Convenient methods for the synthesis of a library of hemilabile phosphines

Article abstract of DOI:10.1055/s-0028-1088060

A series of novel functionalized phosphines of hemilabile character, R ₂P(CH₂)_nZ, have been prepared from diarylphosphines using several synthetic methodologies. The synthetic methods include the alkylation of lithium diar

Full text of DOI:10.1055/s-0028-1088060

1916
PAPER
Convenient Methods for the Synthesis of a Library of Hemilabile Phosphines
Synthesis of
a
Library
.of Hemilabil
V
e
Phosphines ictoria Jiménez,* Jesús J. Pérez-Torrente, M. Isabel Bartolomé, Luis A. Oro
Departamento de Química Inorgánica, Instituto Universitario de Catálisis Homogénea-Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-C.S.I.C., 50009-Zaragoza, Spain
Fax +34(976)762284; E-mail: vjimenez@unizar.es
Received 5 December 2008; revised 6 February 2009
In this context, functionalized phosphines have been in-
Abstract: A series of novel functionalized phosphines of hemi-
tensively studied3 as hemilabile ligands for soft metal cen-
labile character, R2P(CH2)nZ, have been prepared from diaryl-
ters because of their ability for providing either easily
accessible coordination vacancies or protecting the active
phosphines using several synthetic methodologies. The synthetic
methods include the alkylation of lithium diarylphosphide or (di-
arylphosphino)borane adducts with functionalized halogenoal- catalytic site, through a potentially dynamic ‘on-and-off’
chelating effect for the metal center. Hybrid P,O-2b,4 and
kanes, X(CH2)nZ, and the photochemical hydrophosphination of
P,N-based ligands5 have been the most investigated since
suitable functionalized allyl or vinyl derivatives, H2C=CHZ or
H2C=CHCH2Z, using white light. A range of R2PH (R = Bn, 4-
phosphorus usually binds strongly to the metal center
MeOC6H4, 4-MeC6H4, 2-MeC6H4, Ph, 4-F3CC6H4) has been used in
whereas the other donor atom (O or N) is generally only
weakly bonded.
order to tune the electronic density on the phosphorus donor atom.
The coordination ability of the hemilabile fragment was modified
by selection of the donor group (Z = OMe, OEt, OBu, NMe2) or the
length of the flexible carbon chain (n = 2, 3). Hemilabile fluorinated
allylphosphines, R2PCH2CH=CH2 (R = 4-FC6H4, C6F5), have been
prepared from diarylchlorophosphines and allylmagnesium bro-
mide.
We have recently become interested in the design of
hemilabile ligands for transition metal catalytic applica-
tions.6 In particular, we have been intensively studying the
scope and potential of a series of functionalized phos-
phines of the type R2P(CH2)nZ (Figure 1). Although a
number of these phosphines have been described in the lit-
erature,7–9 we have noticed a lack of well-defined synthet-
ic protocols for the synthesis of a library of hemilabile
phosphines that allow the ‘fine tuning’ of the catalytic
systems. These ligands offer potential for the modulation
of the electronic density on the phosphorus donor atom by
introducing electron-donating or electron-withdrawing
substituents in the aryl groups of the phosphine fragment,
as well as for the control of the coordination ability of the
hemilabile fragment by the selection of the donor group
(OR, NR2, or SR) or the length of the flexible carbon
chain.
Key words: hemilabile ligands, functionalized phosphines, hydro-
phosphination, allylphosphine
Catalytic activity in transition-metal-catalyzed reactions
is strongly affected by the electronic and steric character-
istics of the coordinated ligands to the metallic center. In
fact, this influence has found application in the ‘fine tun-
ing’ of the catalyst properties. At the same time, it is de-
sirable that the ligands are able to furnish open
coordination sites and stabilize reactive transition metal
species during the course of the catalysis. Actually, this
reversible protection of one or more coordination sites is
the most important property of hemilabile ligands.
X
The concept of hemilability was first introduced by
Rauchfuss referring to the labile coordination of some
ligands bearing electronically divergent soft and hard do-
nor atoms.1 These hemilabile ligands and their coordina-
tion chemistry have received increased interest in recent
years. In general, with late transition metals, the hard do-
nor center is only weakly coordinated to the metal center
and allows, by decoordination, the binding of substrates
that induce ulterior reactivity. Metal complexes contain-
ing hemilabile ligands have been found to be active in a
range of catalytic reactions, including hydrogenation, hy-
drosilylation, carbonylation, hydroformylation, allylation,
epoxidation, olefin (co)dimerization or copolymerization,
and ring-opening metathesis polymerization (ROMP).2
P
Z = OR, NMe2, SR
Z
n
coordination ability
X
n = 0, 1
metallocycle size
X = electron-donating or
-withdrawing group
electronic effect
Figure 1
We describe herein the improvement and optimization of
synthetic methodologies applied to the successful synthe-
sis of a library of functionalized phosphines R2P(CH2)nZ
(R = Bn, 4-MeOC6H4, 4-MeC6H4, 2-MeC6H4, Ph, 4-
F3CC6H4; n = 2, 3; Z = OMe, OEt, OBu, NMe2). In addi-
tion, the synthesis of potentially hemilabile fluorinated al-
SYNTHESIS 2009, No. 11, pp 1916–1922
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Advanced online publication: 27.04.2009
DOI: 10.1055/s-0028-1088060; Art ID: Z27308SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Synthesis of a Library of Hemilabile Phosphines
1917
Table 1 Method 1: The Alkylation of Lithium Dialkylphosphidesa
lylphosphines, R2PCH2CH=CH2 (R = 4-FC6H4, C6F5), is
also described.
X(CH2)nZ
n-BuLi
R2P(CH2)n
Z
R2PH
LiPR2
The synthesis of functionalized phosphines, R2P(CH2)nZ,
can be easily accomplished from diarylphosphine (R2PH)
or diarylchlorophosphine (R2PCl) derivatives. Diphenyl-
phosphine (Ph2PH) is commercial available and different
strategies have been developed for the synthesis of diaryl-
or dialkylphosphine (R2PH) compounds. However, from a
practical point of view, the synthetic protocols outlined in
Schemes 1 and 2 are the more efficient.
