Heterocycles from phosphonium-iodonium ylides. Photochemical synthesis of λ5-phosphinolines

Article abstract of DOI:10.1021/jo901984q

(Chemical Equation Presented) A photochemical reaction of mixed phosphonium-iodonium ylides with acetylenes yielding λ⁵- phosphinolines, a rare class of phosphorus heterocycles hardly accessible by other methods, was found. The yields of λ⁵-phosphinolines vary from 35% to 80%. The structures of two phosphinolines were established by single-crystal X-ray diffraction. The X-ray diffraction and NMR spectra data indicate the superposition of ylidic and aromatic structures for phosphinolines.

Full text of DOI:10.1021/jo901984q

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Heterocycles from Phosphonium-Iodonium Ylides. Photochemical
Synthesis of λ5-Phosphinolines
Elena D. Matveeva,*,† Tatyana A. Podrugina,† Anna S. Pavlova,† Andrey V. Mironov,†
Anatoliy A. Borisenko,† 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 September 23, 2009
A photochemical reaction of mixed phosphonium-iodonium ylides with acetylenes yielding λ5-
phosphinolines, a rare class of phosphorus heterocycles hardly accessible by other methods, was
found. The yields of λ5-phosphinolines vary from 35% to 80%. The structures of two phosphinolines
were established by single-crystal X-ray diffraction. The X-ray diffraction and NMR spectra data
indicate the superposition of ylidic and aromatic structures for phosphinolines.
Introduction
cally useful reagents in organic synthesis. Moreover, their
synthetic applications have been widely reviewed.4
The unusual and diverse reactivity of hypervalent iodine
compounds1 and, in particular, iodonium ylides2,3 was
extensively investigated. These compounds became syntheti-
Special interest requires the mixed phosphonium-
iodonium ylides of type 1. They can easily be prepared by
the reaction of carbonyl-stabilized phosphonium ylides
Ph3PdCHR (R = COOC2H5, COAr) with derivatives of
iodine(III) as ArIHal2, ArIO, and ArI(OAc)2.5 Mixed
ylides are well described by resonance structures (1a-d)
(Scheme 1). In the case of ylide 1 we have shown that it
prevails in the Z-configuration (1d) in the solid state5a,6 and
undergoes Z/E isomerization in solution6
*To whom correspondence should be addressed. Fax: 7 (495) 939 0290.
(1) (a) Zefirov, N. S.; Zhdankin, V. V.; Makhon’kova, G. V.; Dan’kov,
Yu. V.; Koz’min, A. S. J. Org. Chem. 1985, 50, 1872–1876. (b) Zefirov, N. S.;
Zhdankin, V. V; Dan’kov, Yu. V.; Koz’min, A. S.; Chizhov, O. S. Zh. Org.
Khim. 1985, 21, 2461–2462. (c) Zefirov, N. S.; Zhdankin, V. V; Dan’kov, Yu.
V.; Semerikov, V. N.; Chizhov, O. S.; Koz’min, A. S. Dokl. Acad. Nauk SSSR
1986, 288, 385–389. (d) Zhdankin, V. V.; Tykwinski, R.; Caple, R.; Berglund,
B.; Koz’min, A. S.; Zefirov, N. S. Tetrahedron Lett. 1988, 29, 3717–3720. (e)
Zhdankin, V. V.; Tykwinski, R.; Williamson, B. L.; Stang, P. J.; Zefirov, N.
S. Tetrahedron Lett. 1991, 32, 733–734. (f) Stang, P. J.; Zhdankin, V. V.;
Tykwinski, R.; Zefirov, N. S. Tetrahedron Lett. 1991, 32, 7497–7498. (g)
Stang, P. J.; Zhdankin, V. V.; Zefirov, N. S. Mendeleev Commun. 1992, 159–
160. (h) Stang, P. J.; Zhdankin, V. V.; Tykwinski, R.,R.; Zefirov, N. S.
Tetrahedron Lett. 1992, 33, 1419–1422. (i) Zefirov, N. S.; Kasumov, T. M.;
Koz’min, A. S.; Sorokin, V. D.; Stang, P. J.; Zhdankin, V. V. Synthesis 1993,
1209–1210.
