Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines and Their Application in the Copper-Free Cross-Coupling of Acid Chlorides and Terminal Alkynes

Article abstract of DOI:10.1002/adsc.201500294

A practical synthesis yielding P-perfluoroalkylated phosphines from triarylphosphines and perfluoroalkyl iodides has been developed. The photoinduced reaction involves the substitution of aryl groups on the phosphorus atom with perfluoroalkyl groups to successfully afford P-perfluoroalkylated phosphines. In addition, the P-perfluoroalkylated phosphines were found to promote the Cu-free cross-coupling reaction of acid chlorides with terminal alkynes.

Full text of DOI:10.1002/adsc.201500294

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DOI: 10.1002/adsc.201500294
Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from
Triarylphosphines and Their Application in the Copper-Free
Cross-Coupling of Acid Chlorides and Terminal Alkynes
Shin-ichi Kawaguchi,a Yoshiaki Minamida,a Takumi Okuda,a Yuki Sato,a
Tomokazu Saeki,a Aya Yoshimura,a Akihiro Nomoto,a and Akiya Ogawaa,*
a
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1–1 Gakuen-cho,
Nakaku, Sakai, Osaka 599-8531, Japan
Fax: (+81)-72-254-9910; phone: (+81)-72-254-9290; e-mail: ogawa@chem.osakafu-u.ac.jp
Received: March 25, 2015; Revised: May 11, 2015; Published online: August 3, 2015
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500294.
Abstract: A practical synthesis yielding P-perfluoro- phosphines were found to promote the Cu-free
alkylated phosphines from triarylphosphines and per- cross-coupling reaction of acid chlorides with termi-
fluoroalkyl iodides has been developed. The photoin- nal alkynes.
duced reaction involves the substitution of aryl
groups on the phosphorus atom with perfluoroalkyl
groups to successfully afford P-perfluoroalkylated Keywords: cleavage reactions; cross-coupling; fluori-
phosphines. In addition, the P-perfluoroalkylated nated ligands; palladium; phosphanes
Introduction
when used as a ligand, phosphine 1 had a positive
effect on Pd-catalyzed coupling reactions between
Phosphines bearing fluorous tags are functional li- acid chlorides and terminal alkynes, affording the cor-
gands that can aid in the recycling of metal catalysts responding ynones under Cu-free conditions.
via extraction with a fluorous biphasic system (FBS).
Ynones serve as excellent electrophiles in Michael
This concept was first proposed by Horvµth and addition reactions,[6] versatile components in the syn-
Rµbai in 1994,[1] and numerous studies regarding FBS thesis of heterocycles,[7] and valuable intermediates in
were subsequently reported.[2] A number of ligands the total synthesis of natural products.[8] The genera-
and metal catalysts suitable for FBS have been devel- tion of ynones via the coupling reaction of acid chlor-
oped;[3] however, P-perfluoroalkylated phosphines, in ides with terminal alkynes is one of the most efficient
which a perfluoroalkyl group is directly bonded to the routes towards ynones, and palladium catalysts in the
phosphine, have received little attention as ligands,[4] presence of copper salts are typically employed in
because the electron-withdrawing perfluoroalkyl their synthesis.[9] However, copper salts occasionally
groups presumably influence the coordination of the induce the Glaser reaction,[10] and therefore, it is de-
phosphine ligands to metal catalysts. However, our re- sirable to develop Cu-free coupling reactions.[11,12]
search group recently revealed that P-perfluoroalky- Moreover, the possibility of catalyst recycling is an
lated phosphine 1 (Figure 1) could form a complex advantage in the use of perfluoroalkylated phosphine
with palladium; common coupling reactions such as ligands. Additionally, directly perfluoroalkylated
Suzuki–Miyaura coupling, Sonogashira coupling, and phosphines can be synthesized relatively easily. Our
the Heck reaction proceed successfully in the pres- research group previously reported that perfluoroal-
ence of the complex.[5] Specifically, we found that, kylphosphines could be formed by a photoinduced re-
action between diphosphines and perfluoroalkyl io-
dides.[5] However, diphosphines are difficult to handle
and synthesize their derivatives. We thus investigated
readily available phosphorus sources in order to syn-
thesize perfluoroalkylphosphines. Notably, when tri-
Figure 1. Directly fluorinated phosphines.
phenylphosphine was used as a starting material,
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Table 1. Optimization of the reaction conditions in the reac-
tion between PPh3 and n-C10F21-I.
a photoinduced perfluoroalkylation reaction was ob-
served. Triphenylphosphine is one of the most com-
monly used phosphine compounds. Although substitu-
tion reactions on the phosphorus atom of triarylphos-
phines are synthetically useful, this type of reaction is
still limited,[13] except for the reaction of PAr3 with
alkali metals.[14] Therefore, in this paper, we report
a novel synthesis of P-perfluoroalkylated phosphines
via the photoinduced reaction of triarylphosphines
with perfluoroalkyl iodides and their application as li-
gands in the Cu-free Pd-catalyzed coupling reactions
between acid chlorides and terminal alkynes.
Results and Discussion
Photoinduced Reaction of Triarylphosphines with
Perfluoroalkyl Iodides
First, we examined the reaction between PPh3
(0.1 mmol) and n-C10F21-I (0.2 mmol) under photoirra-
diation by a xenon lamp (500W) in a sealed Pyrex
NMR tube in CDCl3 [Eq. (1)]. Interestingly, n-C10F21-
PPh2 (1a) was formed in a moderate yield after irradi-
ation for 30 h.
[a]
Determined by 19F NMR. Isolated yield is shown in pa-
rentheses.
The reaction was conducted in a sealed quartz NMR
tube.
Irradiation with a tungsten lamp (450W).
