Intramolecular cycloaddition reactions of 1-alkenyl-3,4,5-triaryl-1,2- diphosphacyclopenta-2,4-dienes

Article abstract of DOI:10.1002/ejoc.201100615

1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes obtained by alkylation of sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienide with Br(CH₂)_nCH=CH₂ undergo, depending on the n value, either an intermolecular Diels

Full text of DOI:10.1002/ejoc.201100615

FULL PAPER
DOI: 10.1002/ejoc.201100615
Intramolecular Cycloaddition Reactions of 1-Alkenyl-3,4,5-triaryl-1,2-
diphosphacyclopenta-2,4-dienes
Almaz A. Zagidullin,[a] Vasili A. Miluykov,*[a] Dmitry B. Krivolapov,[a]
Sergey V. Kharlamov,[a] Shamil K. Latypov,[a] Oleg G. Sinyashin,[a] and
Evamarie Hey-Hawkins[b]
Keywords: Cycloaddition / Phospholes / Cage compounds / Conformation analysis
1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes
obtained by alkylation of sodium 3,4,5-triaryl-1,2-diphos-
phacyclopentadienide with Br(CH2)nCH=CH2 undergo, de-
pending on the n value, either an intermolecular Diels–Alder
reaction leading to polymeric compounds (n = 1, 4) or intra-
molecular cycloaddition reactions to give tricyclic cage phos-
phanes with high regio- and stereoselectivity (n = 2, 3). The
structures and conformational behavior of these new tricyclic
phosphanes are discussed.
Introduction
Intramolecular cycloaddition reactions have received sig-
nificant interest in organic chemistry.[1] Highly regio- and
stereoselective intramolecular Diels–Alder (IMDA) reac-
tions have been successfully employed in the synthesis of
various natural products[2,3] and drugs.[4] Although IMDA
reactions of carbo- and heterocyclic compounds are well
studied, little is known about reactions involving phos-
phacyclopentadienes (phospholes), although the resulting
products, phosphorus cages, are very interesting as bulky
ligands in homogeneous catalysis. However, as a result of
aromatic delocalization within the ring,[5,6] 1H-phospholes
are typically poor dienes, as also reflected by the harsh con-
ditions needed for intramolecular cycloaddition reactions.
Thus, heating of 1-butenylphosphole at 140 °C in xylene for
10–12 h gave the expected tricyclic phosphane in acceptable
yield.[7] However, the presence of electron-acceptor substit-
uents (allyl-O, allyl-N)[7] at the phosphorus atom or com-
plexation with transition metal atoms (Cr, Mo, W)[8] can
dramatically increase the reactivity of the diene system of
1H-phospholes, and thus, intramolecular cycloaddition re-
actions take place at room temperature.
Therefore, 1-alkyl-1,2-diphosphacyclopenta-2,4-dienes
(1-alkyl-1,2-diphospholes) are of special interest because
they combine the structural elements of both 1H- and 2H-
phospholes in one molecule. They demonstrate high
thermal stability like 1H-phospholes and dual reactivity in
cycloaddition reactions typical for 2H-phospholes.[11]
We herein report on the synthesis and cycloaddition reac-
tions of 1-alkenyl-3,4,5-triaryl-1,2-diphosphacylopenta-2,4-
dienes and on the structures and conformational behavior
of the resulting tricyclic phosphanes.
Results and Discussion
Synthesis
Although 2H-phospholes containing highly reactive P=C
bonds show higher activity in cycloaddition reactions,[9,10]
no intramolecular cycloaddition reactions of these hetero-
cycles are known due to their instability.
Sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienides
1a–c react with bromoalkenes Br(CH2)nCH=CH2 at low
temperature to give the corresponding 1,2-diphospholes 2–
5 (Scheme 1). However, the stability of 2–5 clearly depends
on the number of CH2 groups.
Thus, 1-allyl-3,4,5-triphenyl-1,2-diphosphole (2a) was
obtained as the main product of the reaction of allyl bro-
mide (n = 1) with sodium 3,4,5-triphenyl-1,2-diphosphacy-
clopentadienide (1a). The 1H NMR spectrum of 2a exhibits
multiplets at δ = 4.7 and 5.5 ppm for vinyl protons, and the
31P{1H} NMR spectrum of 2a consists of two doublets at
δ = 61 and 217 ppm for three- and two-coordinate phos-
[a] A. E. Arbuzov Institute of Organic and Physical Chemistry,
Russian Academy of Sciences,
Arbuzov Str. 8, 420088 Kazan, Russian Federation
E-mail: miluykov@iopc.knc.ru
[b] Institut für Anorganische Chemie, Universität Leipzig,
Johannisallee 29, 04103 Leipzig, Germany
E-mail: hey@rz.uni-leipzig.de
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201100615.
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1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes
Scheme 1.
phorus atoms, respectively, with a large coupling constant,
1JPP ≈ 400 Hz, that is typical for 1-alkyl-1,2-diphos-
pholes.[12] Unfortunately, compound 2a is unstable in solu-
tion. After several hours, the two doublets in the 31P{1H}
NMR spectrum disappeared, and a poorly soluble precipi-
tate formed. Based on our previous studies on the reactivity
of 1-alkyl-1,2-diphospholes,[11] we propose that an intermo-
lecular [4+2] cycloaddition reaction takes place, resulting in
polymers.
Surprisingly, 1,2-diphospholes 3a–c and 4a–c formed
from sodium 3,4,5-triaryl-1,2-diphosphacyclopentadienides
1a–c and 4-bromo-1-butene or 5-bromo-1-pentene are very
unstable and undergo intramolecular [4+2] cycloaddition
reactions to give tricyclic cage phosphanes 6a–c and 7a–c
at room temperature. The 31P{1H} NMR spectra of the re-
action mixtures show only two doublets in the range of δ =
Figure 1. Correlation of calculated GIAO [B3LYP/6-31G(d)//HF/
6-31G(d)] chemical shifts of A/B isomers versus experimental
13C{1H} NMR spectra of 6a.
1
40 and –20 ppm with JPP ≈ 190 Hz for compounds 6a–c
lated GIAO chemical shifts and experimental 13C{1H}
NMR spectra has been observed for isomer A, whereas for
isomer B it is worse (R2 = 0.917, Figure 1).
1
and at about δ = 6 and –30 ppm with JPP ≈ 220 Hz for
compounds 7a–c. This indicates high regio- and stereoselec-
tivity of the intramolecular cycloaddition reactions. No sig-
However, the formation of stable 1,2-diphosphole 5a was
observed in the reaction of 2a with 6-bromo-1-hexene. The
31P{1H} NMR spectrum of 5a exhibits two doublets in the
1
nals for vinyl protons were found in the H NMR spectra
of tricyclic phosphanes 6a–c and 7a–c.