1–10
Entry
R
n
2
2
3
2
1
3
2
2
2
2
Z
Product Yield (%)
1
2
Ph
Ph
Ph
Ph
Ph
Ph
i-Pr
Bn
OMe
NMe2
NMe2
SMe
SMe
OMe
OMe
OMe
OMe
OMe
1
2
60
80
52b
69b
61b
75
43
65
46
41
3
3
4
4
Scheme 1 describes the traditional time-consuming labo-
rious method of alkylation/arylation of aminodichloro-
phosphines with Grignard reagents,10 and the Scheme 2
outlines the alkylation/arylation of diethyl phosphonate11
and followed by reduction of the formed phosphine oxides
by recently reported methods.
5
5
6
6
7
7
8
8
RMgX
Cl2PNEt2
R2PNEt2
HCl (g)
9
4-MeC6H4
2-MeC6H4
9
10
10
LiAlH4
R2PH
R2PCl
a Reaction conditions (unless otherwise stated): Step 1: R2PH, BuLi,
THF, 0 °C; Step 2: X(CH2)Z, 0 °C to r.t.
(excess)
Scheme 1
b Commercially available KPPh2 was used directly in Step 2.
Although most of diaryl(alkyl)phosphines used in this
work were prepared by both methods, the synthesis
through phosphine oxide intermediates usually provides
higher yields. In fact, the ethoxy groups of diethyl phos-
phonate are easily substituted by a variety of alkyl/aryl
groups using the corresponding Grignard reagents. Be-
sides, the resulting phosphine oxides are efficiently re-
duced by using a methylation reagent, for example methyl
iodide or methyl trifluoromethanesulfonate, and a power-
ful reducing reagent, as lithium aluminum hydride, fol-
lowing the procedure described by Imamoto et al.12 In
addition, diethyl phosphonate is commercially available
and easy to handle.
son et al.8 (phosphine 1–6) and Werner et al.9 (phosphine
7).
A slightly modified version of this synthetic protocol has
been applied for the preparation of a range of functional-
ized phosphines 1–10. In particular, diphenylphosphine
derivatives 1–5 were prepared using commercial potassi-
um diphenylphosphide solutions in tetrahydrofuran. The
phosphines were isolated as colorless or pale yellow oils
after distillation under reduced pressure, except 4 that was
isolated as a white solid. Phosphines 1–7 were character-
1
31
ized by comparison of the H and P{1H} NMR spectra
with the NMR data previously reported in the literature.
Interestingly, (3-methoxypropyl)diphenylphosphine (6)
had previously been synthesized in lower yield by reac-
tion of chlorodiphenylphosphine with 3-methoxypropyl-
magnesium chloride.7a
O
O
a) MeI, DME
b) LiAlH4
RMgX
(EtO)2PH
R2PH
R2PH
The synthesis of the new phosphines 8–10 required the
previous preparation of dibenzylphosphine, di-4-
tolylphosphine, and di-2-tolylphosphine, which was ac-
complished following the procedure outlined in
Scheme 2. Compounds 8–10 have been characterized by
Scheme 2
The synthesis of functionalized phosphines, R2P(CH2)nZ,
have been carried out following three different procedures
that involve the alkylation of lithium diarylphosphides or
phosphine–borane adducts (Methods 1 and 2), and the
photochemical hydrophosphination of appropriate unsat-
urated compounds (Method 3). Method 4 provides access
to potentially hemilabile fluorinated allylphosphines,
R2PCH2CH=CH2.
1
elemental analysis, mass spectrometry, and H, 31P{1H},
13C{1H} NMR spectroscopy (see experimental section).
In particular, the 31P{1H} NMR spectra showed a singlet
at d = –21.84 (8), –24.60 (9), and –43.97 (10). The meth-
ylene protons of the 2-methoxyethyl fragment were ob-
served as a doublet of triplets (OCH2) and triplet (PCH2)
between d = 3.8–3.5 and 2.4–1.7, respectively, whereas
that the methoxy group was observed as a singlet around
d = 3.
The nucleophilic substitution on functionalized halo-
genoalkanes derivatives, X(CH2)nZ (X = Cl, Br), by lithi-
um diarylphosphides is
a
convenient entry to
functionalized phosphines of the type R2P(CH2)nZ (Meth-
The oxygen-sensitive nature of phosphines sometimes re-
quires their protection during different synthetic steps.
Phosphine–borane complexes have proved to be stable
od 1, Table 1) as described by McEwen et al.7 and Ander-
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York

1918
M. V. Jiménez et al.
PAPER
under a variety of reaction conditions and this, makes bo- hydrophosphinated with several diarylphosphines
rane a versatile protecting group widely used in phosphine (R2PH). The reactions were conducted with an excess of
synthesis.13
unsaturated vinyl or allyl derivative and, interestingly,
without ultraviolet lamps or catalysts, because only visi-
ble light from standard white lamps was necessary to
drive the reactions to completion. This procedure is very
convenient since the reactions, as monitored by 31P{1H}
NMR spectroscopy, are quantitative with no byproducts
formation. In fact, the phosphines were directly obtained
as colorless oils in high yields without the need of further
purification by simple removing the excess of olefin in
vacuum.
The alkylation of borane adducts of secondary phosphines
by electrophiles in a biphasic solution in the presence of
tetrabutylammonium bromide as phase-transfer catalyst
(Method 2, Table 2) is also a convenient method that
avoid the use of strong bases.14 Although this methodolo-
gy requires the formation of phosphine–borane adducts
and the deprotection of the resulting products, this method
is very appropriate for the synthesis of particularly air-
sensitive phosphines. In fact, the functionalized phos-
phines 8–10 have been prepared in excellent yields (high-
er than 80%) directly from the secondary phosphines
using this procedure without the necessity of isolation and
purification of some intermediate products.