Irradiation with a super-high pressure mercury lamp
[b]
[c]
[d]
(250W).
Table 2. Scope and limitations of reaction between triaryl-
phosphines and perfluoroalkyl iodides under photoirradia-
tion.
Based on this positive result, the reaction condi-
tions were optimized (Table 1). First, we examined
the molar ratio of PPh3/n-C10F21-I (entries 1–5). Nota-
bly, 0.3/0.1 mmol afforded the highest yield (entry 3).
When the solvent was varied, benzotrifluoride
(BTF)[15] (entries 6–8) gave the desired product in
decent yields. However, when BTF was used, pheny-
lated BTF and perfluoroalkylated BTF were also ob-
served (~5% of both). Conducting the reaction in
a sealed quartz tube and irradiation with a tungsten
lamp or super-high pressure mercury lamp did not im-
prove the yield (entries 10–12).
Next, the scope and limitations of the photoinduced
reaction between triarylphosphines and perfluoroalkyl
iodides were investigated (Table 2). Several triaryl-
phosphines such as (4-CF3C6H4)3P, (3-CF3C6H4)3P, and
(4-ClC6H4)3P gave the corresponding perfluoroalky-
lated phosphines in moderate to good yields (en-
tries 2–4). On the other hand, the electron-deficient
phosphine (3,4,5-F3C6H2)3P, and electron-rich phos-
[a]
Isolated yield.
The product was isolated as a phosphine sulfide.
[b]
phines (4-CH3C6H4)3P and (4-CH3OC6H4)3P did not (entries 8 and 9). The branched perfluoroalkyl iodide
afford the corresponding perfluoroalkylated phos- i-C5F11I gave the corresponding fluorinated phos-
phines (entries 5–7). The perfluoroalkylation reaction phines in moderate yields (entries 10). Because of the
proceeded when both long-chain, n-C12F25I, and short low fluorine content of this fluorinated phosphine, it
chain, n-C8F17I, perfluoroalkyl iodides were employed, could not be extracted via FBS. Therefore, its isola-
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Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines
tion was carried out via silica gel column chromatog-
raphy as the corresponding phosphine sulfide (1j),
after treatment with sulfur.
Moreover, in order to elucidate the tolerance of
this reaction, trialkylphosphines were examined.
When (n-Bu)3P and (n-octyl)3P were used, the corre-
sponding P-perfluoroalkylated phosphines (1k and 1l)
were obtained rapidly in good yields [Eq. (2)]. Over-
all, the present reaction was tolerant to several triar-
Scheme 1. A proposed reaction pathway for the photoin-
duced reaction between PAr3 with Rf-I.
yl- or trialkylphosphines and perfluoroalkyl iodides (4-CF3C6H4)3P afforded diphosphines,[18] but (3,4,5-
and successfully afforded the corresponding P-per- F3C6H2)3P did not afford the corresponding diphos-
fluoroalkylated phosphines.
phine. Triarylphosphines that could give the corre-
sponding diphosphines were required for the
perfluoroalkylation reaction.
A proposed reaction pathway for the photoinduced
reaction between PAr3 with Rf-I is illustrated in
Scheme 1. It was previously reported that PAr3 could
be excited with a UV laser flash to generate diary-
lphosphino radicals (Ar2PC).[18,19] In the present reac-
tion, we assumed that Ar2P· was also generated via
À
To obtain insight into the reaction pathway, the per- the cleavage of the C P bond of PAr3 upon irradia-
fluoroalkylation reactions were conducted under sev- tion with the Xe lamp. The generated Ar2PC forms di-
eral conditions [Eq. (3)]. When a mixture of PPh3 and phosphine Ar2P-PAr2. Photoirradiation of Rf-I also
generated perfluoroalkyl radicals (RfC),[17] and the gen-
erated RfC could attack Ar2P-PAr2 to afford the prod-
uct (Ar2PRf). The SH2 reaction between the phospho-
rus atom of Ar3P and the perfluoroalkyl radical does
not proceed, because there is no leaving group. How-
ever, the formation of Ar2P-PAr2 facilitates the attack
by the radical and Ar2PC serves as the leaving group.
Overall, by using triarylphosphines, a practical syn-
thesis of P-perfluoroalkylated phosphines 1 has been
developed. Next, we investigated the utility of the
synthesized P-perfluoroalkylated phosphines as li-
gands.
n-C10F21-I was heated without irradiation, the desired
perfluoroalkylphosphine was not obtained. Heating in
the presence of the radical initiator AIBN[16] did not Cu-Free Pd-Catalyzed Coupling Reaction between
facilitate the perfluoroalkylation reaction. Photoirra- Acid Chlorides and Terminal Alkynes Using
diation through a filter (>350 nm) also prevented the Perfluoroalkylated Phosphines as Ligands
reaction. As heating of Rf-I with AIBN and irradia-
tion of Rf-I[17] around 350 nm can cause homolytic We previously reported that n-C10F21PPh2 reacted
cleavage of Rf-I and generate perfluoroalkyl radicals with PdCl2(PhCN)2 to form the palladium complex
(RfC), these results suggested that RfC did not trigger PdCl2(n-C10F21PPh2)2.[5] Therefore, reactions using
the perfluoroalkylation reaction on the phosphorus PdCl2(n-C10F21PPh2)2 as a catalyst were examined.
atom.
When the coupling reaction between benzoyl chloride
Next, photoirradiation of Ar3P was performed in (2a) and 1-octyne (3a) was conducted in the presence
the absence of Rf-I [Eq. (4)]. Irradiation of PPh3 and of PdCl2(n-C10F21PPh2)2 under Cu-free conditions, sur-
prisingly, the coupling product (1-phenylnon-2-yn-1-
one, 4aa) was obtained in quantitative yield [Eq. (5)].