The structures of tricyclic phosphanes 6a–c and 7a–c
were unequivocally established by NMR spectroscopy cor-
relation experiments. The combination of different 2D ex-
periments[13,14] (1H–1H COSY, 31P–31P COSY, 1H–31P
1
range of δ = 200 and 70 ppm with JPP ≈ 410 Hz, which is
typical for 1-alkyl-1,2-diphospholes.[14] Compound 5a dem-
onstrates good thermal stability: cycloaddition proceeds
only on heating of a solution of 5a in toluene to 100 °C for
3 h with formation of a precipitate that is insoluble in com-
mon organic solvents, presumably a polymeric compound.
Thus, it can be concluded that reactions of sodium 3,4,5-
triaryl-1,2-diphosphacyclopentadienides 1a–c with bromo-
alkenes clearly depend on the length of the alkylene spacer
between the bromo substituent and the C=C double bond.
Only in the case of n = 2 and 3 are tricyclic phosphanes
6a–c and 7a–c obtained.
1
HMBC, H–13C HSQC/HMBC and 19F–1H HETCOR) al-
lowed straightforward identification of spin systems of pro-
tons and phosphorus atoms, assignment of all carbon sig-
nals, and thus, proof of the overall structure (see the Sup-
porting Information for details). In addition, good corre-
lation of calculated [gauge-including atomic orbital
(GIAO)][15–17] versus experimental 13C{1H} chemical shifts
additionally supports the above conclusions on the struc-
tures of these compounds. Moreover, according to the di-
versity of NMR spectroscopy correlations, only one re-
gioisomer is present in solution (Figure 1).
X-ray Crystallography
Analysis of the chemical shifts of the aliphatic carbon
atoms, which “sense” the difference between two possible
The molecular structures of 6a and 7c (Figures 2 and 3)
isomers, allows unambiguous exclusion of the formation of were obtained by X-ray crystallography. The two molecules
isomer B. Indeed good correlation (R2 = 0.997) of calcu- are quite similar, except for the number of methylene groups
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V. A. Miluykov et al.
FULL PAPER
(two in 6a vs. three in 7c). Each phosphorus atom has a tively. However, no pyramidalization of carbon atoms of
typical pyramidal environment. The inner angle at the the double bond (C3 and C4) was observed for 7c (ψ = 4.64
bridging phosphorus atom (P1) is very acute [C5–P1–P2 and 3.79°, respectively).
84.36(6)° for 6a and C10–P1–P7 83.94(8)° for (7c)]. Both
Both tricyclic molecules 6a and 7c have four chiral cen-
carbon atoms of the double bond (C3 and C4) in 6a are ters: two carbon atoms (C2 and C7) and two non-racemiz-
slightly pyramidalized[18] with ψ = 11.56 and 3.36°, respec- able phosphorus atoms (P1 and P5). However, according
to structural data, only one diastereomer of 6a and 7c is
formed.
The crystal packing of tricyclic phosphanes 6a and 7c is
different. Each enantiomer of 6a forms columns that are
connected with columns of the other enantiomer by π–π
stacking of phenyl rings (distance between rings 3.227 Å;
Figure 4).
Figure 2. ORTEP view of (PSPRCRCR)-7,8,9-triphenyl-1,6-diphos-
phatricyclo[4.3.0.03,7]non-8-ene (6a). Only one of the two enantio-
mers is shown. All hydrogen atoms, except those on aliphatic CH
and CH2 groups, are omitted for clarity. Ellipsoids are given at the
50% probability level. Selected bonds lengths [Å] and angles [°]:
P1–C2 1.889(2), P1–C9 1.854(3), P1–P5 2.2021(9), P5–C4 1.846(2),
P5–C6 1.872(2); C2–P1–P5 84.36(6), C9–P1–C2 92.9(1), C9–P1–P5
98.6(1), C4–P5–C6 91.1(1), C4–P5–P1 87.84(7), C6–P5–P1
91.91(8).
Figure 4. Crystal packing of 7,8,9-triphenyl-1,6-diphosphatricy-
clo[4.3.0.03,7]non-8-ene (6a).
The intermolecular C–H···F contacts observed for 7c re-
sult in a 2D supramolecular architecture (Figure 5). Each
enantiomer of 7c forms a column through three C–F···H
contacts (C14–F14···H212Ј 2.649 Å, C20–F20···H27Ј
2.659 Å, C20–F20···H28Ј 2.555 Å). Additionally, C–F···H
contacts (C26–F26···H12Ј 2.649 Å,
Є C2–H212–F14Ј
157.66°) between the different enantiomers result in the for-
mation of a two-dimensional net (Figure 5).
Conformational Analysis
Figure 3. ORTEP view of (PRPSCSCS)-8,9,10-tris(p-fluorophenyl)-
1,7-diphosphatricyclo[5.3.0.03,8]dec-9-ene (7c). Only one of the two
enantiomers is shown. All hydrogen atoms, except those on ali-
phatic CH and CH2 groups, are omitted for clarity. Ellipsoids are
given at the 50% probability level. Selected bonds lengths [Å] and
angles [°]: P1–C2 1.878(2), P1–C10 1.848(4), P1–P5 2.224(1), P5–
C4 1.853(3), P5–C6 1.849(3); C2–P1–P5 83.94(8), C10–P1–C2
102.0(2), C10–P1–P5 107.2(1), C4–P5–P1 84.69(9), C6–P5–C4
91.0(1), C6–P5–P1 95.8(1).
At room temperature, some signals in the 1H NMR spec-
tra of tricyclic phosphanes 6a–c and 7a–c are very broad
(e.g., H11/15, Figure 6) and were revealed only in NOE
spectra when proton H7 was irradiated (see also the Sup-
porting Information).
Moreover, a detailed inspection of the 13C{1H} spectra
of 6a showed that the signals of the aromatic ortho-carbon
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1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes
Figure 5. Crystal packing of 8,9,10-tris(p-fluorophenyl)-1,7-diphosphatricyclo[5.3.0.03,8]dec-9-ene (7c).
1
Figure 6. 13C{1H} and H NMR spectra of 7,8,9-triphenyl-1,6-diphosphatricyclo[4.3.0.03,7]non-8-ene (6a) in CDCl3 at different tempera-
tures; rate constants (k, Hz) derived by DNMR (at 273–303 K) and magnetization transfer (233 K) analyses.
atoms were also strongly broadened, particularly those of
the carbon atoms C11/15 and C17/21 (Figure 6).