Table 3 Method 3: Photochemical Hydrophosphination of Unsatur-
ated Compoundsa
CH2=CH(CH2)nZ
R2PH
R2P(CH2)(n+2)
Z
hν
The deprotection of the functionalized phosphine–borane
adducts, R2(BH3)P(CH2)nZ, can be accomplished follow-
ing different procedures using acids or amines. However,
we have obtained better yields by using tetrafluoroboric
acid followed by neutralization with potassium carbon-
ate.15
9–22
Entry
1
R
n + 2
Z
Product Yield (%)
4-MeC6H4
3-MeC6H4
4-MeC6H4
Ph
2
2
2
3
3
3
3
3
3
3
3
2
3
3
OMe
OMe
OEt
9
10
11
12
13
14
15
16
17
18
19
20
21
22
87
89
79
92
64
92
65
55
75
55
75
55
75
79
2
3
Table 2 Method 2: Alkylation of Phosphine–Borane Adducts under
Phase-Transfer Catalysisa
4
OEt
5
Ph
OBu
OMe
OEt
BH3
BH3⋅THF
R2PH
R2PH
6
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeOC6H4
4-MeOC6H4
4-MeOC6H4
4-F3CC6H4
4-F3CC6H4
4-F3CC6H4
Br(CH2)2OMe
7
BH3
8
NMe2
OMe
OEt
HBF4⋅OEt2
R2P(CH2)2OMe
R2P(CH2)2OMe
9
8–10
10
11
12
13
14
Entry
R
Product
Yield (%)
NMe2
OEt
1
2
3
Bn
8
9
90
83
81
4-MeC6H4
3-MeC6H4
OEt
10
NMe2
a Reaction conditions: Step 1: R2PH, BH3–THF, THF, 0 °C, 3 h; Step
2: aq KOH, TBAB, toluene, r.t., 1 h; Step 3: HBF4·OMe2, CH2Cl2, r.t.,
12 h.
a Reaction conditions: R2PH, H2C=CH(CH2)nZ, neat, hn.
The phosphines 11–19 were prepared in excellent yields
following this photochemical procedure. This method is
particularly appropriate for the synthesis of 20–22 be-
cause diarylphosphines with fluorinated substituents in
the aryl moiety are difficult to deprotonate and conse-
quently, the classical method depicted in Method 1
The hydrophosphination of unsaturated compounds under
photochemical conditions has been successfully applied
to the synthesis of diphosphine ligands having alkoxyeth-
yl pendant arms by Lindner et al.,16 or in the preparation
of phosphinoalkylsilanes by Stobart et al.17
We have found that functionalized allyl or vinyl deriva- (Table 1) is not applicable. The new phosphines were ob-
tives are photochemically hydrophosphinated in an effi- tained as air-sensitive colorless oils and characterized by
cient and regioselective way to give exclusively the anti- elemental analysis, MS, and multinuclear NMR spectros-
Markonikov products (Method 3, Table 3). This proce- copy. Interestingly, this method allows the synthesis of
dure has a wide scope in the synthesis of functionalized phosphines 9 and 10 in higher yields than those obtained
phosphine ligands. Thus, diverse unsaturated fragment as
vinyl ethers (H2CH2=CHOR, R = Me, Et), allyl ethers
(H2C=CHCH2OR, R = Me, Et, Bu), or allylamine
with the previously described methods. This methodology
has also been adapted for the synthesis of several phos-
phines, for example (2-ethoxyethyl)diphenylphosphine,18
(H2C=CHCH2NMe2) derivatives have been effectively with improved yields.
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York

PAPER
Synthesis of a Library of Hemilabile Phosphines
1919
Microflex spectrometer using DCTB as matrix.20 Distillations un-
der reduced pressure were carried out in a standard Kugelrohr oven.
Hybrid phosphine–olefin ligands can work as hemilabile
because of the presumed ability to easily dissociate the
C=C bond. In fact, the hemilabile character of allyldiphe-
nylphosphine ligands is well documented.19 We have en-
visaged the introduction of fluorinated aryl groups on
allyldiarylphosphines as a way of enhancing the coordina-
tion ability of the olefin side arm by reducing the electron-
ic density on the phosphine fragment.
Diarylchlorophosphines; General Procedure
The bromoalkylbenzene (0.06 mol) was added to a suspension of
Mg turnings (1.54 g, 0.06 mol) in THF or Et2O (50 mL) containing
I2 (5 mg) and the mixture was stirred at r.t. or under reflux until con-
sumption of Mg. The suspension was filtered through Celite to give
a clear soln of RMgCl. The soln was added dropwise to a soln of
(Et2N)PCl2 (5.48 g, 0.027 mol) in Et2O or THF (50 mL) at –5 °C un-
der argon. The mixture was stirred at r.t. for several hours and fil-
tered through Celite to give a clear soln of R2P(NEt2). Anhyd HCl
(g) was bubbled through the soln for 30 min to give a white suspen-
sion that was filtered through Celite. The soln was evaporated under
vacuum to give compounds R2PCl. The compounds were purified
by distillation under reduced pressure and isolated as colorless oils.
The synthesis of these fluorinated phosphine ligands has
been accomplished from diarylchlorophosphine deriva-
tives owing to the difficulties to prepare lithium di-
arylphosphide salts from the corresponding fluorinated
diarylphosphines precursors. Thus, the reaction of chloro-
bis(4-fluorophenyl)phosphine or chlorobis(pentafluo-
rophenyl)phosphine with allylmagnesium bromide
(Scheme 3) gave the phosphines 23 and 24 in good yield.
The compounds were purified by extraction with n-hex-
ane because distillation under reduced pressure resulted in
partial decomposition. The new phosphine–olefin com-
pounds were characterized by elemental analysis, mass
spectra, and multinuclear NMR spectroscopy. In particu-
lar, the 31P{1H} NMR spectra showed high field reson-
ances at d = –17.95 (23) and –48.84 (24).
Diarylphosphine Oxides General Procedure
A freshly prepared soln of the Grignard reagent RMgX (0.08
mmol), prepared in THF as described above, was added dropwise to
a soln of (EtO)2P(O)H (2.24 g, 0.016 mol) in THF (75 mL) at 5 °C
and stirred for 2 h. The mixture was quenched by slow addition of
H2O (50 mL) followed by addition of aq 6 M HCl (12 mL) and tol-
uene (40 mL). The organic layer was removed and the aqueous layer
extracted with Et2O (2 × 20 mL). The combined organic layers were
washed with 5% aq NaHCO3 (40 mL) and 5% aq NaCl (40 mL) and
dried (MgSO4). The soln was concentrated under reduced pressure
and the residue recrystallized (hexane) to give the compounds as
white solids.
