Synthesis and properties of perfluoroalkyl phosphine ligands: Photoinduced reaction of diphosphines with perfluoroalkyl iodides

Article abstract of DOI:10.1002/anie.201207383

A 'F'lurry of activity: The title reaction provides a convenient procedure for direct synthesis of perfluoroalkylated phosphines. The synthesized phosphine n-C₁₀F₂₁PPh₂ forms a complex with palladium(II) to give 1 and several runs of coupling reactions are attained with n-C₁₀F₂₁PPh₂ by using a fluorous/organic biphasic system. Copyright

Full text of DOI:10.1002/anie.201207383

Angewandte
Chemie
DOI: 10.1002/anie.201207383
Synthetic Methods
Synthesis and Properties of Perfluoroalkyl Phosphine Ligands:
Photoinduced Reaction of Diphosphines with Perfluoroalkyl Iodides**
Shin-ichi Kawaguchi, Yoshiaki Minamida, Takashi Ohe, Akihiro Nomoto, Motohiro Sonoda,
and Akiya Ogawa*
Organophosphorus compounds are widely used as ligands in
metal catalysts. Specifically, perfluoroalkylated phosphines
are gaining attention because of their fluorous affinity.[1] In
1994, Horvꢀth and co-workers reported that rhodium com-
plexes with perfluoroalkylated phosphine ligands, which were
employed in the hydroformylation of alkenes, could be
recycled using a fluorous/organic biphasic system.[2] The
fluorinated phosphine ligand 1a (Figure 1) employed in this
including its coordination ability. Furthermore, we discuss
a cross-coupling reaction that uses 2 as a recyclable ligand.
Irradiation of a mixture of perfluorodecyl iodide 3a
(0.20 mmol) and tetraphenyldiphosphine 4a (0.24 mmol) in
CDCl3 with a xenon lamp through Pyrex, under an inert
atmosphere for 12 h, afforded (perfluorodecyl)diphenylphos-
phine (2a) in quantitative yield [Eq. (2)]. The complete
consumption of 3a was confirmed by 19F NMR and 31P NMR
spectroscopy.
Figure 1. Perfluoroalkylated phosphine ligands 1a, 1b, and 2.
reaction has two methylene groups between the phosphorus
atom and the perfluoroalkyl moiety, so the electron-with-
drawing effect of the perfluoroalkyl groups is suppressed.
However, the reported synthetic methods for 1a suffer from
poor yields.[3] Although there are known synthetic routes to
the perfluoroalkylated triaryl phosphine ligand 1b, these
methods involve multiple steps which make the synthesis and
isolation time-consuming.[4] In contrast, much less attention
has been paid to the phosphine 2, in which a perfluoroalkyl
group is directly linked to the phosphorus atom,[5] because the
strong electron-withdrawing effect of the ligand is believed to
degrade the catalytic activity. Inspired by two series of
reactions we previously developed—photoinduced radical
addition reactions of perfluoroalkyl iodide to carbon–carbon
unsaturated bonds[6] and photoinduced radical addition
reactions of diphosphine to alkynes[7]—we identified a con-
venient synthetic route to the phosphines 2. This approach
involves the photoinduced reaction of diphosphines with
perfluoroalkyl iodides [Eq. (1)]. Herein, we report the
fluorous affinity as well as the electronic properties of 2,
To investigate the scope and limitations of the above-
mentioned photoinduced reaction, we used several perfluoro-
alkyl iodides with diphosphines (Table 1). Linear perfluoro-
alkyl iodides (3a–d) reacted with 4a to afford the perfluoro-
alkyldiphenylphosphines 2a–d quantitatively. Treatment of
2a–d with S8 and purification by silica gel column chroma-
tography afforded the perfluoroalkyldiphenylphosphine sul-
fides 5a–d in good yields (entries 1–4). Secondary iodides
such as perfluorocyclohexyl iodide (3e) and perfluoroiso-
propyl iodide (3 f), as well as w-diiodides such as 1,6-
diiodoperfluorohexane (3g) and 1,4-diiodoperfluorobutane
(3h), gave the corresponding phosphine sulfides 5e–h in good
yields (entries 5–8). Tetrakis(tert-butyl)diphosphine (4b)
could also be employed successfully to synthesize the desired
perfluoroalkylated phosphine (entry 9).[8]
The perfluoroalkylated phosphines 2 were not readily
oxidized in air (into the corresponding phosphine oxides) but
were partly oxidized during purification by silica gel or
alumina column chromatography. Therefore, an appropriate
isolation method which prevents the oxidation of 2 had to be
chosen. We attempted to isolate (perfluorodecyl)diphenyl-
phosphine (2a) from the reaction system by using a fluorous/
organic biphasic system (Figure 2), as this phosphine has
a long-chain perfluoroalkyl group.[1a,2] To the mixture of the
product and phosphorus residue (Ph2P(O)H, Ph2P(O)OH,
etc.) in the reaction flask, MeOH (organic solvent) and
Fluorinert (FC-72: perfluorohexanes; fluorous solvent) were
added, and 2a was isolated in 90% yield after the extraction
[*] Dr. S.-i. Kawaguchi, Y. Minamida, T. Ohe, Dr. A. Nomoto,
Dr. M. Sonoda, Prof. Dr. A. Ogawa
Department of Applied Chemistry
Graduate School of Engineering, Osaka Prefecture University
1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531 (Japan)
E-mail: ogawa@chem.osakafu-u.ac.jp
[**] This work is supported by a Grant-in-Aid for Scientific Research (C,
23550057) from the Ministry of Education, Culture, Sports, Science,
and Technology. We gratefully acknowledge the suggestions by
Associate Professor H. Matsubara at Osaka Prefecture University.