To verify these findings, low-temperature NMR spec-
troscopy experiments were carried out on compound 6a.
To understand the processes that affect the NMR spectra Indeed, decreasing the temperature produced essential
1
so dramatically, the barrier of rotation around the Ar–C changes in the H and 13C{1H} NMR spectra, particularly
bonds was analyzed theoretically. Indeed, the potential-en- for the aromatic ortho- and meta-protons of Ph2 and Ph1
ergy surface (PES) calculated for the three Ph–C bonds of (Figure 6). At about 273–253 K, coalescence of the signals
6a (Figure 7) revealed at least two bonds (Ph2–C and Ph1– of carbon atoms C17/21 was also observed (Figure 6b, c).
C) for which the barriers were high, and therefore, rotation Finally, at 233 K, due to slow exchange, each ortho-proton
may have been slow on the NMR timescale at room tem- resonated separately (Figure 6a), as shown by NOE spectra
perature. The rotation barrier was only too low to influence with irradiation of proton H7 (see the Supporting Infor-
the NMR line shape for the bond Ph3–C. The highest bar- mation, Figure S9). The corresponding ortho-carbon atoms
rier was expected for the Ph1–C bond.
(C11 and C15) of Ph1 were also inequivalent, as unequivo-
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V. A. Miluykov et al.
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The experimentally observed inequivalence of the ortho-
protons and ortho-carbon atoms of Ph1 is in agreement with
theoretically predicted values [B3LYP/6-31G(d)//HF/6-
31G(d)]. Thus, signals of H11 and C11 are observed at
lower field than those of H15 and C15 by about +0.5 and
+4.0 ppm, respectively, and calculations predict the same
sign and close values for these nuclei {+0.4 (1H) and
+5.6 ppm [13C(1H)]}. Hence, the method and level of theory
used in geometry optimizations and NMR parameter calcu-
lations adequately reproduce experimental values and can
be used, for example, to estimate inherent differences in
chemical shifts for ortho nuclei of Ph2 to obtain an insight
into dynamic properties of these aromatic systems.
Unfortunately, estimation of the barrier of rotation for
the second phenyl ring is not as straightforward thanks to
several obstacles. First, because almost no differentiation of
the two ortho-protons occurs, line-shape analysis could not
be employed. Only the 13C NMR spectra show notable line-
Figure 7. Potential-energy profile (HF/6-31g) for rotation around
the Ph–C bonds of 6a.
cally established by low-temperature 2D HSQC correlations shape evolution of the ortho-carbon atoms with tempera-
(see the Supporting Information, Figure S10). Assignment ture and therefore could be used. However, due to a lower
of C11 versus C15 was additionally supported by carbon– barrier of rotation around the Ph2–C bond, we were unable
phosphorus spin–spin coupling data: for C11 (which is in to obtain meaningful 13C NMR spectra at 233 K. Further-
3
the syn orientation with respect to P1) JPC = 22.5 Hz is in more, decreasing the temperature led to extensive precipi-
good agreement with the calculated value (3JPC = 17 Hz), tation of the compound and resulted in a very low signal-
whereas for C15 (which is in an anti orientation with respect to-noise ratio in the spectra. Only low-temperature (233 K)
to P1) there is no notable coupling according to experiment 2D HSQC spectra allowed two ortho-carbon atom cross-
and theory. The signals of the ortho-carbon atoms of Ph2 peaks to be observed separately in slow exchange regimes
are also extremely broadened at this temperature and were (see the Supporting Information, Figure S9). The chemical
revealed only by the 2D HSQC method (see the Supporting shift difference of the signals of the ortho-carbon atoms C17
Information, Figure S10). Thus, at 233 K rotation around and C21 was used to calculate exchange-average 13C{1H}
the C–C(Ph1) bond is slow on the NMR spectroscopy time- spectra for these carbon atoms at higher temperatures (see
scale [1H and 13C(1H)], while rotation around the C–C(Ph2) the Supporting Information, Figure S9). Thus, by using the
bond is faster. All other nuclei exhibit only small changes Eyring equation,[20] estimation of ΔH# and ΔS# for rotation
with variable temperature.
around the C–C(Ph2) bond was also possible (Table 1).
Comparison of experimental and calculated values re-
The temperature dependence of the rate constant was an-
alyzed to obtain the experimental value of the energy bar- veals some particularities: (1) experimental ΔH# values are
rier, which could be directly compared with the calculated notably lower than calculated ones for both phenyl rings;
barrier of rotation. The energy barrier of the first phenyl (2) there is a remarkable negative entropy contribution to
ring could be estimated quite easily: first, since the ortho- the energy barrier (ca. –20 calmolϪ1); and (3) ΔΔH#
=
protons and ortho-carbon atoms become inequivalent on 2 kcalmol–1 for the two aromatic rings is close to the pre-
1
the NMR timescale (233 K), line-shape analysis of H and/ dicted difference.
or 13C{1H} spectra at room and moderately low tempera-
To rationalize the discrepancies between experimental
tures provides rate constants (Figure 6); in addition, at and theoretical data, several factors were analyzed. First, it
233 K magnetization transfer due to chemical exchange was ruled out that the reason was simply due to limitations
monitored by NOE experiments (see the Supporting Infor- of the level of theory used in the calculations, since in-
mation, Figure S9) allows the rate constants to be estimated clusion of polarization function (as recommended for aro-
at low temperature.[19] The dependence of ln(k/T) versus matic and heteroaromatic systems) and optimization with
1/T was obtained to construct an Eyring plot,[20] which the B3LYP functional (to take into account correlation ef-
gave values for ΔH# (8.4 kcalmol–1) and ΔS# fects) did not modify the predictions (Table 1). Therefore,
(–20.1 calmol–1 K–1; Table 1).
we concluded that the optimization in the framework of the
Table 1. Calculated energy barriers and experimental enthalpy and entropy barriers for the rotation of phenyl groups in 6a.