The significant contribution of the resonance structure 1d
with separated charges on the P, I, and O atoms rationalizes
(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.; Brel, 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.; Proskurnina, M. V.; Zefirov, N. S. Heteroatom Chem. 2006,
17, 595–617. (f) Stang, P. J. J. Org. Chem. 2003, 68, 2997–3008.
(5) (a) Matveeva, E. D.; Podrugina, T. A.; Grishin, Y. K.; Tkachev, V. V.;
Zhdankin, V. V.; Aldoshin, S. M.; Zefirov, N. S. Zh. Org. Chem. 2003, 39,
536–541. (b) 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.; Pavlova, A. S.;
Zefirov, N. S. Zh. Org. Chem. 2007, 43, 209–214.
(2) (a) Neiland, O.; Vanag, G. Dokl. Acad. Nauk SSSR 1964, 159, 373–
376. (b) Moriarty, R. M.; Prakash, I.; Prakash, O.; Freeman, W. A. J. Am.
Chem. Soc. 1984, 106, 6082–84. (c) Zefirov, N. S.; Zhdankin, V. V.; Koz’min,
A. S.; Semerikov, V. N.; Agaev, A. T.; Magerramov, A. M. Russ. Chem. Bull.
1987, 2672. (d) Zefirov, N. S.; Kozhushkov, S. I.; Zhdankin, V. V. Zh. Org.
Khim. 1988, 24, 1560–1561.
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9428 J. Org. Chem. 2009, 74, 9428–9432
Published on Web 11/18/2009
DOI: 10.1021/jo901984q
r
2009 American Chemical Society

Matveeva et al.
JOCArticle
SCHEME 1. Resonance Structures (a-d) of Ylide 1
However, the reaction of the ylide 2 with 4-methoxyphenyl-
acetylene (4a) under UV irradiation afforded the mixture of
two isolated compounds (see Scheme 3). One of them is the
furan 5 in 30% yield. Spectroscopic evidence showed that the
second product was [4-(4-methoxyphenyl)-1,1-diphenyl-1λ5-
phosphinolin-2-yl](phenyl)methanone (6), which was ob-
tained in 45% yield (see Scheme 3). Thus this photochemical
reaction led to the serendipitous discovery of novel pathways
to λ5-phosphinolines.
SCHEME 2. Interaction between Ylides 1, 2, and Triple Bond
Compounds
In the literature the first synthesis of 1,1-diphenyl-λ5-
phosphinoline by the intermolecular alkylation of the phos-
phonium salt o-MeO(CH2CH2)C6H4Pþ(Ph2)CH2RX- (R=
H, C6H5) with subsequent treatment with NaNH2 or t-
BuOK was reported in 1963.11 This method was applied
for the synthesis of 1,1-dibenzyl-λ5-phosphinoline.12 In 1996
the preparation of the λ5-phosphinoline by the [2þ2] cy-
cloaddition of the four-membered λ5-phosphete to DMAD
was described.13 Since then no new methods for the synthesis
of λ5-phosphinolines were published. At the same time the
question whether the six-membered λ5-phosphinines are
aromatic or ylidic is under discussion in the literature.14,15
On the basis of geometric, energetic, and magnetic criteria it
was concluded that the structure of these compounds repre-
sents a hybrid of zwitterions (ylidic) and a “Hueckel” aro-
matic system.14,15 The reactivity of λ5-phosphinolines was
poorly studied. The development of a novel synthesis of λ5-
phosphinolines provides an excellent opportunity to inves-
tigate this class of phosphorus heterocycles.
the reactivity of the ylide. Indeed, we have shown that ylide 1
can be used as the O-nucleophile in alkylation, acylation, and
silylation due to a negative charge on the O-carbonyl atom.6
Mixed ylides such as 1 contain the excellent leaving phenyl-
iodonium group and thus a nucleophilic substitution reac-
tion with halogen anions and S-nucleophiles occurs.5b,7 The
presence of the phosphonium group in ylidic molecules has
allowed us to perform one-pot reactions of the nucleophilic
substitution and the Wittig reaction.5b,7
Recently we have suggested that mixed ylides of type (1)
have the possibility to react as 1,3 dipoles and, hence,
undergo [3þ2]-cycloaddition reactions8 (Scheme 2).