As a control, the coupling reaction was conducted in
the absence of the P-perfluoroalkylated phosphine
ligand and the desired product was obtained in a low
yield. With Pd(OAc)2 alone, the desired product was
also obtained in a low yield. In contrast, the use of
Pd(OAc)2 with ligand 1a afforded the product in ex-
cellent yield. These results showed that perfluoroal-
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cluded in Table 3. When electron-poor phosphines (as
compared to PPh3) such as (4-CF3C6H4)2P(n-C10F21),
(4-CF3C6H4)3P, and (3,4,5-F3C6H2)3P were used, the
coupling reaction proceeded to give 4aa in excellent
yield (entries 2, 7 and 8). In contrast, upon addition
of relatively electron-rich phosphines such as (4-
CH3C6H4)3P, (4-CH3OC6H4)3P, and (2-CH3C6H4)3P,
the coupling reaction did not occur (entries 4–6).
These results suggested that electron-deficient ligands
were favorable for this coupling reaction.
The tolerance of the base and solvent for the cou-
pling reaction was investigated (Table 4). As expect-
ed, the coupling reaction did not proceed in the ab-
sence of a base (entry 2). Other organic and inorganic
bases were examined in place of Et3N; however, the
coupling reaction did not proceed (entries 3–6). The
kylphosphine ligand 1a had a positive effect on the coupling reaction proceeded well using THF, CHCl3,
coupling reaction.
CH3CN, and BTF as the solvent (entries 8–11). De-
Therefore, the effect of phosphine ligand 1 on the creasing the amount of toluene was also tolerated in
coupling reaction between acid chlorides and terminal the coupling reaction and the use of toluene together
alkynes was investigated. We first investigated the ef- with Et3N represented the optimal conditions for the
fects of the electronic properties of the phosphine li- coupling reaction (entry 12).
gands on the coupling reaction, because a characteris-
With the optimal conditions in hand, the scope of
tic feature of P-perfluoroalkylated phosphines is the the Cu-free coupling reaction was investigated
electron deficiency (Table 3). The 31P, 77Se coupling (Table 5). When several benzoyl chlorides such as p-
constant (1JP, Se) is known to correlate with the elec-
tronic properties of phosphines.[20] Specifically, a large
1JP, Se indicates that the phosphine ligand has a poor
electron-donating ability. As such, these values are in-
Table 4. Influence of base and solvent on the coupling reac-
tion between benzoyl chloride and 1-octyne.[a]
Table 3. Effect of ligands on coupling reaction of benzoyl
chloride with 1-octyne.[a]
[a]
Reaction conditions: benzoyl chloride (0.6 mmol), 1-
[a]
octyne (0.5 mmol), PdCl2(PhCN)2 (1 mol%), ligand
(2 mol%), Et3N (0.2 mL), toluene (0.5 mL), room tem-
perature.
Reaction conditions: benzoyl chloride (0.6 mmol), 1-
octyne (0.5 mmol), PdCl2(PhCN)2 (1 mol%), ligand
(2 mol%), Et3N (0.2 mL), toluene (1.5 mL).
[b]
[b]
Determined by 1H NMR.
Determined by 1H NMR (isolated yield).
[c]
[c]
The data are from ref.[5]
Solvent (0.5 mL).
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Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines
methylbenzoyl chloride, p-methoxybenzoyl chloride, the desired products in good yields (entries 5 and 6).
and p-chlorobenzoyl chloride were coupled with 1- Furthermore, an aliphatic acid chloride, cyclohexane-
octyne, the corresponding 1-arylnon-2-yn-1-ones were carbonyl chloride, afforded the corresponding ynone
obtained in moderate to good yields (entries 2–4). successfully and in a good yield (entry 7). On the
The use of heteroaromatic acid chlorides also gave other hand, with acetyl chloride, the desired coupling
Table 5. Scope and limitations of Cu-free coupling reaction between acid chlorides and terminal al-
kynes.[a]
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[a]
Reaction conditions: benzoyl chloride (0.6 mmol), 1-octyne (0.5 mmol), PdCl2(PhCN)2 (1 mol%),
ligand (2 mol%), Et3N (0.2 mL), toluene (0.5 mL), room temperature.
Isolated yield.
[b]
[c]
The reaction was conducted at 408C for 1.5 h.
product was not obtained (entry 8). When several ali- isolated in their respective layers. Next, the reaction
phatic terminal alkynes such as hex-5-ynenitrile, 6- between 2a with 3a was conducted with the recovered
chlorohex-1-yne, and 3,3-dimethylbut-1-yne were em- catalyst from the fluorous layer. The palladium cata-
ployed, the coupling reactions proceeded efficiently lyst could be reused at least twice[22] to afford the de-
(entries 9–11). Although the reaction between acid sired coupling product 4aa in good yields (entry 1).
chlorides and alcohols generally produces esters, the Additionally, we conducted the recycling reaction
reaction between benzoyl chloride and 2-methylbut-3- with addition of a P-perfluoroalkylated phosphine
yn-2-ol gave the desired coupling product in moderate ligand 2a after every coupling reaction. As the result,
yield (entry 12). The coupling reactions with conjugat- the coupling products were obtained in higher yields
ed and aromatic alkynes also proceeded efficiently than those without addition of the P-perfluoroalkylat-
(entries 13–17). However, the use of an alkyne bear- ed phosphine ligand after every reaction (entry 2).
ing a pyridyl group prevented the coupling reaction
(entry 18). Finally, although the coupling reaction that
employed triisopropylsilylacetylene required a longer Conclusions
reaction time and higher temperature, the coupling
product was obtained in excellent yield (entry 19). As We have developed a facile photoinduced reaction
shown in Table 5, the PdCl2(n-C10F21PPh2)2-catalyzed between triarylphosphines and perfluoroalkyl iodides
coupling reaction had a relatively high tolerance for to afford P-perfluoroalkylated phosphines. The utility
a wide range of acid chlorides and terminal alkynes.