Calculated ΔE# [kcalmolϪ1
]
Experimental
HF/6-31G
HF/6-31G(d)
B3LYP/6-31G(d)
ΔH# [kcalmolϪ1
]
ΔS# [calmolϪ1 KϪ1
]
ΔG# [kcalmolϪ1
]
303
Ph1
Ph2
17.3
15.3
16.7
14.3
16.5
14.8
8.4
6.3
–20.1
–20.3
14.7
12.5
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1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes
HF level with a simple basis set (6-31G) was good enough a lower barrier in concert with twisting of the spacer. Thus,
to obtain reliable energy data.
the effective rate and barrier of Ph1 rotation will be deter-
Next, we tried to attribute the high energy barrier of ro- mined by the rate and barrier of the twisting of the spacer.
tation about the C–C(Ph1) bond to strong interactions with
adjacent groups. We therefore carried out calculations for
model compounds in which the vicinal phenyl group on C3
was replaced by a methyl group, or the aliphatic alkylene
Conclusions
Sodium 3,4,5-triphenyl-1,2-diphosphacyclopentadienide
(1) reacts with allyl bromide or 6-bromo-1-hexene to give
the corresponding 1-alkenyl-3,4,5-triphenyl-1,2-diphos-
phacyclopenta-2,4-dienes 2a, 5a, which undergo [4+2] inter-
molecular cycloaddition reactions to form polymeric com-
pounds. However, alkylation of 1 with 4-bromo-1-butene or
5-bromo-1-pentene proceeds with the formation of tricyclic
cage phosphanes, which are the products of intramolecular
[4+2] cycloaddition reactions. A combination of theoretical
calculations and experimental NMR spectroscopy has been
used to study the conformational behavior of tricyclic phos-
phanes 6, 7 in solution. Hindered rotation around C–C(Ar)
bonds was observed and was caused by interaction with the
alkylene spacer.
chain between P1 and C7 was omitted (Figure 8).
Experimental Section
Figure 8. PES (HF/6-31G) for rotation around the C–C(Ph1) bond
with and without the P1–CH2–CH2–C7 chain and with Me instead
of Ph at C3.
General: All reactions and manipulations were carried out under
dry pure N2 in a standard Schlenk apparatus. All solvents were
distilled from sodium/benzophenone and stored under nitrogen be-
fore use. NMR spectroscopy investigations were carried out in the
NMR department (A. E. Arbuzov Institute of Organic and Physi-
cal Chemistry) of the federal collective spectral analysis center for
physical and chemical investigations of structure, properties, and
According to these calculations, the vicinal Ph group on
C3 has almost no influence on the energy barrier. On the
contrary, elimination of the aliphatic spacer reduces the en-
ergy barrier by about 50%, that is, hindered rotation is
largely due to unfavorable interaction of Ph1 with the ali- composition of matter and materials. All NMR spectroscopy ex-
periments were performed with Bruker AVANCE-600 or AV-
ANCE-400 spectrometers equipped with a 5 mm diameter gradient
inverse broad-band probe head and a pulsed gradient unit capable
of producing magnetic field pulse gradients in the z direction of
53.5 Gcm–1. Frequencies are 600 MHz in 1H, 150 MHz in 13C,
242.9 MHz in 31P, and 376.5 MHz in 19F (Bruker AVANCE-600)
experiments. Chemical shifts are reported on the δ (ppm) scale rela-
tive to the 1H and 13C signals of tetramethylsilane (TMS, δ =
0.00 ppm). 31P chemical shifts were referenced to the 31P signal of
85% H3PO4 (δ = 0 ppm), and 19F chemical shifts to the 19F signal
of C6F6 (δ = –164.9 ppm). Sodium 3,4,5-triaryl-1,2-diphosphacy-
clopentadienides 1 were obtained according to a literature pro-
cedure.[21] Allyl bromide, 4-bromo-1-butene, 5-bromo-1-pentene,
and 6-bromo-1-hexene were purchased from Aldrich and used
without additional purification.
phatic spacer. Taking into account that the experimental
ΔH# value is in good agreement with the value calculated
for the model that lacks the bulky spacer, we can hypothe-
size that the reason lies in the correlated intramolecular mo-
tion of spacer and aromatic rings (Figure 9).
X-ray Analyses: Data for crystals of 6a and 7c were collected with
a Bruker Smart Apex II CCD diffractometer by using graphite-
monochromated Mo-Kα (0.71073 Å) radiation. Data collection
images for crystals of 6a and 7c were indexed, integrated, and
scaled by using the APEX2 data reduction package.[22] Details con-
cerning data collection and refinement are collected in Table S2 in
the Supporting Information. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were located from a difference
Fourier map and refined isotropically. Structure solution and re-
finements were carried out with the programs SIR,[23]
SHELXL97,[24] and WinGX.[25] Pictures were generated with OR-
TEP3 for Windows.[26] CCDC-820410 (6a) and -820411 (7c) con-
Figure 9. Energy profiles (b) for conformational transformations of
tricyclic phosphanes (a).
For example, if the twisting of the aliphatic spacer has a
low energy barrier (close to the local minima or a metasta-
ble state, Figure 9b), with no highly unfavorable interac-
tions between the spacer and the aryl ring, Ph1 rotates with tain the supplementary crystallographic data for this paper. These
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V. A. Miluykov et al.
FULL PAPER
data can be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
906 (w), 930 (w), 988 (w), 1028 (m), 1076 (m), 1135 (w), 1163 (w),
1221 (w), 1261 (w), 1331 (w), 1419 (w), 1441 (m), 1488 (m), 1574
(w), 1579 (w), 1749 (w), 1808 (w), 1808 (w), 1881 (w), 1947 (w),
2861 (w), 2904 (m), 2913 (m), 2931 (m), 2960 (w), 3022 (w), 3053
(w), 3076 (m) cm–1. C25H22P2 (384.39): calcd. C 78.12, H 5.77, P
16.12; found C 77.89, H 5.42, P 16.59.
Computation: The ab initio quantum chemical calculations were
performed by using Gaussian 98.[27] Full geometry optimizations
to a minimum energy were executed at the ab initio HF/6-31G level
unless otherwise noted. Chemical shifts were determined by the
GIAO method within the DFT framework by using a hybrid ex-
change-correlation functional, B3LYP, at the 6-31G(d) level of
theory. All data were referenced to TMS (δ = 0.00 ppm) for 1H and
13C that were calculated at the same level of theory.
7,8,9-Tris(p-methylphenyl)-1,6-diphosphatricyclo[4.3.0.03,7]non-8-
ene (6b): In a manner similar to the procedure used for 6a, com-
pound 6b was obtained from sodium 3,4,5-tris(p-methylphenyl)-
1,2-diphosphacyclopentadienide (1.50 g, 2.26 mmol) and 4-bromo-
1-butene (0.38 g, 2.83 mmol, 25% excess) as a light yellow powder
(0.63 g, 65%). M.p. 142 °C. 31P{1H} NMR (CDCl3): δ = –21.9 (d,
Synthesis
1
1JPP = 194.3 Hz), 39.6 (d, JPP = 194.3 Hz) ppm. 1H NMR
3,4,5-Triphenyl-1-(prop-1-enyl)-1,2-diphosphacyclopenta-2,4-diene
(2a): A solution of allyl bromide (0.19 g, 1.61 mmol) in toluene
(5 mL) was added to a solution of sodium 3,4,5-triphenyl-1,2-di-
phosphacyclopentadienide (1.00 g, 1.61 mmol) in toluene (30 mL)
at –80 °C and then stirred for 2 h while warming to room tempera-
ture. Then the solvent was evaporated under reduced pressure, and
the residue was extracted with toluene/n-hexane (1:10) (2ϫ30 mL).