The experimental verification of this hypothesis has led us
to a series of interesting results. The reaction of mixed ylide 1
with dimethyl acetylenedicarboxylate (DMAD) in aceto-
nitrile resulted to our surprise not in the furan 3a (X=Y=
C), but led to oxazole 3b (X-R2=N; Y=C); in other words,
the solvent acetonitrile acts as a reagent in this process. It
should be noted that no reaction was observed in the absence
of DMAD. Thus, the interesting catalysis of one dipolaro-
philic reaction by another dipolarophile has been observed.8
We have shown that the process of the thermal pseudo-
cycloaddition of the ylides 1 and 2 in the presence of DMAD
can be applied to some other aliphatic nitriles to yield a rare
class of phosphonium-substituted oxazoles.9 Moreover, we
have serendipitously discovered that under UV irradiation
conditions (Hg lamp) this cycloaddition leads to oxazoles
with good yields in the absence of DMAD and may be
considered as a general process for mixed ylides such as
1 and 2 and various nitriles.10 These results encouraged us to
investigate the reaction of mixed ylides 1 and 2 with alkynes
under UV irradiation.
Considering the principal novelty of our synthetic ap-
proach to such rare P-heterocyclic systems, we decided to
study the scope and limitations of the reaction shown in
Scheme 3 by using the ylides 1 and 2 and various alkynes (4a
to 4h). The general results obtained are summarized in
Table 1.
The resulting λ5- phosphinolines were isolated for all
processes in 35-80% yields. Moreover in all the cases of
4b to 4h the corresponding furan was not observed. The
regioselectivity of the process looks straightforward: for
monosubstituted acetylenes observed so far the bulky sub-
stituent (R2) prefers a position removed from the substituent
R1-CO.
To rationalize our results we assume that the irradiation
causes an elimination of phenyliodide to generate an inter-
mediate A with a carbocationic center at the carbon atom
adjacent to the Ph3P moiety. The following attack by the
nucleophilic alkyne via the transition state Bq with sub-
sequent cyclization to the intermediate C results in the
formation of the phosphinoline (see Scheme 4).
Results and Discussion
To find out the nature of the proposed intermediate A
we have heated a solution of 1 in degassed methylene
chloride under argon atmosphere. After workup we isolated
iodobenzene (100%) and the product 21 (85%) (Scheme 5).
Triphenylphosphinoxide (15%) was isolated as the minor
product. Irradiation of 1 in the presence of styrene
yielded the same products as obtained by thermolysis.
Attempts to perform the photochemical reactions of
different ylides with arylalkynes containing electron-
withdrawing groups in the phenyl ring afforded complex
mixtures (in the 31P NMR spectrum at least eight signals were
found) whereas the desired furans of type 3 were not isolated.
(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.
(8) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Zefirov, N. S. Russ. Chem. Bull. 2008, 2195–2197.
(9) (a) Brovarets, V. S. Zh. Obshch. Khim. 1998, 68, 167–168. (b)
Vydzhak, R. N.; Brovarets, V. S.; Pil’o, S. G.; Drach, B. S. Russ. J. Gen.
Chem. 2002, 72, 207–211.
€
(11) Markl, G. Angew. Chem. 1963, 75, 168.
€
(12) Markl, G.; Heier, K.-H. Angew. Chem. 1972, 84, 1066–1067.
(13) Heim, U.; Pritzkow, H.; Fleischer, U.; Grutzmacher, H.; Sanchez,
€
M.; Reau, R.; Bertrand, G. Chem. Eur . J. 1996, 2, 68–74.
(14) Wang, Zh-X.; Schleyer, P. v. R. Helv. Chim. Acta 2001, 84, 1578–
1600.
(10) Matveeva, E. D.; Podrugina, T. A.; Pavlova, A. S.; Mironov, A. V.;
Gleiter, R.; Zefirov, N. S. Eur. J. Org. Chem. 2009, 2323–2327.
(15) Nyulaszi, L. Chem. Rev. 2001, 101, 1229–1246.