allylMgBr
R2P
R2PCl
Diarylphosphines (R2PH); General Procedures
23 R = 4-FC6H4 75%
24 R = C6F5 52%
Preparation from R2PCl: Solid LiAlH4 (0.95 g, 25.03 mmol) was
added to a soln of R2PCl (10 mmol) in Et2O (25 mL) at –15 °C over
a period of 30 min. The suspension was stirred at r.t. for 1 h and then
treated with aq 0.1 M HCl (100 mL). The organic layer was re-
moved by cannula under argon and the aqueous layer extracted with
Et2O (2 × 20 mL). The combined organic layers were dried
(MgSO4) and the solvent evaporated under vacuum to give colorless
oils that were distilled under reduced pressure
Scheme 3 Method 4: Preparation of allylphosphines
In summary, we have described the synthesis of a series of
functionalized phosphines of hemilabile character,
R2P(CH2)nZ (n = 2, 3; Z = OMe, OEt, OBu, NMe2), from
diarylphosphines and functionalized halogenoalkanes,
X(CH2)nZ, or unsaturated compounds as vinyl or allyl
Reduction of R2P(O)H: A soln of the diarylphosphine oxide (8.0
mmol) in DME (10 mL) was reacted with MeI (0.56 mL, 9.0 mmol)
ethers and allylamine derivatives. The more convenient at r.t. under an argon atmosphere. After 2 h, solid LiAlH4 (0.76 g,
20 mmol) and THF (20 mL) were added at 0 °C and the mixture was
approach for the preparation of a variety of secondary
stirred for 30 min. The reaction was quenched with deoxygenated
arylphosphines, R2PH, is the arylation of diethyl phospho-
H2O (10 mL) and the organic layer removed by cannula under ar-
gon. The aqueous layer was extracted with Et2O (2 × 20 mL) and
the combined organic layers were dried (MgSO4). The solvent was
nate and posterior reduction, whereas that the more effi-
cient methodology to introduce the hemilabile fragment is
the photochemically hydrophosphination of functional-
ized unsaturated compounds. This reaction usually takes
place under visible light with complete regioselectivity.
These phosphines constitute a library of hemilabile phos-
phine ligands that is built by modification of the electronic
density on the phosphorus donor atom, the donor group on
the hemilabile fragment or the length of the flexible car-
bon chain, and that can be easily enlarged by using both
synthetic proposed methods successively.
evaporated under vacuum and the viscous oils distilled under re-
duced pressure.
Functionalized Phosphines 1–10 by Method 1: General Proce-
dure
A soln of R2PH (8.11 mmol) in THF (50 mL) was reacted with 1.6
M BuLi in hexane (5.07 mL, 8.11 mmol) under argon at 0 °C to give
a soln of LiPR2. Then, the X(CH2)nZ (8.11 mmol) was added drop-
wise under argon at 0 °C and the soln allow to warm to r.t. and
stirred for 1 h at this temperature. Deoxygenated H2O (25 mL) was
added slowly, the organic layer was removed by cannula under ar-
gon, and the aqueous layer extracted with Et2O (2 × 20 mL). The
combined organic layers were dried (MgSO4) and the solvent evap-
orated to give viscous oils that were distilled under reduced pressure
to give the compounds as colorless oils.
C, H and N analysis were carried out in a Perkin-Elmer 2400
CHNS/O analyzer. NMR spectra were recorded on a Varian Gemini
2000 or Bruker Avance 300 spectrometers, 1H and 13C NMR chem-
ical shifts were referenced relative to partially deuterated solvent
peaks and TMS. 31P and 19F NMR chemical shifts were referenced
relative to H3PO4 (85%) and CFCl3, respectively. MS data (EI) were
recorded on a VG Autospec double-focusing mass spectrometer op-
erating in the positive mode; ions were produced with the Cs+ gun
at ca. 30 kV. MALDI-TOF mass spectra were obtained on a Bruker
Diaryl(2-methoxyethyl)phosphines 8–10 by Method 2; General
Procedure
R2PH (3.1 mmol) and BH3–THF (3.4 mmol) were reacted in THF
(5 mL) at 0 °C for 3 h to give the adduct R2(BH3)PH. Then, the sol-
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York

1920
M. V. Jiménez et al.
PAPER
vent was removed under vacuum and a soln of TBAB (0.30 mmol)
in 30% aq KOH (15 mL) and toluene (10 mL) were added and re-
acted with 2-bromoethyl methyl ether (2.99 mmol). The mixture
was stirred vigorously at r.t. for 1 h and the organic layer diluted
with Et2O (50 mL), washed with H2O and brine, and dried (MgSO4).
The solvent was removed under reduced pressure and the residue
purified by chromatography (silica gel, 2% EtOAc–hexanes) to give
the compounds R2(BH3)P(CH2CH2OMe). The phosphine–borane
adducts were treated with HBF4·OMe2 (15 mmol) in CH2Cl2 (50
mL) at –5 °C and stirred at r.t. for 12 h followed by hydrolysis at 0
°C with aq K2CO3 soln (15 mmol). The organic layer was removed
by cannula under argon and the aqueous layer extracted with
CH2Cl2 (2 × 20 mL). The combined organic layers were dried
(MgSO4) and the solvent removed under vacuum to give the com-
pounds as colorless oils that were distilled under reduced pressure.
MS (EI+): m/z (%) = 273.4 (M+, 40), 215.1 (M+ – CH2CH2OMe,
50).
Anal. Calcd for C17H21OP: C, 75.02; H, 7.77. Found: C, 74.77; H,
8.22.
(2-Methoxyethyl)di-2-tolylphosphine (10)
Yield: 41% (Method 1), 81% (Method 2), 89% (Method 3); bp 200
°C/0.1 mbar (Kugelrohr).
1H NMR (298 K, CDCl3): d = 7.27–7.16 (m, 8 H, Ph), 3.51 (dt,
JH-H = 7.5 Hz, JH-P = 7.5 Hz, 2 H, CH2O), 3.33 (s, 3 H, CH3O), 2.43
(s, 6 H, CH3C6H4), 2.34 (t, 2 H, JH-H = 7.5 Hz, CH2P).
13C{1H} NMR (298 K, CDCl3): d = 142.34 (d, JC-P = 25.5 Hz, C4io),
136.43 (d, JC-P = 19.9 Hz, Ci), 131.07 (CH), 130.03 (d, JC-P = 4.7
Hz, Co), 128.47, 126.08 (CH), 69.80 (d, JC-P = 24.1 Hz, CH2O),
58.44 (OCH3), 27.62 (d, JC-P = 13.2 Hz, CH2), 21.15 (d, JC-P = 21.9
Hz, CH3C6H4).
31P{1H} NMR (298 K, CDCl3): d = –43.97 (s).