The solvent of the extract was evaporated in vacuo to leave 2a as
a light yellow oil (0.31 g, 52%). 31P{1H} NMR (C6D6): δ = 217.2
2
2
(CDCl3): δ = 1.64 (m, 2 H, 9-H), 1.82 (dd, JHH = 13.2, JHP
=
2
2
17.0 Hz, 1 H, 6eq-H), 1.90 (dd, JHH = 13.2, JHP = 10.4 Hz, 1 H,
6ax-H), 2.01 (m, 1 H, 8endo-H), 2.17 (m, 1 H, 8exo-H), 2.15 (s, 3 H,
Me-19), 2.23 (s, 3 H, Me-25), 2.23 (s, 3 H, Me-13), 3.18 (m, 1 H,
3
3
7-H), 6.50 (d, JHH = 7.9 Hz, 2 H, 17-H), 6.74 (d, JHH = 7.9 Hz,
2 H, 18-H), 6.89 (d, JHH = 8.1 Hz, 2 H, 23-H), 6.92 (d, JHH
3
3
=
3
7.4 Hz, 2 H, 12-H), 6.95 (d, JHH = 8.1 Hz, 2 H, 24-H), 7.18 (br.
m, 2 H, 11-H) ppm. 13C{1H} NMR (CDCl3): δ = 17.1 (d, JCP
=
1
1
1
(d, JPP = 403.0 Hz), 60.9 (d, JPP = 403.0 Hz) ppm. 1H NMR
23.6 Hz, C-9), 20.9 (s, Me-25), 21.0 (s, Me-13), 21.1 (s, Me-19), 30.5
3
1
2
(C6D6): δ = 2.45 (m, 2 H, CH2), 4.58 (d, JHH = 16.6 Hz, 1 H,
=CH2), 4.64 (m, JHH = 9.8 Hz, 1 H, =CH2), 5.52 (m, 1 H, CH=),
(d, JCP = 26.0 Hz, C-6), 37.6 (s, C-8), 41.6 (br. d, JCP = 2.9 Hz,
C-7), 79.3 (d, 1JCP = 17.0 Hz, C-2), 128.0 (s, C-18), 128.3 (s, C-24),
128.4 (s, C-12), 128.8 (br. s, C-11), 128.9 (br. s, C-17), 129.1 (d,
3JCP = 9.6 Hz, C-23), 135.37 (s, C-13), 135.37 (s, C-19), 135.7 (s,
3
3
3
6.96 (t, JHH = 6.4 Hz, 4 H, Ph), 7.00 (d, JHH = 4.9 Hz, 4 H, Ph),
7.03 (d, 3JHH = 5.9 Hz, 2 H, Ph), 7.07 (d, 3JHH = 7.3 Hz, 2 H, Ph),
3
3
2
7.23 (d, JHH = 5.4 Hz, 1 H, Ph), 7.31 (t, JHH = 8.3 Hz, 1 H, Ph),
C-25), 135.8 (d, JCP = 20.4 Hz, C-22), 136.3 (s, C-16), 138.0 (d,
7.34 (d, JHH = 7.3 Hz, 1 H, Ph) ppm. 13C{1H} NMR (C6D6): δ =
3
2JCP = 6.3 Hz, C-10), 142.0 (dd, JCP = 22.2, 2JCP = 10.4 Hz, C-4),
1
1
2
2
2
25.1 (dd, JCP = 16.7, JCP = 5.8 Hz, CH2), 126.4 (s, p-Ph), 126.52
(s, p-Ph), 126.9 (s, p-Ph), 127.5 (s, m-Ph), 128.0 (s, m-Ph), 128.3 (s,
m-Ph), 128.7 (dd, 2JCP = 11.2, 3JCP = 2.48 Hz, o-Ph), 129.2 (d, 3JCP
= 9.3 Hz, o-Ph), 131.4 (t, JCP = 9.10 Hz, o-Ph), 132.1 (s, =CH2),
133.8 (s, JCP = 9.4 Hz, -CH=), 137.3 (d, JCP = 5.4 Hz, ipso-Ph),
152.0 (dd, JCP = 15.8, JCP = 4.6 Hz, C-3) ppm. IR (KBr): ν =
˜
465 (w), 474 (w), 498 (w), 523 (w), 542 (m), 696 (w), 725 (w), 749
(w), 817 (m), 867 (w), 919 (w), 942 (w), 991 (w), 1020 (m), 1039
(m), 1092 (m), 1113 (m), 1174 (m), 1260 (w), 1407 (w), 1450 (w),
1510 (m), 1571 (m), 1604 (w), 1656 (w), 1899 (w), 2863 (w), 2918
(m), 2961 (w), 3019 (w), 3044 (w), 3076 (w) cm–1. C28H28P2
(426.17): calcd. C 78.86, H 6.62, P 14.53; found C 78.65, H 6.22,
P 14.89.
2
2
2
2
2
2
138.3 (dd, JCP = 10.34, JCP = 4.14 Hz, ipso-Ph), 142.9 (d, JCP
=
2
19.02 Hz, ipso-Ph), 150.3 (pseudo t, JCP = 15.1 Hz, Cring), 164.1
(dd, 1JCP = 10.8, 2JCP = 4.5 Hz, Cring), 191.9 (dd, 1JCP = 56.8, 2JCP
= 14.3 Hz, Cring) ppm. C24H20P2 (370.11): calcd. C 77.83, H 5.44,
P 16.73; found C 77.55, H 5.32, P 16.97.