J. Org. Chem. Vol. 74, No. 24, 2009 9429

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JOCArticle
SCHEME 3. The Reaction of Ylide 2 with 4-Metoxyphenylacetylene 4a: Synthesis of Furan 5 and λ5-Phosphinoline 6
TABLE 1. Photochemical Reaction of Phosphonium-Iodonium Ylides
with Different Acetylenes
of the phosphinolines, especially in the benzoyl-substituted
ones. The 13C NMR signal of C1 is observed at δ 73 (1JCP
=
100-105 Hz) whereas for an aromatic environment it is
expected at δ 125-140. The above-mentioned bond alter-
nance is contrasted by the results reported for 1,1-dimethyl-
2,4,6-triphenylphosphorin 22.18 In this compound the
˚
P-C2, P-C6 bonds amount to 1.74 A, whereas the C-C
bond lengths within the six-membered ring vary between
˚
1.38 and 1.40 A, only. These values agree quite well with
the results of calculations on 1,1-dimethylphosphorin14
for which calculated NICS values support a nonaromatic
character.
The disubstituted acetylene 1,1,3-triphenylpropyne 4d
reacts with ylide 2 yielding the mixture of two regioisomers
of phosphinoline 12 (Scheme 6); attempts to separate both
were unsuccessful. However, the mixture of isomers could be
identified by their NMR spectra. In the 13C NMR spectra the
signals of both isomers are observed (two doublets of
quaternary C-atom at δ 113 (1JCP= 85.1 Hz) and 115
(1JCP= 85.9 Hz)).
The reaction of diphenylbutadiyne 4f with ylide 2 yielded
only one phosphinoline 16a (Scheme 7); the NMR data of
this product have allowed us to define exactly the positions of
the substituents (the doublet of acetylene carbon at δ 92.69
with 3JPC=16.9 Hz).
Phosphinolines (6, 8, 10, 12, 14, 17, and 19) of the benzoyl-
substituted series are stable compounds, while phosphino-
lines of the carboethoxy-substituted series are labile ones.
Only one phospholine 16a (Scheme 7) was isolated. The
other possible isomer 16b was not detected.
starting material
ylide
alkyne
products
yields, %
no.
R1
Ph
R2
R3
no.
no.
2
1
2
1
2
1
2
1
2
1
2
2
1
2
1
4-CH3OC6H4
4-CH3OC6H4
Ph
H
4a
4a
4b
4b
4c
4c
4d
4d
4e
4e
4f
6
45a
65
50
75
50
50
50
45
60
40
35
65
65
80
60b
OC2H5
Ph
H
7
H
8
OC2H5
Ph
Ph
C8H17
H
9
H
10
11
12
13
14
15
16
17
18
19
20
OC2H5
Ph
C8H17
Ph2CH
Ph2CH
H
Ph
Ph
H
OC2H5
Ph
(CH2)4CtCH
(CH2)4CtCH
PhCtC
OC2H5
Ph
Ph
H
Ph
H
cycloC3H5
cycloC3H5
R2 þ R3 = (CH2)6
R2 þ R3 = (CH2)6
4g
4g
4h
4h
OC2H5
Ph
OC2H5
H
aFuran 5 (30%) only was isolated from this reaction. bThe corre-
sponding λ5-phosphinoline is labile and we could not isolate it in pure
form.
No cyclopropane derivative was isolated. These experiments
reveal no evidence for a carbenic nature of intermediate A.
Our X-ray results reveal a nearly planar phosphorin ring
for 8. The six-membered ring of 19 (Chart 1), however, shows
a strongly flattened screw (intermediate between half-chair
and twist boat) conformation with nearly flat fragments
C1-C2-C4-C26 and C4-C26-C21-P (see also the Sup-
porting Information). This geometry was reproduced by the
RICON program16 showing the following ZP puckering
parameters:17 total puckering amplitude s = 0.220, θ =
63.2°, Ψ2=31.4°, and σ=1.0 (the respective torsional angles
are equal to 1.9° and 1.0°). The six-membered rings in 8 and
The structure of all phosphinolines was confirmed by their
NMR spectroscopic data. In the 31P NMR spectrum the
signals of the phosphinolines are observed in a wide area of
δ 2-13 depending on the substituents of the CdC fragment. In
1
the H NMR spectra of the benzoyl-substituted phosphino-
lines, synthesized from terminal acetylenes, the doublet of the
vinylic proton is observed at δ 7.0-7.15 (3JPH=31-32 Hz).