MS (EI+): m/z (%) = 272.7 (M+, 80), 214.5 (M+ – CH2CH2OMe,
Diaryl(x-substituted-alkyl)phosphines 9–22 by Method 3; Gen-
eral Procedure
A glass reaction tube fitted with a greaseless high-vacuum stopcock
was charged with the corresponding vinyl ether, allyl ether, or allyl-
amine (10 mmol) and the appropriate diarylphosphine (2 mmol).
The mixture was placed between 4 white lamps of 400 W and stirred
for 3–7 d. The obtained viscous oil was dissolved in toluene (10
mL) and transferred to a Schlenck tube under argon. The volatiles
were removed under vacuum to give the compounds as colorless
oily products.
100).
Anal. Calcd for C17H21OP: C, 75.02; H, 7.77. Found: C, 76.06; H,
8.83.
(2-Ethoxyethyl)di-4-tolylphosphine (11)
Yield: 79% (Method 3).
1H NMR (298 K, CDCl3): d = 7.26–7.05 (m, 8 H, Ph), 3.44 (dt,
Allyldiarylphosphines 23 and 24 by Method 4; General Proce-
dure
JH-H = 6.8 Hz, JH-P = 6.8 Hz, 2 H, CH2O), 3.37 (q, JH-H = 7.0 Hz, 2
H, OCH2CH3), 2.32 (m, 2 H, CH2P), 2.26 (s, 6 H, CH3C6H4), 1.09
(t, JH-H = 7.0 Hz, 3 H, OCH2CH3).
13C{1H} NMR (298 K, CDCl3): d = 138.49 (C4io), 134.99 (d,
A soln of allylmagnesium bromide (0.06 mol) in anhyd Et2O (100
mL) was added dropwise under argon to a soln of R2PCl (0.06 mol)
in Et2O (20 mL) at 0 °C. After stirring for 2 h, the mixture was hy-
drolyzed with deoxygenated sat. aq NH4Cl (100 mL). The organic
layer was removed by cannula under argon and the aqueous layer
was extracted with Et2O (2 × 20 mL). The combined organic layers
were dried (Na2SO4) and the solvent was removed under reduced
pressure to give a colorless oil that was purified by extraction from
n-hexane.
JC-P = 10.9 Hz, Ci), 132.61 (d, JC-P = 19.2 Hz, Co), 129.22 (m,
JC-P = 6.9 Hz, Cm), 67.82 (d, JC-P = 25.4 Hz, CH2O), 66.05
(CH2CH3), 29.03 (d, JC-P = 12.5 Hz, CH2P), 21.24 (CH3C6H4),
15.16 (CH2CH3).
31P{1H} NMR (298 K, CDCl3): d = –24.47 (s).
MS (EI+): m/z (%) = 287.5 (M+, 17), 214.1 (M+ – CH2CH2OEt, 85).
Dibenzyl(2-methoxyethyl)phosphine (8)
Yield: 65% (Method 1), 90% (Method 2); bp 225 °C/0.1 mbar
(Kugelrohr).
Anal. Calcd for C18H23OP: C, 75.50; H, 8.10. Found: C, 75.58; H,
8.23.
1H NMR (298 K, CDCl3): d = 7.35–7.18 (m, 10 H, Ph), 3.79 (m, 2
H, CH2O), 3.27 (s, 3 H, CH3O), 2.86 (m, 4 H, C6H5CH2), 1.69 (t,
JH-H = 7.4 Hz, 2 H, CH2P).
13C{1H} NMR (298 K, CDCl3): d = 137.72 (d, JC-P = 4.6 Hz, Ci),
129.18 (d, JC-P = 5.7 Hz, Co), 128.39 (Cm), 125.81 (d, JC-P = 2.1 Hz,
Cp), 70.34 (d, JC-P = 21.8 Hz, CH2O), 58.40 (OCH3), 27.06 (d,
JC-P = 18.0 Hz, CH2P), 34.84 (d, JC-P = 17.3 Hz, C6H4CH2).
(3-Ethoxypropyl)diphenylphosphine (12)
Yield: 92% (Method 3).
1H NMR (298 K, CDCl3): d = 7.52–7.28 (m, 10 H, Ph), 3.47 (m, 4
H, CH2, CH2CH3), 2.10 (m, 2 H, CH2), 1.72 (m, 2 H, CH2), 1.19 (t,
JH-H = 7.2 Hz, 3 H, CH2CH3).
13C{1H} NMR (298 K, CDCl3): d = 138.12 (d, JC-P = 10.1 Hz, Ci),
132.74 (d, JC-P = 18.2 Hz, Co), 128.67 (Cp), 128.42 (d, JC-P = 6.7 Hz,
Cm), 70.94 (d, JC-P = 13.8 Hz, CH2O), 67.95 (OCH2), 26.18 (d,
31P{1H} NMR (298 K, CDCl3): d = –21.84 (s).
MS (EI+): m/z (%) = 272.8 (M+, 70).
JC-P = 15.6 Hz, CH2P), 24.34 (d, JC-P = 9.5 Hz, CH2), 15.18 (CH3).
31P{1H} NMR (298 K, CDCl3): d = –15.90 (s).
MS (EI+): m/z (%) = 273.6 (M+ + H, 50), 243.4 (M+ – Et, 100).
Anal. Calcd for C17H21OP: C, 74.98; H, 7.77. Found: C, 75.34; H,
7.99.
Anal. Calcd for C17H21OP: C, 74.98; H, 7.77. Found: C, 74.86; H,
7.37.
(2-Methoxyethyl)di-4-tolylphosphine (9)
Yield: 46% (Method 1), 83% (Method 2), 87% (Method 3); bp 220
°C/0.1 mbar (Kugelrohr).
1H NMR (298 K, CDCl3): d = 7.36–7.15 (m, 8 H, Ph), 3.50 (dt,
JH-H = 7.7 Hz, JH-P = 7.7 Hz, 2 H, CH2O), 3.32 (s, 3 H, CH3O), 2.39
(t, JH-H = 7.7 Hz, 2 H, CH2P), 2.36 (s, 6 H, CH3C6H4).
(3-Butoxypropyl)diphenylphosphine (13)
Yield: 64% (Method 3).