of triarylphosphines as a phosphorus source was high-
Finally, we attempted to recycle the Pd catalyst in lighted. The synthesized P-perfluoroalkylated phos-
the coupling reaction (Scheme 2). In the presence of phines can form a complex with palladium, which cat-
a catalytic amount of PdCl2(PhCN)2 and ligand 1b,[21] alyzes the coupling reaction between acid chlorides
the reaction between acid chloride 2a and alkyne 3a and terminal alkynes in the absence of copper iodide.
was examined. After the reaction, the crude product Electron-deficient phosphine ligands had a positive
and palladium catalyst were separated via FBS and effect on the coupling reaction. This palladium–P-per-
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Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines
Scheme 2. Effects of recycling the palladium catalyst on the coupling reaction between acid chlorides and alkynes.
(100 MHz, CDCl3): d=123.6 (d, JC,P =272.8 Hz), 125.7 (dq,
C,F =JC,P =3.8 Hz), 132.8 (q, JC,F =15.3 Hz), 133.1 (q, JC,F
fluoroalkylated phosphine complex-catalyzed cou-
pling reaction has a tolerance for various aromatic
acid chlorides and terminal alkynes. The recyclability
of the complex was also demonstrated. Because of
the facile synthesis of P-perfluoroalkylated phos-
phines, investigations regarding their potential syn-
thetic applications as well as those of their palladium
complexes are ongoing in our laboratory.
J
=
33.4 Hz), 135.3 (d,
J
C,P =22.9 Hz); 31P NMR (162 MHz,
CDCl3): d=0.4–1.2 (m); 19F NMR (376 MHz, CDCl3): d=
À126.2 (2F), À122.7 (2F), À121.9 (2F), À121.7 (6F), À121.3
(2F), À117.3 (d,
J
F,P =28.3 Hz, 2F), À108.2 (dt, JF,P
=
57.0 Hz, J=14.3 Hz, 2F), À80.7 (t, J=9.9 Hz, 3F), À63.3
(6F); HR-MS (FAB): m/z=841.0031, calcd. for C24H9F27P
[M+H]+: 841.0011.
(Perfluorodecyl)bis[3-(trifluoromethyl)phenyl]phosphine
1
(1c): white solid; H NMR (400 MHz, CDCl3): d=7.54 (dd,
Experimental Section
J
H,H =7.7, JH,P =8.6 Hz, 2H), 7.70 (d, J=7.7 Hz, 2H) 7.78
(dd, JH,H =7.7, JH,P =7.3 Hz, 2H), 7.85 (d, J=8.6 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=123.9 (q, JC,F =272.6 Hz),
128.0 (q, JC,F =2.9 Hz), 129.5 (d, JC,P =7.7 Hz), 131.7 (q,
General Comments
(4-CF3C6H4)3P, [23] (3-CF3C6H4)3P, [24] (4-ClC6H4)3P, [25] and
(3,4,5-F3C6H2)3P[26] were synthesized according to the litera-
ture. Other materials were obtained from commercial sup-
pliers. All liquids were purified by distillation before use
except deuterated solvents and alkynes.
J
C,F =24.4 Hz), 131.8 (dq, JC,P =20.1 Hz, JC,F =3.8 Hz), 138
(d, JC,P =20.0 Hz); 31P NMR (162 MHz, CDCl3): d=0.3–1.1
(m); 19F NMR (376 MHz, CDCl3): d À126.0 (2F), À122.7
(2F), À121.8 (2F), À121.7 (6F), À121.2 (2F) À117.4 (2F),
À108.3 (dt, JF,P =56.9 Hz, JF,P =11.4 Hz, 2F), À80.7 (t, J=
11.4 Hz, 3F), 62.9 (6F); HR-MS (FAB): m/z=878.9791,
calcd. for C22H8F27PONa [M+Na]+: 878.9776.
General Procedure for the Photoinduced Reaction of
Triarylphosphines with Perfluoroalkyl Iodides
Bis(4-chlorophenyl)(perfluorodecyl)phosphine (1d): white
solid; 1H NMR (400 MHz, CDCl3): d=7.41 (d, J=8.8 Hz,
4H), 7.58 (t, JH,H =JH,P =8.4 Hz, 4H); 13C NMR (100 MHz,
CDCl3): d=129.0 (d, JC,P =7.7 Hz), 134.8 (d, JC,P =20.0 Hz),
135.5; 31P NMR (162 MHz, CDCl3): d=À0.7- À0.1 (m);
19F NMR (376 MHz, CDCl3): d=À126.1 (2F), À123.6 (2F),
À121.2 (8F), À120.8 (2F), À117.8 (d, JF,P =21.3 Hz, 2F),
À108.8 (dt, JF,P =51.5 Hz, J=14.3 Hz, 2F), À80.6 (t, J=
11.2 Hz, 3F); HR-MS (FAB): m/z=788.9436, calcd. for
C22H9Cl2F21OP [M+H]+: 788.9433.