A comparison of the NMR spectra of the benzoyl-
substituted phosphinoline (6, 8, 10, 12, 14, 16, 17, and 19)
with those of the carboethoxy-substituted phosphinolines (7,
9, 11, 15, 18) shows for the latter systems strongly broadened
lines with low intensity of the signals for the protons of the
ylidic fragment. This fact complicated their interpretation.
The same appearance of spectra was observed for the mixed
ylide 1. The broadness of the signals in the NMR spectra we
attribute to a dynamic equilibrium between two geometric
isomers of the phosphinolines shown in Scheme 8.
˚
19 show a considerable bond alternation: a long (1.78 A)
˚
bond for the P-C21 bond as compared to P-C1 (1.74 A,
˚
˚
1.73 A) and shorter C-C bonds C21-C26 (1.41 A) and
˚
˚
˚
C4-C2 (1.35 A, 1.36 A) as compared to C4-C26 (1.46 A)
(see Supporting Information). These X-ray diffraction data
point to an ylidic character of the phosphorin rings in 8 and
19. In agreement with these views are the 13C NMR spectra
In the 13C NMR spectra of the carboethoxy-substituted
phosphinolines (7, 9, 11, 15, and 18) the signal for the ylidic
C-atom was not observed, even at higher temperature
(30-40 °C). The same effect was found for the ylide 1.
(16) Zotov, A. Yu.; Palyulin, V. A.; Zefirov, N. S. J. Chem. Inf. Comput.
Sci. 1997, 37, 766–773.
(17) Zefirov, N. S.; Palyulin, V. A.; Dashevskaya, E. E. J. Phys. Org.
Chem. 1990, 3, 147–158.
(18) Daly, J. J. J. Chem. Soc. A 1970, 1832–1836.
9430 J. Org. Chem. Vol. 74, No. 24, 2009

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SCHEME 4. Proposed Mechanism for the Photochemical Formation of Phosphinolines
SCHEME 5. Thermolysis of 1
SCHEME 8. A Dynamic Equilibrium between Two Geometric
Isomers of Carboethoxy-Substituted Phosphinolines
CHART 1. Formulas of 8 and 19
equilibrium between two geometric isomers of the phos-
phinoline.
The reaction of ylide 1 with 1,1,3-triphenylpropyne leads
to the mixture of two regioisomers of phosphinoline 13 (see
Scheme 9), and each of them can be in a dynamic equilibrium
between two geometric isomers. One of the regioisomers,
13a, has been isolated by chromatographic separation.
1
NMR spectra of this isomer are highly resolved: in the H
NMR spectrum the signals of the ethoxy group represent a
triplet at δ 0.5 (CH3) and a quadruplet at δ 3.25 (OCH2), in
the 13C NMR spectrum the signal of the ylidic C atom is
observed at δ 53 (1JCP=110 Hz).
Conclusion
Our investigations of the chemistry of the phosphonium-
iodonium ylides 1 and 2 suggest that the irradiation of
these species with UV light generates a highly electrophilic
intermediate. In the presence of nucleophilic alkynes
this intermediate can be trapped by cycloaddition to yield
λ5-phosphinolines. This reaction provides a novel access to
these heterocycles. Our structure investigations of the result-
ing products reveal a nearly planar phosphinoline ring.
SCHEME 6. The Reaction of Ylide 2 with 1,1,3-Triphenyl-
propyne 4d
SCHEME 7. Synthesis of λ5-Phosphinoline 16a from
Diphenylbutadiyne 4f and Ylide 2
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. 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
separation was carried out on columns with Silica gel 60.
Cyclooctyne was prepared by bromination of cyclooctene
followed by two dehydrobrominations with t-BuOK and
LDA.19
In the 31P NMR spectrum at -50 °C the signal of
carboethoxy-substituted phosphinoline 9 is observed as the
superposition of two signals. And in the 13C NMR spectrum
of this phosphinoline the signal of the ylidic C-atom repre-
sents two doublets at δ 55.81 and 57.26 (1JCP =109.5 Hz,
1JCP=110 Hz). This fact indicates the presence of a dynamic
General Procedure for the Reaction of Ylides with Alkynes.