1H NMR (298 K, CDCl3): d = 7.46–7.31 (m, 10 H, Ph), 3.47 (t,
JH-H = 6.4 Hz, 2 H, CH2), 3.38 (t, JH-H = 6.6 Hz, 2 H, OCH2Pr), 2.10
13C{1H} NMR (298 K, CDCl3): d = 138.54 (C4io), 134.90 (d,
JC-P = 11.8 Hz, Ci), 132.60 (d, JC-P = 19.0 Hz, Co), 129.25 (m,
JC-P = 6.9 Hz, Cm), 69.92 (d, JC-P = 29.4 Hz, CH2O), 58.43 (OCH3),
28.89 (d, JC-P = 12.5 Hz, CH2P), 21.24 (CH3C6H4).
(m, 2 H, CH2), 1.71 (m, 2 H, CH2), 1.55 (m, 2 H, CH2CH2), 1.36 (m,
2 H, CH2CH2), 0.92 (t, JH-H = 7.3 Hz, 3 H, CH3).
13C{1H} NMR (298 K, CDCl3): d = 138.74 (d, JC-P = 12.7 Hz, Ci),
132.73 (d, JC-P = 18.4 Hz, Co), 128.51 (m, Cp, Cm), 71.23 (d,
JC-P = 13.9 Hz, CH2O), 70.57 (OCH2Pr), 31.83 (CH2CH2), 26.21 (d,
31P{1H} NMR (298 K, CDCl3): d = –24.60 (s).
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York

PAPER
Synthesis of a Library of Hemilabile Phosphines
1921
JC-P = 16.2 Hz, CH2P), 24.46 (d, JC-P = 11.2 Hz, CH2), 19.38
(CH2CH2), 13.97 (CH3).
31P{1H} NMR (298 K, CDCl3): d = –16.15 (s).
1H NMR (298 K, CDCl3): d = 7.38–7.01 (m, 8 H, Ph), 3.70 (s, 6 H,
CH3O), 3.45 (q, JH-H = 6.8 Hz, m, 2 H, CH2O), 3.31 (s, 3 H, CH3O),
2.05 (m, 2 H, CH2), 1.71 (m, 2 H, CH2).
13C{1H} NMR (298 K, CDCl3): d = 160.03 (C4io), 133.68 (d,
JC-P = 19.3 Hz, Co), 129.76 (d, JC-P = 10.8 Hz, Ci), 113.95 (d,
MS (MALDI-TOF, DCTB matrix, CH2Cl2): m/z = 300.4 (M+),
226.7 (M+ – OBu).
JC-P = 7.1 Hz, Cm), 72.91 (d, JC-P = 13.6 Hz, CH2O), 58.40 (OMe),
Anal. Calcd for C19H25OP: C, 75.97; H, 8.39. Found: C, 75.91; H,
8.35.
54.89 (CH3O), 26.10 (d, JC-P = 16.6 Hz, CH2P), 24.74 (d, JC-P = 10.4
Hz, CH2).
31P{1H} NMR (298 K, CDCl3): d = –19.69 (s).
MS (MALDI-TOF, DCTB matrix, CH2Cl2): m/z = 318.7 (M+).
(3-Methoxypropyl)di-4-tolylphosphine (14)
Yield: 92% (Method 3).
1H NMR (298 K, CDCl3): d = 7.37–7.15 (m, 8 H, Ph), 3.45 (t,
JH-H = 6.8 Hz, 2 H, CH2O), 3.32 (s, 3 H, CH3O), 2.35 (s, 6 H,
CH3C6H4), 2.08 (m, 2 H, CH2), 1.72 (m, 2 H, CH2).
Anal. Calcd for C18H23O3P: C, 67.91; H, 7.28. Found: 67.98; H,
7.31.
(3-Ethoxypropyl)bis(4-methoxyphenyl)phosphine (18)
Yield: 55% (Method 3).
1H NMR (298 K, CDCl3): d = 7.36–6.86 (m, 8 H, Ph), 3.78 (m, 8 H,
CH3O, OCH2), 3.45 (q, JH-H = 6.8 Hz, m, 2 H, CH2O), 2.03 (m, 2 H,
CH2), 1.68 (m, 2 H, CH2), 1.18 (t, JH-H = 6.8 Hz, 3 H, CH2CH3).
13C{1H} NMR (298 K, CDCl3): d = 138.36 (C4io), 135.40 (d,
JC-P = 11.9 Hz, Ci), 132.64 (d, JC-P = 19.0 Hz, Co), 129.18 (m,
JC-P = 7.1 Hz, Cm), 73.23 (d, JC-P = 13.4 Hz, CH2O), 58.43 (OMe),
26.12 (d, JC-P = 16.6 Hz, CH2P), 24.63 (d, JC-P = 10.3 Hz, CH2),
21.23 (CH3C6H4).
31P{1H} NMR (298 K, CDCl3): d = –18.00 (s).
13C{1H} NMR (298 K, CDCl3): d = 160.00 (C4io), 133.93 (d,
JC-P = 19.8 Hz, Co), 129.76 (d, JC-P = 10.3 Hz, Ci), 113.94 (d,
JC-P = 7.4 Hz, Cm), 70.90 (d, JC-P = 14.0 Hz, CH2O), 65.78
(CH2CH3), 54.89 (CH3O), 25.97 (d, JC-P = 16.4 Hz, CH2P), 24.76
(d, JC-P = 10.4 Hz, CH2), 14.90 (CH2CH3).
MS (MALDI-TOF, DCTB matrix, CH2Cl2): m/z = 287.1 (M+ + H),
271.1 (M+ – OMe).
Anal. Calcd for C18H23OP: C, 75.50; H, 8.09. Found: C, 75.61; H,
8.15.
31P{1H} NMR (298 K, CDCl3): d = –19.89 (s).
(3-Ethoxypropyl)di-4-tolylphosphine (15)
MS (MALDI-TOF, DCTB matrix, CH2Cl2): m/z = 332.9 (M+).
Yield: 65% (Method 3).
Anal. Calcd for C19H25O3P: C, 68.66; H, 7.58. Found: C, 68.76; H,
7.65.
1H NMR (298 K, CDCl3): d = 7.23–7.02 (m, 8 H, Ph), 3.45 (m, 4 H,
CH2O, CH2CH3), 2.23 (s, 6 H, CH3C6H4), 1.96 (m, 2 H, CH2), 1.59
(m, 2 H, CH2), 1.08 (t, JH-H = 7.0 Hz, 3 H, CH2CH3).