We also thank Kyoto-Nara Advanced Nanotechnology Network
(Japan), for the X-ray measurement.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201207383.
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Table 1: Photoinduced reaction of perfluoroalkyl iodides with diphosphines.
ficient is important. Hence, we
investigated the partition coeffi-
cients for 2a and 5a between FC-
72 and several organic solvents
(Table 3).[10] The highest partition
coefficient for 2a (to FC-72) was
observed when using a combination
of MeOH and FC-72, but the par-
tition coefficients for the phosphine
sulfide 5a were much lower. The
partition coefficient for 2j, which
Entry
3
4
5
Yield [%][a]
1
2
3
4
5
6
3a: n-C10F21-I
3b: n-C8F17-I
3c: n-C6F13-I
3d: n-C4F9-I
3e: c-C6F11-I
3 f: (CF3)2CF-I
3g: I-(CF2)6-I
3h: I-(CF2)4-I
3a
4a: (Ph2P)2
4a
4a
4a
4a
4a
4a
4a
5a: n-C10F21-P(S)Ph2
5b: n-C8F17-P(S)Ph2
5c: n-C6F13-P(S)Ph2
5d: n-C4F9-P(S)Ph2
5e: c-C6F11-P(S)Ph2
5 f: (CF3)2CF-P(S)Ph2
5g: Ph2P(S)-(CF2)6-P(S)Ph2
5h: Ph2P(S)-(CF2)4-P(S)Ph2
5i: n-C10F21-P(S)tBu2
80 (>99)
88 (>99)
86 (>99)
85 (>99)
89 (>99)
60 (>99)
78 (>99)
76 (>99)
53 (>99)
7[b]
8[b]
9[c]
has
a long perfluorinated alkyl
chain, was sufficiently high for this
compound to be separated by the
aforementioned extraction method
[n-C12F25PPh2 (2j): MeOH/FC-72 =
1/5.00]. In contrast, the partition
coefficient for 2b, which has
a shorter perfluorinated chain, was
low [n-C8F17PPh2 (2b): MeOH/FC-
4b: (tBu2P)2
[a] Yield of product isolated after purification by silica gel column chromatography. The yields in
parentheses were determined by 31P or 19F NMR spectroscopy. [b] The diphosphine 4a (2.4 equiv) was
used. After photoirradiation, the mixture was treated with S8 (7.2 equiv) for 12 h. [c] After photo-
irradiation, the mixture was treated with S8 for 36 h.
72 = 1/0.40]; therefore, the biphasic system could not be used
for extraction.
Table 3: Partition coefficients of the perfluoroalkylated compounds 2a
and 5a between organic solvents and FC-72.[a]
Solvent
2a
5a
MeOH
acetone
AcOEt
CHCl3
benzene
1/1.17
1:0.28
1/0.16
1/0.27
1/0.40
1/0.36
1/0.12
1/0.05
1/0.05
1/0.05
Figure 2. Isolation by using fluorous biphasic system.
Table 2: Extraction of perfluoroalkylated phosphines using a fluorous
biphasic system.
[a] Partition coefficients given for organic solvent/FC-72; values deter-
mined by gravimetric method.
The photoinduced reaction of diphosphines with
perfluoroalkyl iodides was performed under several condi-
tions to elucidate the reaction mechanism (Table 4). The
reaction of 3a with 4a did not proceed under dark conditions
(entry 1), but was successful in the presence of the radical
initiator AIBN (1.3 equiv; entry 2), thus indicating that the
mechanism involved a radical pathway. Intriguingly, the
reaction of 3a with 4a also proceeded adequately under
sunlight conditions (entry 3).
Entry
3
2
Yield [%][a]
1
2
3
4
3a: n-C10F21-I
3j: n-C12F25-I
3b: n-C8F17-I
3c: n-C6F13-I
2a: n-C10F21-PPh2
2j: n-C12F25-PPh2
2b: n-C8F17-PPh2
2c: n-C6F13-PPh2
90 (>99)[b]
94 (>99)[b]
41 (>99)[b]
19 (>99)[b]
[a] Isolation by extraction with Fluorinert (FC-72). [b] The yields in
parentheses are determined by 31P or 19F NMR spectroscopy before
isolation.