PAr3 (0.3 mmol), perfluoroalkyl iodide (Rf-I, 0.1 mmol), and
CDCl3 (1 mL) were placed in a sealed Pyrex glass NMR
tube under an argon atmosphere. The mixture was stirred
for 30 s and was then irradiated with a xenon lamp (500W)
at room temperature for 30 h. After the reaction, the gener-
ation of Ar2PRf was confirmed by 19F NMR analysis. The
crude mixture was poured into a 30-mL Schlenk flask and
evaporated. MeOH (2 mL) was added to the flask, and the
product was extracted with FC-72 (3 mL”5). The obtained
product was sufficiently pure without further purification
The spectral and analytical data of 1a are shown in ref.[5]
(Perfluorodecyl)bis[4-(trifluoromethyl)phenyl]phosphine
(Perfluorododecyl)bis[4-(trifluoromethyl)phenyl]phos-
phine (1h): white solid; 1H NMR (400 MHz, CDCl3): d=
7.71 (d, J=7.6 Hz, 4H), 7.78 (t, JH,H =JH,P =8.4 Hz, 4H);
13C NMR (100 MHz, CDCl3): d=123.8 (q, JC,F =271.6 Hz),
125.6 (q, JC,F =2.9 Hz), 131.5 (q, JC,F =16.7 Hz), 134.0 (d,
1
(1b): white solid; H NMR (400 MHz, CDCl3): d=7.70 (d,
J=7.9 Hz, 4H), 7.78 (t, JH,H =JH,P =8.2 Hz, 4H); 13C NMR
J
C,P =20.0 Hz); 31P NM R (162 MHz, CDCl3): d=0.1–1.0
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(m); 19F NMR (376 MHz, CDCl3): d=À126.0 (2F), À121.8
(4F), À121.6 (10F), À121.2 (2F), À117.2 (d, JF,P =28.5 Hz,
2F), À108.4 (dt, JF,P =56.9 Hz, J=11.4 Hz, 2F), À80.6 (t, J=
11.4 Hz, 3F), À63.2 (6F): HRMS (FAB): m/z=955.9811,
calcd. for C26H8F31PO [M]+: 955.9818.
(Perfluorooctyl)bis[4-(trifluoromethyl)phenyl]phosphine
(1i): white solid; 1H NMR (400 MHz, CDCl3): d=7.71 (d,
J=8.2 Hz, 4H), 7.78 (t, JH,H =JH,P =8.2 Hz, 4H); 13C NMR
(100 MHz, CDCl3): d=123.6 (q, JC,F =273.7 Hz), 125.7 (q,
two-necked round-bottomed flask equipped with a condens-
er. The mixture was heated at 1008C for 48 hours. Then un-
reacted selenium powder was removed by filtration. Purifi-
cation of phosphine selenide was performed by preparative
TLC on silica gel using AcOEt and hexane as eluent to give
pure phosphine selenide. The phosphine selenides (n-
C10F21)Ph2P=Se,[5] Ph3P=Se,[27] (4-CH3C6H4)3P=Se,[27] (4-
CH3OC6H4)3P=Se,[27]
(2-CH3C6H4)3P=Se,[27]
and
(4-
CF3C6H4)3P=Se[27] are described in the literature.
J
C,F =3.8 Hz), 132.8 (q,
J
C,F =14.3 Hz), 135.3 (d, JC,P
=
(Perfluorodecyl)bis[4-(trifluoromethyl)phenyl]phosphine
selenide: white solid; H NMR (400 MHz, CDCl3): d=7.84
1
22.9 Hz); 31P NMR (162 MHz, CDCl3): d=0.26–1.1 (m);
19F NMR (376 MHz, CDCl3): d=À126.1 (2F), À122.7 (2F),
(dd, JH,H =8.2 Hz, JH,F =2.7 Hz, 4H), 8.17 (dd, JH,P =13.6 Hz,
À121.9 (2F), À121.8 (2F), À121.3 (2F), À117.6 (d, JF,P
=
J
J
H,H =8.2 Hz, 4H); 31P NMR (162 MHz, CDCl3): d=38.1 (t,
P, F =67.1 Hz, JP, Se =847 Hz); 19F NMR (376 MHz, CDCl3):
19.9 Hz, 2F), À108.2 (dt, JF,P =56.9 Hz, J=11.4 Hz, 2F),
À80.8 (t, J=11.4 Hz, 3F), À63.5 (6F); HR-MS (FAB): m/
z=757.0009, calcd. for C22H9F23PO [M+H]+: 757.0023.
In the case of product 1j: after the reaction of Ph3P with
Rf-I, the generation of Ph2PRf was confirmed by 31P NMR
analysis. Sulfur (28.8 mg, 0.9 mmol) was added to the tube,
and then the tube was heated at 608C after which it was
shaken for 30 seconds. The crude mixture was purified by
preparative TLC on silica gel.
d=À126.1 (2F), À122.7 (2F), À121.8 (2F), À121.7 (6F),
À121.3 (2F), À114.4 (2F), À108.5 (dt, JF,P =65.5 Hz, J=
14.2 Hz, 2F), À80.7 (t, JF,P =9.9 Hz, 3F), À63.4 (6F).
Tris(3,4,5-trifluorophenyl)phosphine selenide: white solid;
1H NMR (400 MHz, CDCl3): d=7.34 (dt, J=14.0 Hz,
6.6 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=117.2 (m),
126.5 (dd, J=80.1, 4.8 Hz), 142.8 (dt, J=264.2, 15.3 Hz),
151.4 (dqd, J=258.0, 10.5, 2.9 Hz); 31P NMR (162 MHz,
CDCl3): d=35.3 (m, JP, Se =795 Hz); 19F NMR (376 MHz,
CDCl3): d=À128.6 (d, J=22.8 Hz, 6F), À150.8 (t, J=
22.8 Hz, 3F); 77Se NMR (76 MHz, CDCl3): d=À260.0 (d,
(Perfluoroisopentyl)diphenylphosphine sulfide (1j): white
solid; 1H NMR (400 MHz, CDCl3): d=7.55–7.57 (m, 4H),
7.62–7.64 (m, 2H), (dd, JH,H =8.0 Hz, JH,P =13.5. Hz, 4H);
13C NMR (100 MHz, CDCl3): d=126.3 (d, JC,P =83.4 Hz),
129.0 (d, JC,P =13.8 Hz), 133.0 (d, JC,P =10.5 Hz), 133.3 (d,
J
P, Se =794 Hz).