[3-(Dimethylamino)propyl]bis(4-methoxyphenyl)phosphine
(19)
13C{1H} NMR (298 K, CDCl3): d = 138.36 (C4io), 135.36 (d,
JC-P = 11.4 Hz, Ci), 132.65 (d, JC-P = 18.5 Hz, Co), 129.17 (m,
JC-P = 6.9 Hz, Cm), 71.12 (d, JC-P = 13.9 Hz, CH2O), 66.01
(CH2CH3), 26.24 (d, JC-P = 16.5 Hz, CH2P), 24.65 (d, JC-P = 11.2
Hz, CH2), 21.27 (CH3C6H4), 15.22 (CH2CH3).
Yield: 75% (Method 3).
1H NMR (298 K, CDCl3): d = 7.38–6.86 (m, 8 H, Ph), 3.80 (s, 6 H,
CH3O), 2.37 (m, 2 H, CH2), 2.20 (s, 6 H, NMe2), 1.98 (m, 2 H, CH2),
1.58 (m, 2 H, CH2).
31P{1H} NMR (298 K, CDCl3): d = –18.14 (s).
MS (EI+): m/z (%) = 301 (M+, 30), 271 (M+ – Et, 85), 227 (M+ –
13C{1H} NMR (298 K, CDCl3): d = 160.05 (C4io), 134.03 (d,
JC-P = 19.8 Hz, Co), 129.91 (d, JC-P = 10.4 Hz, Ci) 114.10 (d,
JC-P = 7.2 Hz, Cm), 60.72 (d, JC-P = 13.5 Hz, CH2N), 55.11 (CH3O),
45.31 (NMe2), 26.32 (d, JC-P = 10.3 Hz, CH2), 24.02 (d, JC-P = 17.2
Hz, CH2).
CH2CH2OEt, 100).
Anal. Calcd for C19H25OP: C, 76.02; H, 8.33. Found: C, 75.86; H,
8.37.
31P{1H} NMR (298 K, CDCl3): d = –19.46 (s).
[3-(Dimethylamino)propyl]di-4-tolylphosphine (16)
MS (MALDI-TOF, DCTB matrix, CH2Cl2): m/z = 330.2 (M+).
Yield: 55% (Method 3).
Anal. Calcd for C19H26NO2P: C, 68.86; H, 7.91; N, 4.22. Found: C,
68.91; H, 7.77; N, 4.23.
1H NMR (298 K, CDCl3): d = 7.34–7.12 (m, 8 H, Ph), 2.38 (m, 2 H,
CH2), 2.33 (s, 6 H, CH3C6H4), 2.17 (s, 6 H, NMe2), 2.03 (m, 2 H,
CH2), 1.57 (m, 2 H, CH2).
(2-Ethoxyethyl)bis[4-(trifluoromethyl)phenyl]phosphine (20)
Yield: 55.0% (Method 3).
1H NMR (298 K, CDCl3): d = 7.61–7.51 (m, 8 H, Ph), 3.58 (q,
13C{1H} NMR (298 K, CDCl3): d = 138.69 (C4io), 135.76 (d,
JC-P = 11.5 Hz, Ci), 132.99 (d, JC-P = 18.4 Hz, Co), 129.49 (m,
JC-P = 6.4 Hz, Cm), 61.04 (d, JC-P = 13.8 Hz, CH2N), 45.61 (CH3,
JH-H = 7.5 Hz, 2 H, CH2CH3), 3.46 (q, JH-H = 7.2 Hz, 2 H, CH2O),
NMe2), 26.00 (d, JC-P = 11.1 Hz, CH2P), 24.29 (d, JC-P = 16.6 Hz,
CH2), 21.19 (CH3C6H4).
2.43 (t, JH-H = 7.3 Hz, 2 H, CH2), 1.15 (t, JH-H = 7.1 Hz, 3 H,
CH2CH3).
31P{1H} NMR (298 K, CDCl3): d = –17.98 (s).
13C{1H} NMR (298 K, CDCl3): d = 143.21 (d, JC-P = 15.7 Hz, Ci-P),
133.46, 133.20 (Co Hz, CP), 131.29 (q, JCF = 32.6 Hz, C4io-CF3),
125.58 (m, Cm), 124.26 (d, JCF = 271.1 Hz, CF3), 70.61 (d,
MS (EI+): m/z (%) = 299.3 (M+, 30), 241.2 (M+ – CH2NMe2, 100),
227.2 (M+ – CH2CH2NMe2, 100).
JC-P = 12.8 Hz, PCH2), 67.41 (d, JC-P = 22.1 Hz, PCH2), 66.54
Anal. Calcd for C19H26NP: C, 76.22; H, 8.75; N, 4.68. Found: C,
76.28; H, 8.77; N, 4.61.
(CH2CH3), 28.83 (d, JC-P = 14.7 Hz, CH2), 15.14 (CH2CH3).
31P{1H} NMR (298 K, CDCl3): d = –20.19 (s).
19F NMR (298 K, CDCl3): d = –65.11 (s).
Bis(4-methoxyphenyl)(3-methoxypropyl)phosphine (17)
Yield: 75% (Method 3).
MS (EI+): m/z (%) = 395.7 (M+ + H, 65), 322.5 (M+ – CH2CH2OEt
+ H, 100).
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York

1922
M. V. Jiménez et al.
PAPER
Anal. Calcd for C18H17F6OP: C, 54.83; H, 4.34. Found: C, 54.79; H,
4.28.
19F NMR (298 K, CDCl3): d = –132.44 (m, Fo), –152.44 (m, Fm),
–162.95 (m, Fp).
MS (EI+): m/z (%) = 406.3 (M+, 100).
(3-Ethoxypropyl)bis[4-(trifluoromethyl)phenyl]phosphine (21)
Yield: 75% (Method 3).
Anal. Calcd for C15H5F10P: C, 44.35; H, 1.23. Found: C, 44.43; H,
2.06.
1H NMR (298 K, CDCl3): d = 7.62–7.53 (m, 8 H, Ph), 3.46 (m, 4 H,
CH2), 2.18 (m, 2 H, CH2), 1.71 (m, 2 H, CH2), 1.21 (t, JH-H = 7.2 Hz,
3 H, CH2CH3).
13C{1H} NMR (298 K, CDCl3): d = 143.07 (d, JC-P = 16.6 Hz,
Ci-P), 133.12, 132.88 (Co, Cp), 132.42 (d, JCF = 35.9 Hz, C4io-CF3),
125.27 (m Hz, Cm), 124.09 (d, JC-P = 285.7 Hz, CF3), 70.62 (d,
JC-P = 12.8 Hz, CH2), 66.20 (CH2CH3), 26.12 (d, JC-P = 16.6 Hz,
CH2), 24.23 (d, JC-P = 11.8 Hz, CH2), 15.15 (CH2CH3).