(Table 2, entry 1).[9] The phosphorus residue, obtained from
the reaction of Ph2PI with MeOH or oxidation, was trans-
ferred to the organic layer. Furthermore, (perfluorododecyl)-
diphenylphosphine (2j), which has a longer alkyl chain than
does 2a (entry 2), could be successfully isolated. However,
the yields of the isolated (perfluorooctyl)diphenylphosphine
(2b) and (perfluorohexyl)diphenylphosphine (2c), both of
which have shorter chains than 2a, were unacceptably low
because of the poor partition of the compounds between
MeOH and FC-72 (entries 3 and 4).
Table 4: Reaction of diphosphine with perfluoroalkyl iodide under
different reaction conditions.
Entry
Reaction conditions
Yield [%]
1
dark, CDCl3, RT, 12 h
AIBN (1.3 equiv), C6H6, 808C, 6 h
sunlight, CDCl3, RT, 10 h
8[a]
90[b]
91[b]
2
3[c]
[a] Determined by 31F NMR spectroscopy. [b] Yield of product isolated by
fluorous/organic biphase system. [c] 0.70 mmol of 3a was used. For
detailed reaction conditions, see the Supporting Information.
To effectively use the fluorous/organic extraction method
for product separation, understanding of the partition coef-
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bis(triphenylphosphine)palladium(II) dichloride did not
result in any such ligand exchange [Eq. (4)].
Scheme 1. A plausible reaction pathway for the photoinduced reaction
of diphosphines with perfluoroalkyl iodides.
We also succeeded in obtaining single crystals of 7a for X-
ray crystallography analysis.[15] The structure of 7a is shown in
Figure 3. Interestingly, 7a adopted the trans conformation in
the solid state, and the perfluoroalkyl groups were oriented in
the same direction. Figure S1 (see the Supporting Informa-
tion) revealed intermolecular stacking through the perfluoro-
alkyl groups. These unique results are attributed to the
introduction of a long perfluoroalkyl chain into the ligand
molecule.
A plausible pathway for the present reaction is shown in
Scheme 1. The absorption maxima (lmax) of the perfluoroalkyl
iodides and tetraphenyldiphosphine are 270 nm[6] and
260 nm,[11] respectively, and the absorption reaches the near-
UV region. Therefore, near-UV light irradiation would
induce bond cleavage in the perfluoroalkyl iodide and the
diphosphine. The perfluoroalkyl radical generated by the
cleavage of perfluoroalkyl iodide reacts with the diphosphine
to form the perfluoroalkyl phosphine 2 and a phosphine
radical. This radical, which can also be formed by the cleavage
of tetraphenyldiphosphine upon near-UV light irradiation,
abstracts an iodine atom from the perfluoroalkyl iodide to
regenerate a perfluoroalkyl radical along with an iodophos-
phine species, which is finally converted into phosphorous
residues such as Ph2P(O)H and Ph2P(O)OH during
workup.[12]
Next, we investigated the electronic properties of 2
because they actually estimate the efficiency of the transi-
tion-metal catalyst. The perfluoroalkyl group in 2 is directly
substituted at the phosphorus atom and hence may have
a marked electronic effect.[13] The 31P-77Se coupling constant
(1JP-Se) is known to be correlated with the electronic proper-
1
ties of the phosphine, that is, a large JP-Se value reflects the
Figure 3. ORTEP representation (thermal ellipsoids at 50% probability)
of 7a. R=0.0346, Rw =0.1059, GOF=1.132.
poor electron-donating ability of the phosphine.[14] Hence, we
measured JP-Se for several phosphines (see Table S1 in the
1
Supporting Information). Tertiary phosphines reacted readily
with selenium in refluxing chloroform or toluene solution to
form the corresponding phosphine selenides 6 (see the
Supporting Information for structures). The JP-Se values of
the perfluoroalkylated phosphines selenides were much
Finally, we demonstrated a number of coupling reactions
that use 2a as a recyclable ligand for the palladium catalyst.
Although Sonogashira coupling[16] proceeded in the presence
of 2a to give the coupling product 8 in quantitative yield, no
reaction occurred in the absence of 2a [Eq. (5)].[17] The
Mizoroki–Heck[18] and Suzuki–Miyaura coupling[19] reactions
also proceeded efficiently in the presence of 2a [Eqs. (6) and
(7); dba = dibenzylideneacetone]. These results indicated
that 2a plays a vital role in the reactions. The recyclability
of 2a from the reaction systems was also investigated on the
1
=
=
larger than those of Ph3P Se and (p-CF3C6H4)3P Se, thus
implying that the perfluoroalkylated phosphines are electron
deficient.