7,8,9-Tris(p-fluorophenyl)-1,6-diphosphatricyclo[4.3.0.03,7]non-8-
ene (6c): In a manner similar to the procedure used for 6a, com-
7,8,9-Triphenyl-1,6-diphosphatricyclo[4.3.0.03,7]non-8-ene (6a): A pound 6c was obtained from sodium 3,4,5-tris(p-fluorophenyl)-1,2-
solution of 4-bromo-1-butene (0.60 g, 4.43 mmol, 25% excess) in
THF (5 mL) was added to a solution of sodium 3,4,5-triphenyl-
1,2-diphosphacyclopentadienide (2.20 g, 3.54 mmol) in THF
(30 mL) at –80 °C and then stirred for 12 h while warming to room
temperature. Then the solvent was evaporated under reduced pres-
sure, and the residue was extracted with toluene/n-hexane (1:1,
2ϫ30 mL). The extract was filtered, concentrated in vacuo, and
washed with n-hexane (20 mL). Recrystallization from toluene at
cooling gave 6a as light yellow crystals (0.82 g, 60%). M.p. 135 °C.
diphosphacyclopentadienide (1.50 g, 2.23 mmol) and 4-bromo-1-
butene (0.38 g, 2.78 mmol, 25% excess) as a light yellow powder
(0.59 g, 61%). M.p. 143 °C. 31P{1H} NMR (CDCl3): δ = –20.8 (d,
1
1JPP = 195.6 Hz), 43.9 (d, JPP = 195.6 Hz) ppm. 1H NMR
(CDCl3): δ = 1.66 (m, 2 H, 9-H), 1.86 (m, 2 H, 6-H), 1.98 (m, 1 H,
3
8endo-H), 2.20 (m, 1 H, 8exo-H), 3.15 (m, 1 H, 7-H), 6.52 (dd, JHH
4
3
3
= 8.5, JHF = 6.0 Hz, 2 H, 17-H), 6.66 (dd, JHH = 8.5, JHF
=
3
3
9.3 Hz, 2 H, 18-H), 6.78 (dd, JHH = 8.6, JHF = 9.5 Hz, 2 H, 24-
3
4
H), 6.82 (m, 2 H, 12-H), 6.98 (dd, JHH = 8.6, JHF = 8.0 Hz, 2 H,
31P{1H} NMR (CDCl3): δ = –21.4 (d, JPP = 194.7 Hz), 42.1 (d,
23-H), 7.50 (br. m, 2 H, 11-H) ppm. 13C{1H} NMR (CDCl3): δ =
1
1JPP = 194.7 Hz) ppm. 1H NMR (CDCl3): δ = 1.69 (m., 2 H, 9-H), 17.2 (d, JCP = 23.5 Hz, C-9), 30.4 (d, JCP = 26.5 Hz, C-6), 37.6
1
1
2
2
2
2
1
1.89 (dd, JHH = 13.1, JHP = 17.9 Hz, 1 H, 6eq-H), 1.98 (dd, JHH
(s, C-8), 41.8 (br. d, JCP = 3.0 Hz, C-7), 78.7 (d, JCP = 17.3 Hz,
= 13.1, 2JHP = 6.1 Hz, 1 H, 6ax-H), 2.05 (m, 1 H, 8endo-H), 2.22 (m, C-2), 114.7 (d, 2JCF = 21.5 Hz, C-24), 114.8 (d, JCF = 21.1 Hz, C-
2
1 H, 8exo-H), 3.26 (m, 1 H, 7-H), 6.60–7.80 (m, 15 H, Ph) ppm. 18), 115.0 (br. s, C-12), 130.6 (br. s, C-17), 130.7 (dd, JCP = 9.8,
3
13C{1H} NMR (CDCl3): δ = 17.2 (d, JCP = 23.7 Hz, C-9), 30.5
3JCF = 8.5 Hz, C-23), 131.0 (br. s, C-11), 134.2 (d, JCP = 21.0 Hz,
1
2
1
2
1
(d, JCP = 26.5 Hz, C-6), 37.6 (s, C-8), 41.5 (br. d, JCP = 3.1 Hz, C-22), 134.8 (s, C-16), 136.6 (br. s, C-10), 142.4 (dd, JCP = 23.3,
C-7), 79.7 (d, JCP = 17.0 Hz, C-2), 126.08 (s, C-13), 126.10 (s, C- 2JCP = 10.1 Hz, C-4), 151.4 (m, C-3), 161.2 (d, JCF = 245.0 Hz,
1
1
19), 126.3 (s, C-25), 127.3 (s, C-18), 127.6 (s, C-24), 127.7 (s, C-12),
C-13), 161.3 (d, 1JCF = 247.0 Hz, C-19), 161.4 (d, 1JCF = 247.0 Hz,
3
129.0 (br. s, C-17), 129.2 (d, JCP = 9.3 Hz, C-23), 131.4 (br. s, C- C-25) ppm. IR (KBr): ν = 482 (w), 519 (w), 532 (w), 545 (w), 580
˜
11), 138.5 (d, 2JCP = 20.1 Hz, C-22), 139.1 (s, C-16), 141.0 (d, 2JCP
(w), 675 (w), 695 (w), 715 (w), 747 (w), 808 (m), 834 (m), 893 (w),
919 (w), 1014 (w), 1097 (w), 1157 (m), 1223 (m), 1404 (w), 1506 (m),
1598 (m), 1659 (w), 1895 (m), 2922 (w), 3039 (w) cm–1. C25H19F3P2
= 6.1 Hz, C-10), 142.6 (dd, 1JCP = 23.1, 2JCP = 10.4 Hz, C-4), 152.7
2
2
(dd, JCP = 15.9, JCP = 4.6 Hz, C-3) ppm. IR (KBr): ν = 455 (w),
˜
473 (w), 486 (w), 520 (w), 546 (w), 586 (w), 614 (w), 696 (m), 710 (438.09): calcd. C 68.50, H 4.37, P 14.13; found C 68.22, H 4.25,
(w), 722 (w), 744 (w), 761 (w), 770 (w), 792 (m), 828 (w), 883 (w), P 13.86.
4916
www.eurjoc.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2011, 4910–4918

1-Alkenyl-3,4,5-triaryl-1,2-diphosphacyclopenta-2,4-dienes
8,9,10-Triphenyl-1,7-diphosphatricyclo[5.3.0.03,8]deca-9-ene (7a): A
C29H30P2 (440.5): calcd. C 79.07, H 6.86, P 14.06; found C 78.85,
solution of 5-bromo-1-pentene (0.45 g, 3.03 mmol, 25% excess) in H 6.92, P 13.95.