J
C,P =3.1 Hz); 31P NMR (162 MHz, CDCl3): d=46.3 (t, JP, F
=
67.2 Hz); 19F NMR (376 MHz, CDCl3): d=À185.4 (1F),
À113.6 (d, J=80.1 Hz, 2F), À110.6 (d, J=80.1 Hz, 2F),
Experimental Procedure for Catalyst Recycling in the
Cu-Free Cross Coupling Reactions between Acid
À71.8 (t, J=11.5 Hz, 6F); HR-MS (FAB): m/z=487.0131, Chlorides and Terminal Alkynes Using P-
calcd. for C17H11F11PS [M+H]+: 487.0143.
Perfluoroalkylated Phosphines
Dibutyl(perfluorodecyl)phosphine (1k): colorless oil;
1H NMR (400 MHz, CDCl3): d=0.93 (d, J=7.5 Hz, 6H),
Under an inert atmosphere, PdCl2(PhCN)2 (1.9 mg,
0.005 mmol), (n-C10F21)P(4-CF3C6H4)2 (8.4 mg, 0.010 mmol),
toluene (0.5 mL), acid chloride (0.60 mmol), terminal alkyne
1.40–1.53 (m, 8H), 1.57–1.63 (m, 2H), 1.80–1.85 (m, 2H);
13C NMR (100 MHz, CDCl3): d=13.6, 21.6 (d, JC,P
=
(0.50 mmol), and Et3N (0.20 mL, 1.7 mmol) were added into
a 20-mL two-necked round-bottomed flask in this order.
After the mixture was stirred at room temperature for 1 h,
solvents were removed under vacuum. After MeOH (5 mL)
was added, the mixture was extracted with FC-72 (5 mL”5).
After the fluorous layer was poured into a 20-mL two-
necked round-bottomed flask, the solvent was removed
under vacuum. Under an inert atmosphere, toluene
(0.5 mL), acid chloride (0.60 mmol), terminal alkyne
(0.50 mmol), and Et3N (0.20 mL, 1.7 mmol) were added to
the flask. The second reaction was conducted in a similar
fashion. In the recycled reaction, purification was performed
via preparative TLC on silica gel using AcOEt and hexane
(=1:30 in the case of 4aa) as the eluents to give the coupling
product. Structural identification was conducted using
1H NMR, 13C NMR, and GC-MS (EI).
15.2 Hz), 24.2 (d, JC,P =13.3 Hz), 28.0 (d, JC,P =16.2 Hz);
31P NMR (162 MHz, CDCl3): d=À3.4 to À2.6 (m);
19F NMR (376 MHz, CDCl3): d=À126.1 (2F), À122.7 (2F),
À121.8 (2F), À121.5 (8F), À119.2 (2F), À114.5 (dt, JF,P
=
45.4 Hz, J=11.4 Hz, 2F), À80.8 (t, J=11.2 Hz, 3F); HR-MS
(FAB): m/z=681.0850, calcd. for C18H19F21PO [M+H]+:
681.0838.
Dioctyl(perfluorodecyl)phosphine (1l): colorless oil;
H NMR (400 MHz, CDCl3): d=0.81 (t, J=6.3 Hz, 6H),
1.21–1.52 (m, 26H), 1.71–1.79 (m, 2H); 13C
N
MR
(100 MHz, CDCl3): d=14.0, 21.8 (d, JC,P =5.7 Hz), 22.0 (d,
J
C,P =4.8 Hz) 22.7, 25.9 (d, JC,P =16.8 Hz), 29.1, 31.1 (d, JC,P =
12.4 Hz), 31.8; 31P NMR (162 MHz, CDCl3): d=À3.6 to
À2.7 (m); 19F NMR (376 MHz, CDCl3): d=À126.1 (2F),
À122.7 (2F), À121.7 (8F), À121.5 (2F), À119.2 (2F), À114.5
(dt, JF,P =45.6 Hz, J=11.4 Hz, 2F), À80.8 (t, J=11.2 Hz,
3F); HR-MS (FAB): m/z=777.2156, calcd. for C26H35F21P
[M+H]+: 777.2141.
1-Phenyl-2-nonyn-1-one (4aa):[11a] pale yellow oil;
1H NMR (400 MHz, CDCl3): d=0.91 (t, J=6.9 Hz, 3H),
1.29–1.35 (m, 4H), 1.43–1.51 (m, 2H), 1.67 (quint, J=
7.3 Hz, 2H), 2.49 (t, J=7.3 Hz, 2H), 7.46 (dd, J=7.8,
7.8 Hz, 2H), 7.58 (t, J=7.8 Hz, 1H), 8.18 (d, J=7.8 Hz,
2H); 13C NMR (100 MHz, CDCl3) d=13.9, 19.1, 22.4, 27.7,
28.5, 31.1, 79.6, 96.8, 128.4, 129.4, 133.7, 136.8, 178.1; MS
(EI): m/z=214 (M+).
