Ar). MS, m/z: 401 [M]þ,
324 [M - C6H5]þ, 183 [Ph2P - 2H]þ. HRMS calcd for C28H20NP
(Mþ) m/z 401.1333, found 401.1328.
1,1-Diphenyl-4-(3-thienyl)-1λ5-phosphinoline-2-carbonitrile (28).
Yield: 48 mg (40%), yellow oil. 1H NMR (CDCl3), δ: 6.93 (d, 1H,
J=26.1 Hz); 7.01 (dd, 1H, J=5.0 Hz, J = 1.1 Hz); 7.03-7.08 (m,
2H); 7.25 (dd, 1H, J = 5.0 Hz, J = 3.0 Hz); 7.30-7.38 (m, 2H);
7.41-7.50 (m, 5H); 7.52-7.55 (m, 2H); 7.58-7.63 (m, 4H). 13C
NMR (CDCl3), δ: 32.0 (d, C1, 1JCP = 118.4 Hz); 104.8 (d, arom.,
1JCP = 92.7 Hz); 111.2 (d, CN, 2JCP = 9.2 Hz); 121.8 (s, arom.);
123.9 (d, arom., 3JCP = 12.9 Hz); 124.1 (d, CHdC, 3JCP = 11.7
1
1
30.1 (d, C1, JCP = 119.7 Hz); 104.6 (d, arom., JCP = 90.8
Hz); 113.0 (d, CN, 2JCP=8.8 Hz); 123.3 (d, arom., 3JCP=12.9
=
Hz); 123.7 (d, arom., 3JCP=8.8 Hz); 124.9 (d, CH=C, 3JCP
1
12.1 Hz); 128.0 (d, arom., JCP = 89.1 Hz); 129.2 (d, arom.,
3JCP=12.9 Hz); 130.7 (d, CH, 2JCP=3.6 Hz); 131.9 (d, arom.,
4JCP = 1.6 Hz); 132.0 (d, arom., JCP = 8.4 Hz); 132.6 (d,
2
3
Hz); 124.9 (s, arom.); 125.6 (d, arom., JCP = 9.5 Hz); 127.6 (d,
arom., 4JCP2=2.8 Hz); 132.8 (d, arom., 2JCP = 10.8 Hz); 140.8
(d, arom., JCP = 6.0 Hz). 31P NMR (CDCl3), δ: 10.34. IR,
ν~/cm-1: 2170 (CN), 1580 (CdC), 720-750, 1470 (Ar). MS,
m/z: 437 [M]þ, 338 [M - C7H15]þ, 183 [Ph2P - 2H]þ. HRMS
calcd for C30H32NP (Mþ) m/z 437.2272, found 437.2267.
arom., 1JCP = 90.0 Hz); 129.4 (d, arom., 3JCP=12.8 Hz); 129.7 (s,
arom.); 131.8 (d, arom., 2JCP=8.8Hz);131.9(d, arom.,4JCP=1.6
Hz); 132.8 (d, arom., 4JCP = 3.2 Hz); 132.9 (d, arom., 2JCP=10.5
Hz); 133.5 (d, CH, 2JCP = 4.0 Hz); 141.0 (d, arom., 2JCP=4.8 Hz);
142.4 (s, arom.). 31P NMR (CDCl3), δ: 9.49. IR, ν~/cm-1: 2180
(CN), 1570 (CdC), 720-750, 1460 (Ar). MS, m/z: 407 [M]þ, 330
[M - C6H5]þ, 183 [Ph2P - 2H]þ. HRMS calcd for C26H18NPS
(Mþ) m/z 407.0898, found 407.0892.
Acknowledgment. We are grateful to Russian Foundation
for Basic Research (Project No. 08-03-00611) and the Divi-
sion of Chemistry and Materials Science of the Russian
Academy of Sciences (OChNM-1, and OChNM-9). R. Glei-
ter. is grateful to Mrs. P. Kraemer for arranging the manu-
script properly.
4-(4-Methoxyphenyl)-1,1-diphenyl-1λ5-phosphinoline-2-car-
bonitrile (29). Yield: 52 mg (40%), yellow oil. 1H NMR (CD2Cl2),
δ: 3.74 (s, 3H); 6.76 (d, 1H, J = 26.0 Hz); 6.83 (dd, 2H, J =8.8Hz,
J = 2.2 Hz); 7.03-7.07 (m, 1H); 7.33-7.39 (m, 1H); 7.15 (dd, 2H,
J=8.8 Hz, J=2.2 Hz); 7.28-7.30 (m, 2H); 7.48-7.52 (m, 4H);
7.54-7.63 (m, 6H). 13C NMR (CD2Cl2), δ: 32.0 (d, C1, 1JCP
=
117.7 Hz); 56.8 (s, OCH3); 106.3 (d, arom., 1JCP = 93.2 Hz); 115.4
Supporting Information Available: H, 31P, 13CNMRspectra
1
(s, arom.); 117.7 (d, CN, 2JCP = 9.6 Hz); 125.4 (d, arom., 3JCP
12.9 Hz); 125.6 (d, CHdC, 3JCP=12.1 Hz); 127.1 (d, arom., 3JCP
8.4 Hz); 129.3 (d, arom., 1JCP = 90.4 Hz); 130.9 (d, arom., 3JCP
=
=
=
of the new compounds 1, 8, 9, 14, 16-18, 20-24, 27-31, X-
ray analysis of the molecular structure of 27 and a table of the
most relevant distances as well as CIF files of compound 27.
This material is available free of charge via the Internet at
http://pubs.acs.org.
12.9 Hz); 132.6 (s, arom.); 133.3 (d, arom., 4JCP = 1.6 Hz); 133.4
(d, arom., 2JCP=8.8 Hz); 134.3 (d, arom., 2JCP=10.8 Hz); 134.38
572 J. Org. Chem. Vol. 76, No. 2, 2011