THF (5 mL) was added to a solution of sodium 3,4,5-triphenyl-
8,9,10-Tris(p-fluorophenyl)-1,7-diphosphatricyclo[5.3.0.03,8]deca-9-
1,2-diphosphacyclopentadienide (1.50 g, 2.42 mmol) in THF
(30 mL) at –80 °C and then stirred for 12 h while warming to room
temperature. Then the solvent was evaporated under reduced pres-
sure and the residue was extracted with a mixture of toluene/n-
hexane (1:1) (2ϫ30 mL). The extract was filtered, concentrated in
vacuo and washed with n-hexane (20 mL). Recrystallization from
ene (7c): In a manner similar to the procedure used for 7a, com-
pound 7c was obtained from sodium 3,4,5-tris(p-fluorophenyl)-1,2-
diphosphacyclopentadienide (1.50 g, 2.22 mmol) and 5-bromo-1-
pentene (0.42 g, 2.82 mmol, 25% excess) as light yellow crystals
(0.62 g, 62%). M.p. 155 °C. 31P{1H} NMR (CDCl3): δ = –29.3 (d,
1JPP = 221.7 Hz), 7.1 (d, 1JPP = 221.7 Hz) ppm. 1H NMR (CDCl3):
δ = 1.56 (m, 1 H, 9endo-H), 1.66 (m, 1 H, 9exo-H), 1.69 (m, 2 H, 10-
toluene at cooling gave 7a as light yellow crystals (0.58 g, 60%).
1
M.p. 150 °C. 31P{1H} NMR (CDCl3): δ = –30.3 (d, JPP
=
H), 1.71 (m, 1 H, 8endo-H), 1.79 (m, 1 H, 8exo-H), 1.97 (dd, 2JHH
=
=
220.7 Hz), 5.4 (d, JPP = 220.7 Hz) ppm. 1H NMR (CDCl3): δ =
1
2
2
2
13.3, JHP = 8.2 Hz, 1 H, 6ax-H), 2.26 (dd, JHH = 13.3, JHP
1.54 (m, 1 H, 9endo-H), 1.67 (m, 1 H, 9exo-H), 1.67 (m, 1 H, 8endo
-
3
17.4 Hz, 1 H, 6eq-H), 3.31 (m, 1 H, 7-H), 6.48 (dd, JHH = 8.2,
H), 1.67 (m, 1 H, 10endo-H), 1.75 (m, 1 H, 10exo-H), 1.83 (m, 1 H,
3
4
4JHF = 6.0 Hz, 2 H, 18-H), 6.65 (dd, JHH = 8.2, JHF = 9.6 Hz, 2
8exo-H), 2.02 (dd, JHH = 13.3, JHP = 8.1 Hz, 1 H, 6ax-H), 1.89
2
2
H, 19-H), 6.78 (d, 3JHH = 8.7, 4JHF = 9.4 Hz, 2 H, 25-H), 6.88 (br.
(dd, 2JHH = 13.2, JHP = 17.1 Hz, 1 H, 6eq-H), 3.40 (m, 1 H, 7-H),
2
s, 2 H, 13-H), 7.02 (d, 3JHH = 8.7, JHF = 5.5 Hz, 2 H, 24-H), 7.77
4
6.50–8.00 (m, 15 H, Ph) ppm. 13C{1H} NMR (CDCl3): δ = 17.7
(br. s, 2 H, 12-H) ppm. 13C{1H} NMR (CDCl3): δ = 17.6 (d, JCP
2
2
1
(d, JCP = 3.5 Hz, C-9), 21.6 (d, JCP = 31.7 Hz, C-10), 28.7 (s, C-
1
= 3.4 Hz, C-9), 21.5 (d, JCP = 31.6 Hz, C-10), 28.5 (s, C-8), 31.8
(d, JCP = 25.8 Hz, C-6), 39.2 (br. s, C-7), 69.8 (d, JCP = 17.5 Hz,
C-2), 114.67 (d, JCF = 21.1 Hz, C-19), 114.67 (d, JCF = 21.1 Hz,
C-25), 115.0 (d, JCF = 20.9 Hz, C-13), 130.5 (d, JCP = 10.5, JCF
1
1
8), 31.8 (d, JCP = 25.7 Hz, C-6), 40.0 (br. s, C-7), 70.9 (d, JCP
=
1
1
16.7 Hz, C-2), 126.0 (s, C-14), 126.1 (s, C-20), 126.3 (s, C-26), 127.3
(s, C-19), 127.6 (s, C-25), 128.0 (s, C-13), 128.4 (br. s, C-12), 128.9
(d, 3JCP = 10.3 Hz, C-24), 129.0 (s, C-18), 138.8 (d, 2JCP = 10.5 Hz,
2
2
2
3
3
= 8.9 Hz, C-24), 130.6 (br. s, C-18), 132.0 (br. s, C-12), 134.5 (s, C-
3
2
C-23), 138.9 (d, JCP = 9.9 Hz, C-17), 140.4 (d, JCP = 5.5 Hz, C-
2
17), 136.0 (d, JCP = 25.4 Hz, C-23), 136.0 (br. s, C-11), 147.2 (t,
1
2
2
11), 147.4 (t, JCP = 18.7 Hz, C-4), 158.1 (dd, JCP = 18.4, JCP
=
2
2
1JCP = 19.7 Hz, C-4), 156.7 (dd, JCP = 19.0, JCP = 4.2 Hz, C-3),
4.4 Hz, C-3) ppm. IR (KBr): ν = 480 (w), 499 (w), 514 (w), 541
˜
1
1
161.1 (d, JCF = 246.2 Hz, C-14), 161.38 (d, JCF = 246.2 Hz, C-
(w), 586 (w), 607 (w), 628 (w), 647 (w), 662 (w), 696 (m), 709 (m),
744 (w), 766 (w), 775 (w), 790 (m), 850 (w), 872 (w), 909 (w), 931
(w), 965 (w), 1000 (w), 1029 (w), 1055 (w), 1075 (w), 1155 (w), 1184
(w), 1262 (w), 1336 (w), 1402 (w), 1441 (m), 1462 (w), 1488 (m),
1574 (w), 1597 (w), 1634 (w), 1807 1876 (w), 1946 (w), 2858 (w),
2916 (m), 3021 (w), 3056 (w), 3072 (w) cm–1. C26H24P2 (398.42):
calcd. C 78.38, H 6.07, P 15.55; found C 77.89, H 6.29, P 16.09.
20), 161.41 (d, 1JCF = 246.2 Hz, C-26) ppm. IR (KBr): ν = 409 (w),
˜
475 (w), 508 (w), 533 (m), 543 (m), 578 (w), 615 (w), 643 (w), 662
(w), 676 (w), 698 (w), 714 (w), 725 (w), 746 (w), 771 (w), 804 (m),
839 (m), 877 (w), 915 (w), 961 (w), 1013 (m), 1098 (m), 1155 (m),
1173 (w), 1225 (m), 1261 (w), 1295 (w), 1403 (w), 1424 (w), 1505
(m), 1565 (w), 1602 (m), 1896 (w), 2861 (w), 2928 (w), 3038 (w)
cm–1. C26H21F3P2 (452.11): calcd. C 69.03, H 4.68, P 13.69; found
C 68.85, H 4.93, P 13.84.