Experimental Procedures for the Measurement of
31P,77Se Coupling Constants of Several Phosphine
Selenides
Preparation of phosphine selenide: Under inert atmosphere,
phosphine (0.1 mmol), selenium powder (23.7 mg,
0.3 mmol), and CHCl3 or toluene were added into a 20-mL
1-(4-Methylphenyl)-2-nonyn-1-one (4ba):[11a] pale yellow
1
oil; H NMR (400 MHz, CDCl3): d=0.91 (t, J=6.9 Hz, 3H),
1.28–1.38 (m, 4H), 1.43–1.52 (m, 2H), 1.67 (quint, J=
2516
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Photoinduced Synthesis of P-Perfluoroalkylated Phosphines from Triarylphosphines
7.3 Hz, 2H), 2.43 (s, 3H), 2.49 (t, J=7.3 Hz, 2H), 7.26 (d,
J=8.2 Hz, 2H), 8.02 (d, J=8.2 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=14.2, 19.4, 21.9, 22.6, 27.9, 28.8, 31.4,
79.9, 96.5, 129.3, 129.8, 134.8, 145.0, 178.1; MS (EI): m/z=
228 (M+).
28.1, 30.2, 78.2, 104.0, 128.5, 129.6, 133.9, 137.1, 178.4; MS
(EI): m/z=186 (M+).
1-Phenyl-4-hydroxy-4-methylpent-2-yn-1-one
(4ae):[11a]
pale yellow oil; 1H NMR (400 MHz, CDCl3): d=1.68 (s,
6H), 7.48 (t, J=7.7 Hz, 2H), 7.61 (tt, J=7.5, 1.4 Hz, 1H),
8.12 (dd, J=8.4, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=30.8, 65.4, 80.0, 98.3, 128.7, 129.7, 134.4, 136.6, 178.1; MS
(EI): m/z=188 (M+).
1-(4-Methoxyphenyl)-2-nonyn-1-one (4ca):[11a] yellow oil;
1H NMR (400 MHz, CDCl3): d=0.91 (t, J=6.8 Hz, 3H),
1.29–1.35 (m, 4H), 1.44–1.51 (m, 2H), 1.63–1.71 (m, 2H),
2.49 (t, J=7.3 Hz, 2H), 3.89 (s, 3H), 6.95 (dd, J=6.8,
2.3 Hz, 2H), 8.10 (d, J=6.8, 2.3 Hz, 2H); 13C NMR
(100 MHz, CDCl3) d=14.2, 19.4, 22.6, 28.0, 28.8, 31.4, 55.7,
79.8, 96.1, 113.9, 130.5, 132.0, 164.4, 177.1; MS (EI): m/z=
244 (M+).
1-Phenyl-3-(1-cyclohexenyl)prop-2-yn-1-one
(4af):[11a]
yellow oil; 1H NMR (400 MHz, CDCl3): d=1.62–1.74 (m,
2H), 2.18–2.24 (m, 1H), 2.27–2.31 (m, 1H), 6.58–6.60 (m,
1H), 7.48 (t, J=7.7 Hz, 2H), 7.60 (tt, J=7.7, 1.4 Hz, 1H),
8.14 (dd, J=7.7, 0.9 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=21.2, 22.1, 26.3, 28.5, 85.4, 95.9, 119.3, 128.6, 129.6, 133.9,
137.2, 142.8, 178.3; MS (EI): m/z=210 (M+).
1-(4-Chlorophenyl)-2-nonyn-1-one (4da):[11a] pale yellow
1
oil; H NMR (400 MHz, CDCl3): d=0.91 (t, J=7.1 Hz, 3H),
1,3-Diphenylprop-2-yn-1-one (4ag):[11a] pale yellow solid;
1H NMR (400 MHz, CDCl3): d=7.42 (tt, J=7.3, 1.6 Hz,
2H), 7.46–7.54 (m, 3H), 7.63 (tt, J=7.5, 1.4 Hz, 1H), 7.70
(dd, J=8.4, 1.4 Hz, 2H), 8.23 (dd, J=8.6, 1.4 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=87.0, 93.2, 120.2, 128.7,
128.8, 129.7, 130.9, 133.2, 134.2, 137.0, 178.1; MS (EI): m/z=
206 (M+).
1.30–1.35 (m, 4H), 1.44–1.51 (m, 2H), 1.68 (quint, J=
7.3 Hz, 2H), 2.50 (t, J=7.1 Hz, 2H), 7.45 (dt, J=8.7, 2.0 Hz,
2H), 8.07 (dt, J=8.7, 2.0 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=14.1, 19.4, 22.6, 27.9, 28.8, 31.4, 79.5, 97.7, 129.0,
131.0, 135.5, 140.6, 177.0; MS (EI): m/z=248, 250 (M+).
1
1-(2-Thienyl)-2-nonyn-1-one (4ea):[27] yellow oil; H NMR
(400 MHz, CDCl3): d=0.91 (t, J=7.0 Hz, 3H), 1.30–1.34
(m, 4H), 1.43–1.51 (m, 2H), 1.62–1.70 (m, 2H), 2.47 (t, J=
7.0 Hz, 2H), 7.14 (dd, J=5.0, 3.6 Hz, 1H), 7.68 (dd, J=5.0,
1.4 Hz, 1H), 7.89 (dd, J=4.1, 1.4 Hz, 1H); 13C NM R
(100 MHz, CDCl3): d=14.1, 19.2, 22.6, 27.8, 28.7, 31.3, 79.4,
95.5, 128.3, 134.91, 134.94, 145.1, 170.1; MS (EI): m/z=220
(M+).
3-(4-Methylphenyl)-1-phenylprop-2-yn-1-one
(4ah):[11a]
1
pale yellow solid; H NMR (400 MHz, CDCl3): d=2.40 (s,
3H), 7.22 (d, J=7.7 Hz, 2H), 7.51 (t, J=7.7 Hz, 2H), 7.58
(d, J=8.2 Hz, 2H), 7.62 (tt, J=7.5, 1.4 Hz, 1H), 8.22 (dd,
J=8.2, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=21.9,
86.9, 93.6, 117.1, 128.7, 129.6, 129.7, 133.2, 134.1, 137.0,
141.7, 178.2; MS (EI): m/z=220 (M+).