Acknowledgment
The financial support from Ministerio de Educación y Ciencia
(MEC/FEDER) is gratefully acknowledged (Project CTQ2006-
03973/BQU). M.I.B. (Project BQU2003-05412-C02-01) thanks a
graduate scholarship for financial support.
31P{1H} NMR (298 K, CDCl3): d = –15.35 (s).
19F NMR (298 K, CDCl3): d = –65.11 (s).
References
MS (EI+): m/z (%) = 409.7 (M+ + H, 90), 379.3 (M+ – CH2CH3, 85).
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Anal. Calcd for C19H19F6OP: C, 55.89; H, 4.69. Found: 55.83; H,
4.68.
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[3-(Dimethylamino)propyl]bis[4-(trifluoromethyl)phe-
nyl]phosphine (22)
Yield: 79% (Method 3).
1H NMR (298 K, CDCl3): d = 7.76–7.49 (m, 8 H, Ph), 2.43 (m, 2 H,
CH2), 2.22 (s, 6 H, NMe2), 2.10 (m, 2 H, CH2), 1.60 (m, 2 H, CH2).
13C{1H} NMR (298 K, CDCl3): d = 142.99 (d, JC-P = 16.4 Hz, Ci-P),
133.09, 132.85 (Co, Cp), 132.26 (d, JCF = 35.4 Hz, C4io-CF3), 125.24
(m, Cm), 124.01 (d, JC-P = 286.1 Hz, CF3), 60.20 (d, JC-P = 13.6 Hz,
CH2N), 45.07 (CH3, NMe2), 25.26 (d, JC-P = 12.2 Hz, CH2), 23.70
(d, JC-P = 16.3 Hz, CH2).
(5) Espinet, P.; Soulantica, K. Coord. Chem. Rev. 1999, 193-
195, 499.
31P{1H} NMR (298 K, CDCl3): d = –15.18 (s).
19F NMR (298 K, CDCl3): d = –65.08 (s).
MS (MALDI-TOF, DCTB matrix, MeOH): m/z = 408.1 (M+ + H).
(6) (a) Jiménez, M. V.; Pérez-Torrente, J. J.; Bartolomé, M. I.;
Gierz, V.; Lahoz, F. J.; Oro, L. A. Organometallics 2008, 27,
224. (b) Jiménez, M. V.; Rangel-Salas, I. I.; Lahoz, F. J.;
Oro, L. A. Organometallics 2008, 27, 4229.
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Knapczyk, J. W.; Kyllingstad, V. L.; Shiau, W. I.; Shore, S.;
Smith, J. H. J. Am. Chem. Soc. 1978, 100, 7304.
Anal. Calcd for C19H20F6NP: C, 56.02; H, 4.95; N, 3.44 Found: C,
56.21; 4.88; N, 3.14.
Allylbis(4-fluorophenyl)phosphine (23)
Purification by extraction from n-hexane; yield: 75% (Method 4).
(8) Anderson, G. K.; Kumar, R. Inorg. Chem. 1984, 23, 4064.
(9) (a) Werner, H.; Hampp, A.; Windmüller, B. J. Organomet.
Chem. 1992, 435, 169. (b) Werner, H.; Hampp, A.; Peters,
K.; Peters, E. M.; Walz, L.; von Schnering, H. G.
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(12) Imamoto, T.; Kikuchi, S. I.; Miura, T.; Wada, Y. Org. Lett.
2001, 3, 87.
1H NMR (298 K, CDCl3): d = 7.62–7.17 (m, 8 H, Ph), 5.78 (m, 1 H,
CH=), 5.12 (m, 2 H, =CH2), 2.84 (d, JH-H = 7.2 Hz, 2 H, CH2).
13C{1H} NMR (298 K, CDCl3): d = 164.81 (d, JCF = 248.9 Hz,
C4io-F), 134.78–132.50 (m, CH,), 117.75 (d, JC-P = 10.6 Hz, =CH2),
115.76 (dd, JCF = 20.9 Hz, JC-P = 7.2 Hz, =CH), 34.08 (d, JC-P = 13.4
Hz, CH2).
31P{1H} NMR (298 K, CDCl3): d = –17.95 (s).
19F NMR (298 K, CDCl3): d = –114.86 (s).
MS (EI+): m/z (%) = 262.4 (M+, 80), 221.3 (M+ – CH2CH=CH2,
(13) Brunel, J. M.; Faure, B.; Maffei, M. Coord. Chem. Rev.
1998, 178-180, 665.
100).
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Steimann, M.; Fawzi, R. Inorg. Chim. Acta 1999, 296, 103.
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Soc., Perkin Trans. 1 1983, 861.
Anal. Calcd for C15H13F2P: C, 68.70; H, 5.00. Found: 69.02; H,
5.30.
Allylbis(pentafluorophenyl)phosphine (24)
Purification by extraction from n-hexane; yield: 52% (Method 4).
(18) Struck, R. F.; Shealy, Y. F. J. Med. Chem. 1966, 9, 414.
(19) (a) Thapper, A.; Sparr, E.; Jonson, B. F. G.; Lewis, J.;
Raithby, P. R.; Nordlander, E. Inorg. Chem. Commun. 2004,
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Eur. J. Mass Spectrom. 2000, 6, 49.
1H NMR (298 K, CDCl3): d = 5.75 (m, 1 H, CH=), 5.07 (m, 2 H,
=CH2), 3.33 (d, JH-H = 7.2 Hz, 2 H, CH2).
13C{1H} NMR (298 K, CDCl3): d = 147.80 (d, JCF = 247.4 Hz, Co),
142.45 (d, JCF = 271.3 Hz, CP), 137.62 (d, JCF = 251.5 Hz, Cm),
130.51 (d, JC-P = 10.6 Hz, CH=), 120.06 (d, JC-P = 12.90 Hz, =CH2),
108.58 (m, Ci), 28.81 (m, CH2).
31P{1H} NMR (298 K, CDCl3): d = –48.84 (q, JPF = 23.4 Hz).
Synthesis 2009, No. 11, 1916–1922 © Thieme Stuttgart · New York