The alkyne was added to a solution of ylides 1 and 2 (0.3 g) in
(19) Brandsma, L.; Verkruijsse, H. D. Synthesis 1978, 290.
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SCHEME 9. The Reaction of Ylide 1 with 1,1,3-Triphenylpropyne 4d
anhydrous dichloromethane. The reactions were irradiated in a
quartz flask with a mercury light (366 nm) source in argon
atmosphere. The course 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 the residual alkynes and
PhI benzene were used; the corresponding phosphinoline was
eluted by using a CH2Cl2/MeOH mixture in a ratio of 200:1.
Preparation of Phenyl(1,1,4-triphenyl-1λ5-phosphinolin-2-yl)-
methanone 8. Starting material: 0.1 mL (0.9 mmol) of 4b.
Product: 0.11 g (50%) of 8 as yellow crystals. Mp: 259-
s. IR, ν/cm-1: 1580 (CdO), 1525 (CdC), 770, 1440 (Ar). MS,
m/z: 444 [M]þ, 339 [M - PhCO]þ. HRMS calcd for C31H25OP
(Mþ) m/z 444.1643, found 444.1684.
Preparation of (5,5-Diphenyl-7,8,9,10,11,12-hexahydro-5λ5-
cycloocta[c]phosphinolin-6-yl)(phenyl)methanone 19. Starting
material: 0.1 mL of 4h. Product: 0.175 g (80%) of 19 as a red
oil. This oil was dissolved in a minimum of CH2Cl2 and
subsequent addition of diethyl ether, hexane, and cyclohexane
to this solution resulted in crystallization of phosphinoline 19 as
red crystals. Mp: 179-180 °C. 1H NMR (CDCl3), δ: 0.92-1.04
(m, 4H, 2CH2), 1.18-1.34 (m, 4H, 2CH2), 2.41, 2.82 (both t, 2H,
2CH2), 6.97-7.00 (m, 2H, arom), 7.20-7.38 (m, 10H, arom.),
7.60-7.68 (m, 7H, arom.). 13C NMR (CDCl3), δ: 26.25, 26.39,
1
3
260 °C. H NMR (CD2Cl2), δ: 7.07 (d, JPH = 31,5 Hz, 1H,
CH), 7.12 (m, 1H, arom.), 7.25 (m, 1H, arom.), 7.35-7.45 (m,
10H, arom), 7.51-7.65 (m, 8H, arom.), 7.84-7.90 (m, 4H,
3
26.87, 29.63, 31.49 (all s, CH2), 34.41 (d, JCP=8.0 Hz, CH2),
1
arom.). 13C NMR (CD2Cl2), δ: 73.73 (d, JCP= 100.5 Hz,
69.86 (d, 1JCP=101.2 Hz, C1), 113.90 (d, 1JCP=90.0 Hz, arom.),
117.70 (d, 3JCP=9.7 Hz, CdC), 123.79 (d, 2JCP=12.1 Hz, arom),
124.14 (d, 3JCP = 8.9 Hz, arom.), 127.95 (s, arom.), 128.58 (d,
3JCP= 12.8 Hz, arom.), 128.83 (s, arom.), 129.59 (s, arom.),
1
C1), 110.78 (d, JCP =85.8 Hz, arom.), 116.85 (d, JCP =10.0
=
Hz, CHCPh), 124.00 (d, 2JCP=11.5 Hz, arom.), 125.43 (d, 3JCP
7.6 Hz, arom.), 125.93 (s, arom.), 127.04 (d, JCP = 93.5 Hz,
1
3
arom.), 127.88 (s, arom.), 128.30 (s, arom.), 128.55 (d, JCP
4
=
13.0 Hz, arom.), 128.67 (s, arom.), 129.43 (s, arom.), 129.93 (s,
131.47 (d, JCP=1.6 Hz, arom.), 131.58 (s, arom.), 132.88 (d,
3JCP3=8.1 Hz, arom.), 132.97 (d, 2JCP=10.4 Hz, arom.), 140.24
4
arom.), 131.47 (s, arom.), 131.78 (d, JCP = 3.1 Hz, arom.),
3
(d, JCP= 4.9 Hz, arom.), 141.08 (d, JCP = 4.0 Hz, arom.),
2
133.19 (s, CH), 133.31 (d, JCP = 10.7 Hz, arom.), 133.46 (s,
143.77 (d, JCP=10.4 Hz, arom.), 187.46 (d, 2JCP=5.6 Hz, CO).