1-(2-Furyl)-2-nonyn-1-one (4fa):[28] yellow oil; 1H NMR
(400 MHz, CDCl3): d=0.90 (t, J=7.0 Hz, 3H), 1.30–1.34
(m, 4H), 1.42–1.50 (m, 2H), 1.61–1.68 (m, 2H), 2.46 (t, J=
7.3 Hz, 2H), 6.57 (dd, J=3.6, 1.8 Hz, 1H), 7.32 (dd, J=3.6,
0.9 Hz, 1H), 7.65 (dd, J=1.8, 0.9 Hz, 1H); 13C NM R
(100 MHz, CDCl3): d=14.1, 19.2, 22.6, 27.7, 28.6, 31.3, 79.1,
95.8, 112.6, 120.7, 147.8, 153.3, 165.1; MS (EI): m/z=204
(M+).
3-(4-Methoxyphenyl)-1-phenylprop-2-yn-1-one
(4ai):[11a]
1
yellow solid; H NMR (400 MHz, CDCl3): d=3.86 (s, 3H),
6.94 (d, J=8.2 Hz, 2H), 7.52 (t, J=7.7 Hz, 2H), 7.60–7.66
(m, 3H), 8.20 (d, J=7.7, 2H); 13C NMR (100 MHz, CDCl3):
d=55.6, 87.0, 94.4, 112.1, 114.6, 128.7, 129.6, 134.0, 135.3,
137.2, 161.9, 178.2; MS (EI): m/z=236 (M+).
1-Phenyl-3-(4-trifluoromethylphenyl)prop-2-yn-1-one
1
(4aj):[11a] pale yellow solid; H NMR (400 MHz, CDCl3): d=
1
1-Cyclohexyl-2-nonyn-1-one (4ga):[11a] yellow oil; H NMR
7.54 (dd, J=7.7, 7.3 Hz, 2H), 7.66 (tt, J=7.7, 1.4 Hz, 1H),
7.69 (d, J=8.6 Hz, 2H), 7.79 (d, J=8.2 Hz, 2H), 8.22 (dd,
J=8.4, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=88.2,
90.6, 123.7 (q, JC,F =272.8 Hz), 124.0, 125.9 (q, JC,F =3.8 Hz),
128.9, 129.8, 132.4 (q, JC,F =33.4 Hz), 133.3, 134.6, 136.7,
177.8; 19F NMR (373 MHz, CDCl3): d=À63.0; MS (EI): m/
z=274 (M+).
(400 MHz, CDCl3): d=0.90 (t, J=7.0 Hz, 3H), 1.19–1.35
(m, 6H), 1.36–1.46 (m, 4H), 1.55–1.68 (m, 3H), 1.78 (dt, J=
12.2, 7.3 Hz, 2H), 1.97 (dd, J=13.1, 3.2 Hz, 2H), 2.37 (m,
3H); 13C NMR (100 MHz, CDCl3): d=14.2, 19.1, 22.6, 25.6,
26.0, 27.9, 28.4, 28.7, 31.3, 52.4, 80.3, 95.2, 191.9; MS (EI):
m/z=220 (M+).
7-Oxo-7-phenylhept-5-ynenitrile (4ab):[11a] yellow oil;
1H NMR (400 MHz, CDCl3): d=2.04 (quint, J=7.0 Hz,
2H), 2.58 (t, J=7.0 Hz, 2H), 2.71 (t, J=7.0 Hz, 2H), 7.49 (t,
J=7.5 Hz, 2H), 7.62 (tt, J=7.3, 1.4 Hz, 1H), 8.11 (dd, J=
7.9, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=16.4,
18.2, 23.8, 80.8, 92.7, 118.7, 128.7, 129.5, 134.3, 136.5, 177.8;
MS (EI): m/z=197 (M+).
1-Phenyl-3-(triisopropylsilyl)prop-2-yl-1-one
(4al):[11a]
yellow oil; 1H NMR (400 MHz, CDCl3): d=1.12–1.26 (m,
21H), 7.49 (t, J=7.5 Hz, 2H), 7.61 (tt, J=7.3, 1.4 Hz, 1H),
8.18 (dd, J=7.9, 1.2 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=11.2, 18.7, 98.1, 103.2, 128.7, 129.6, 134.2, 136.9, 177.6;
MS (EI): m/z=286 (M+).
1-Phenyl-7-chlorohept-2-yn-1-one (4ac): pale yellow oil;
1H NMR (400 MHz, CDCl3): d=1.80–1.88 (m, 2H), 1.93–
2.00 (m, 2H), 2.55 (t, J=6.8 Hz, 2H), 3.60 (t, J=6.3 Hz,
2H), 7.48 (t, J=7.7 Hz, 2H), 7.60 (tt, J=7.5, 1.4 Hz, 1H),
8.13 (dd, J=7.3, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=18.6, 25.1, 31.5, 44.3, 80.0, 95.5, 128.6, 129.5, 134.0, 136.8,
178.1; MS (EI): m/z=220, 222 (M+); HR-MS (ESI): m/z=
243.0553, calcd. for C13H13ClONa [M+Na]+: 243.0553.
Acknowledgements
We thank Kyoto-Nara Advanced Nanotechnology Network
and the analytical section of Osaka University, Japan for high
resolution mass spectra measurement.
1-Phenyl-4,4-dimethylpent-2-yn-1-one
(4ad):[12b]
pale
yellow oil; 1H NMR (400 MHz, CDCl3): d=1.39 (s, 9H),
7.47 (t, J=7.7 Hz, 2H), 7.59 (tt, J=7.4, 1.4 Hz, 1H), 8.12
(dd, J=8.6, 1.4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=
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Shin-ichi Kawaguchi et al.
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