The phosphine 2a, despite its electron-poor nature,
underwent a ligand exchange reaction with the benzonitrile
unit of bis(benzonitrile)palladium(II) dichloride. In the
31P NMR spectrum of a mixture of bis(benzonitrile)palla-
dium(II) dichloride and 2a, the signal representative of 2a
(dP = 1.8 ppm) disappeared and a new signal (dP = 41 ppm),
attributable to bis(perfluorodecyldiphenylphosphine)palla-
dium(II)dichloride (7a), appeared [Eq. (3)]. 31P NMR anal-
ysis also indicated that the 2a ligand in 7a was quantitatively
replaced by PPh3 because of the weaker coordination ability
of 2a as compared to PPh3. By contrast, the addition of 2a to
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evaporated, and the residue was extracted with MeOH (4 mL) and
Fluorinert (FC-72) (4 mL ꢁ 3) in a glove box. Subsequent evaporation
of the fluorous layer afforded the pure perfluoroalkyldiphenyl
phosphine. Further details of the experimental procedures and
characterization data for the new compounds are included in the
Supporting Information.
Received: September 13, 2012
Revised: November 6, 2012
Published online: && &&, &&&&
Keywords: fluorinated ligands · phosphane ligands ·
.
photochemistry · radical reactions · synthetic methods
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basis of its fluorous affinity[20] (Table 5). After completion of
the coupling reactions, the ligand was recovered by using
a fluorous/organic biphasic system and reused five times for
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was no appreciable loss of activity of 2a for up to five runs.
Table 5: Recyclability of the ligand 2a for several coupling reactions.
Without
1st run 1st
2nd
3rd
4th
2a
with 2a recycle recycle recycle recycle
Yield of 8[a]
Yield of 9[b]
Yield of 10[b]
<1%
18% 87%
40% 87%
99%
99%
87%
98%
99%
89%
85%
99%
88%
–
98%
83%
–
[c]
[c]
[a] Yield of isolated product. [b] Determined by 1H NMR spectroscopy.
[c] Not measured.
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[8] The yield of the isolated product in this entry is relatively low
because HPLC for the separation of 5i from several phosphine
sulfides was carried out after silica gel column chromatography.
[9] Because the perfluoroalkyl iodide was completely consumed
after photoirradiation, only the perfluoroalkyldiphenylphos-
phine was isolated.
In conclusion, we have developed a convenient synthetic
route to perfluoroalkyl-substituted phosphines from diphos-
phines and perfluoroalkyl iodides. We proposed that this
reaction proceeds by a photoinduced radical pathway. The
affinity of long-chain (ꢀ C10) perfluoroalkylated phosphines
to fluorous solvents was sufficiently high. Hence, these
phosphines could be easily separated using a fluorous biphasic
system. The perfluoroalkyldiphenylphosphine 2a, notwith-
standing its poor electron-donating ability, formed a complex
with palladium(II) and the resulting complex 7a showed
a unique conformation and packing. Furthermore, 2a suc-
cessfully promoted a number of coupling reactions and could
be recycled using a fluorous/organic biphasic system. Future
studies focusing on unique metal-catalyzed reactions in the
presence of this easily accessible ligand are being planned.
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Experimental Section
The general procedure for the synthesis of perfluoroalkyldiphenyl
phosphines was as follows. Under an inert atmosphere, diphosphine
(0.24 mmol), perfluoroalkyl iodide (0.20 mmol), and degassed CDCl3
(600 mL) were placed in a sealed NMR tube (Pyrex). The mixture was
vortexed for 30 s and then irradiated with a xenon lamp (500 W) at
room temperature for 12 h. When degassed MeOH (5 mL) was added
to the mixture after completion of the reaction, and Ph2PI was
converted into Ph2P(O)H, Ph2P(O)OH, and other phosphorus
residues, along with some MeI. The solvents and MeI were then
4
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[15] Crystal structure: see the Supporting Information.
CCDC 898708 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
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[17] We also performed a Sonogashira coupling reaction using PPh3,
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Communications
Synthetic Methods
S.-i. Kawaguchi, Y. Minamida, T. Ohe,
A. Nomoto, M. Sonoda,
A. Ogawa*
&&& — &&&
Synthesis and Properties of Perfluoroalkyl
Phosphine Ligands: Photoinduced
Reaction of Diphosphines with
Perfluoroalkyl Iodides
A ‘F’lurry of activity: The title reaction
provides a convenient procedure for
direct synthesis of perfluoroalkylated
phosphines. The synthesized phosphine
n-C10F21PPh2 forms a complex with palla-
dium(II) to give 1 and several runs of
coupling reactions are attained with n-
C10F21PPh2 by using a fluorous/organic
biphasic system.
6
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