31P NMR (CDCl3), δ: 2.77 s. Anal. Calcd for C34H31OP: C,
83.95; H, 6.38. Found: C, 84.01; H, 6.22. MS, m/z: 486 [M]þ.
arom.), 140.55 (d, 2JCP=9.9 Hz, arom.), 141.41 (d, 3JCP=4.6 Hz,
arom.), 142.75 (s, arom.), 189.39 (d, JCP = 6.1 Hz, CO). 31P
NMR (CDCl3): δ 2.94 s. IR, ν/cm-1: 1580 (CdO), 1520 (CdC),
720-750, 1470 (Ar). Anal. Calcd for C34H25OP: C, 85.00; H,
5.21. Found: C, 85.24; H, 5.07.
Acknowledgment. We are grateful to the Deutsche For-
schungsgemeinschaft (DFG) for financial support. The stay
of N.S.Z. at the University of Heidelberg was made possible
by the Alexander von Humboldt Foundation. We are grate-
ful to Dr. J. H. Gross (Heidelberg) for providing the HRMS
data. We are grateful to the Russian Foundation for Basic
Research (Project No. 08-03-00611) and the Division of
Chemistry and Materials Science of the Russian Academy
of Sciences (OChNM-1, and OChNM-9).
Preparation of (4-Cyclopropyl-1,1-diphenyl-1λ5-phosphinolin-
2-yl)(phenyl)methanone 17. Starting material: 100 mg (1.35
mmol) of 4g. Product: 0.130 g (65%) of 17 as a yellow oil.
1H NMR (CDCl3), δ: 0.45, 0.82 (both m, 2H, CH2), 1.73 (t, 1H,
3
CH), 7.14 (d, JPH =32,1 Hz, 1H, CH), 7.15 (m, 1H, arom.),
7.41-7.57 (m, 11H, arom.), 7.65-7.67 (m, 2H, arom.),
7.81-7.86 (m, 4H, arom.), 8.01-8.04 (m, 1H, arom.). 13C
NMR (CDCl3), δ: 6.08 (s, CH2), 14.64 (s, CH), 73.00 (d,
1
1JCP= 100.4 Hz, arom.), 111.52 (d, JCP = 85.1 Hz, arom.),
3
2
113.70 (d, JCP =9.6 Hz, CHdC), 123.67 (d, JCP= 12.1 Hz,
arom.), 124.01 (d, 2JCP=8.0 Hz, arom.), 127.07 (d, 1JCP=94.0
Hz, arom.), 127.75 (s, arom.), 128.41 (d, 3JCP=12.8 Hz, arom.),
Supporting Information Available: 1H, 31P, 13C NMR
spectra of the new compounds furan 5 and phosphinolines
6-19, X-ray analysis of the molecular structures of 8 and 19
and a table of the most relevant distances as well as CIF files of
compounds 8 and 19, and detailled experimental procedures
for the preparation of 6, 7, 9, 10-16, and 18. This material is
available free of charge via the Internet at http://pubs.acs.org.
3
128.81 (s, arom.), 129.27 (s, arom.), 130.43 (d, JCP= 7.2 Hz,
CH), 131.44 (d, 4JCP= 2.4 Hz, arom.), 131.54 (s, arom.), 133.18
(d, JCP= 7.3 Hz, arom.), 133.25 (d, JCP= 10.4 Hz, arom.),
3
2
2
3
140.57 (d, JCP= 9.6 Hz, arom.), 142.72 (d, JCP= 4.9 Hz,
arom.), 188.68 (d, JCP=5.7 Hz, CO). 31P NMR (CDCl3), δ: 2.84
9432 J. Org. Chem. Vol. 74, No. 24, 2009