8,9,10-Tris(p-methylphenyl)-1,7-diphosphatricyclo[5.3.0.03,8]deca-9-
ene (7b): In a manner similar to the procedure used for 7a, com-
pound 7b was obtained from sodium 3,4,5-tris(p-methylphenyl)-
1,2-diphosphacyclopentadienide (1.50 g, 2.26 mmol) and 5-bromo-
1-pentene (0.42 g, 2.82 mmol, 25% excess) as a light yellow powder
(0.6 g, 61%). M.p. 194 °C. 31P{1H} NMR (CDCl3): δ = –31.1 (d,
1JPP = 220.4 Hz), 3.4 (d, 1JPP = 220.4 Hz) ppm. 1H NMR (CDCl3):
δ = 1.52 (m, 1 H, 9endo-H), 1.63 (m, 1 H, 9exo-H), 1.63 (m, 1 H,
8endo-H), 1.66 (m, 1 H, 10endo-H), 1.74 (m, 1 H, 10exo-H), 1.81 (m,
1-(Hex-1-enyl)-3,4,5-triphenyl-1,2-diphosphacyclopenta-2,4-diene
(5a): In a manner similar to the procedure used for 2a, compound
5a was obtained from sodium 3,4,5-triphenyl-1,2-diphosphacyclo-
pentadienide (1.00 g, 1.61 mmol) and 6-bromo-1-hexene (0.33 g,
2.01 mmol, 25% excess) as a light yellow powder (0.39 g, 59%).
1
M.p. 95 °C. 31P{1H} NMR (C6D6): δ = 211.9 (d, JPP = 416.3 Hz),
68.0 (d, 1JPP = 416.3 Hz) ppm. 1H NMR (C6D6): δ = 1.55–2.04 [m,
8
H, (CH2)4], 4.95 (m,
2
H, =CH2), 5.8 (m,
1
H,
-CH=), 6.90–7.20 (m, 15 H, Ph) ppm. 13C{1H} NMR (C6D6): δ =
2
2
1 H, 8exo-H), 1.98 (dd, JHH = 13.2, JHP = 8.0 Hz, 1 H, 6ax-H),
3
2
21.1 (s, CH2), 23.5 (d, JCP = 7.87 Hz, CH2), 33.6 (d, JCP
=
2
2
2.16 (s, 3 H, Me-20), 2.20 (dd, JHH = 13.2, JHP = 17.0 Hz, 1 H,
1
2
13.95 Hz, CH2), 37.9 (dd, JCP = 16.13, JCP = 5.79 Hz, CH2),
126.4 (s, p-Ph), 126.5 (s, p-Ph), 126.8 (s, p-Ph), 127.5 (s, m-Ph),
128.1 (s, m-Ph), 128.2 (s, m-Ph), 128.6 (s, o-Ph), 129.2 (s, o-Ph),
130.4 (d, JCP = 1.24 Hz, o-Ph), 131.1 (s, =CH2), 133.6 (s, -CH=),
137.5 (d, JCP = 6.20 Hz, ipso-Ph), 138.2 (dd, JCP = 10.34, JCP
3.72 Hz, ipso-Ph), 142.8 (d, JCP = 19.44 Hz, ipso-Ph), 149.2
(pseudo t, JCP = 15.51 Hz, Cring), 164.6 (dd, JCP = 7.24, JCP
3.10 Hz, Cring), 188.8 (dd, JCP = 57.07, JCP = 14.89 Hz, Cring
6eq-H), 2.22 (s, 3 H, Me-26), 2.26 (s, 3 H, Me-14), 3.33 (m, 1 H, 7-
H), 6.43 (d, JHH = 7.7 Hz, 2 H, 18-H), 6.72 (d, JHH = 7.7 Hz, 2
H, 19-H), 6.88 (d, JHH = 8.2 Hz, 2 H, 23-H), 6.97 (br. s, 2 H, 13-
3
3
3
3
3
H), 6.99 (d, JHH = 8.2 Hz, 2 H, 24-H), 7.65 (br. s, 2 H, 12-H)
3
3
3
=
ppm. 13C{1H} NMR (CDCl3): δ = 17.8 (d, JCP = 3.7 Hz, C-9),
2
3
1
20.9 (s, Me-14), 21.0 (s, Me-26), 21.1 (s, Me-20), 21.5 (d, JCP
31.5 Hz, C-10), 28.7 (s, C-8), 31.9 (d, JCP = 25.5 Hz, C-6), 39.1
(br. s, C-7), 70.4 (d, JCP = 15.7 Hz, C-2), 128.0 (s, C-19), 128.3 (s,
C-25), 128.5 (br. s, C-12), 128.6 (s, C-13), 128.9 (d, JCP = 10.9 Hz,
=
3
3
3
=
)
1
3
3
1
ppm. C27H26P2 (412.44): calcd. C 78.63, H 6.35, P 15.02; found C
78.85, H 6.62, P 14.95.
3
C-24), 130.0 (s, C-18), 135.3 (s, C-14), 135.4 (s, C-20), 135.8 (s, C-
2
2
26), 136.0 (s, C-17), 136.1 (d, JCP = 20.8 Hz, C-23), 137.4 (d, JCP
Supporting Information (see footnote on the first page of this arti-
cle): Details of NMR spectroscopy studies and X-ray analyses of
tricyclic phosphanes 6 and 7.
1
2
= 5.5 Hz, C-11), 146.9 (t, JCP = 18.5 Hz, C-4), 157.4 (dd, JCP
=
19.0, 2JCP = 5.0 Hz, C-3) ppm. IR (KBr): ν = 465 (w), 499 (w), 521
˜
(w), 541 (w), 628 (w), 645 (w), 697 (w), 722 (w), 736 (w), 755 (w),
786 (w), 803 (m), 817 (m), 829 (m), 852 (w), 874 (w), 916 (w), 941
(w), 962 (w), 1019 (w), 1036 (w), 1112 (m), 1153 (w), 1181 (w),
1261 (w), 1333 (w), 1378 (w), 1404 (w), 1437 (w), 1455 (w), 1499
Acknowledgments
(w), 1510 (m), 1567 (w), 1634 (w), 1898 (w), 2860 (w), 2887 (w), This work was supported by the Russian Foundation for Basic Re-
2916 (m), 2943 (m), 2961 (w), 2990 (w), 3017 (w), 3048 (w) cm–1. search (09-03-00123-a), the Council on Grants of the Russian Fed-
Eur. J. Org. Chem. 2011, 4910–4918
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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4918
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