Pd(II) Complexes Ligated by 1,3-Bis(diphenylphosphino)calix[4]arene: Preparation, X-ray Structures, and Catalyses

Article abstract of DOI:10.1021/acs.organomet.5b00999

syn-1,3-Bis(diphenylphosphino)-2,4-dimethoxycalix[4]arene (7) was synthesized via an Ullmann-type phosphinoylation of the syn-1,3-bis(triflate ester) (2) of p-tert-butylcalix[4]arene, followed by reduction of the phosphinoyl moieties and subsequent methylation of the remaining hydroxy groups. The treatment of diphosphine 7 with 2 molar equiv of PdCl₂(MeCN)₂ in benzonitrile afforded di-μ-chloro-bridged dinuclear palladium complex 8, formulated as Pd₂(7)Cl₄, whereas the same reaction conducted in acetonitrile with 1 molar equiv of PdCl₂(MeCN)₂ yielded mononuclear palladium complex 9, formulated as [Pd(7)Cl(MeCN)]Cl. Complex 9 was transformed into dicationic complex 11, formulated as [Pd(7) MeCN)₂](BF₄)₂, by treatment with AgBF₄ in dichloromethane, followed by the addition of acetonitrile. On the other hand, refluxing complex 9 in 1,2-dichloroethane yielded neutral complex 12, formulated as Pd(7)Cl₂. In each of the mononuclear complexes, the palladium ion adopts a tetracoordinated square-planar geometry perpendicular to the mean plane defined by the macrocycle, and two phosphorus atoms occupy trans coordination sites. Consequently, an acetonitrile or chlorine ligand coordinates through the cavity of the calixarene, while another acetonitrile or chlorine ligand occupies the exo position. Dicationic complex 11 promoted Suzuki-Miyaura coupling between aryl chlorides and phenylboronic acid and the ring-opening reaction of an epoxide with thiophenol.

Full text of DOI:10.1021/acs.organomet.5b00999

Article
pubs.acs.org/Organometallics
Pd(II) Complexes Ligated by 1,3-
Bis(diphenylphosphino)calix[4]arene: Preparation, X‑ray Structures,
and Catalyses
Kengo Hirasawa, Shinya Tanaka,* Takeru Horiuchi, Takahiro Kobayashi, Takumi Sato, Naoya Morohashi,
and Tetsutaro Hattori*
Department of Biomolecular Engineering, Graduate School of Engineering, Tohoku University, 6-6-11 Aramaki-Aoba, Aoba-ku,
Sendai 980-8579, Japan
S
* Supporting Information
ABSTRACT: syn-1,3-Bis(diphenylphosphino)-2,4-dimethoxy-
calix[4]arene (7) was synthesized via an Ullmann-type
phosphinoylation of the syn-1,3-bis(triflate ester) (2) of p-
tert-butylcalix[4]arene, followed by reduction of the phosphi-
noyl moieties and subsequent methylation of the remaining
hydroxy groups. The treatment of diphosphine 7 with 2 molar
equiv of PdCl2(MeCN)2 in benzonitrile afforded di-μ-chloro-
bridged dinuclear palladium complex 8, formulated as
Pd2(7)Cl4, whereas the same reaction conducted in acetonitrile
with 1 molar equiv of PdCl2(MeCN)2 yielded mononuclear palladium complex 9, formulated as [Pd(7)Cl(MeCN)]Cl. Complex
9 was transformed into dicationic complex 11, formulated as [Pd(7) MeCN)2](BF4)2, by treatment with AgBF4 in
dichloromethane, followed by the addition of acetonitrile. On the other hand, refluxing complex 9 in 1,2-dichloroethane yielded
neutral complex 12, formulated as Pd(7)Cl2. In each of the mononuclear complexes, the palladium ion adopts a tetracoordinated
square-planar geometry perpendicular to the mean plane defined by the macrocycle, and two phosphorus atoms occupy trans
coordination sites. Consequently, an acetonitrile or chlorine ligand coordinates through the cavity of the calixarene, while another
acetonitrile or chlorine ligand occupies the exo position. Dicationic complex 11 promoted Suzuki−Miyaura coupling between
aryl chlorides and phenylboronic acid and the ring-opening reaction of an epoxide with thiophenol.
phosphinoylation (compound 6)14 and investigated its
complexation ability toward palladium(II) ion. In addition,
INTRODUCTION
■
Transition-metal-catalyzed reactions play central roles in
the catalysis of the resulting palladium complexes was briefly
examined. To the best of our knowledge, this is the first report
on a calix[4]arene derivative in which phosphino groups are
directly introduced to the narrow rim.
modern synthetic organic chemistry, which is much indebted
to the development of multidentate ligands.1 Calixarenes (e.g.,
1), possessing unique three-dimensional structures, have been
used as platforms to construct multidentate ligands.2 Among
such entities, phosphorus-based bidentate ligands are of
particular interest in view of their catalytic applications.3 In
order to make better use of the structural features of a calix
macrocycle, it is desirable for a metal ion to be fixed close to the
calix skeleton by chelation. Although phosphorus atomic
groups have been directly introduced into the wide rims of
calix[4]arenes,4−6 there have been few reports of success in
such chelate formation.7 For narrow-rim derivatives, because
there has been no versatile synthetic method to displace the
hydroxy groups with other functions by cleaving the aryl−
oxygen bonds, phosphorus atomic groups had to be introduced
on the phenoxy oxygens either directly or indirectly through
linkers, which locates the coordinating groups apart from the
calix skeleton, thereby making it difficult to form a tight
chelate.8−10 Recently, we found that Ullmann-type reactions are
applicable to 1,3-bis(triflate ester) 2, which provided easy
access to diamine 3,11 diphosphonic acid 4,12 and diiodide 5.13
In this study, we prepared diphosphine 7 via Ullmann-type
RESULTS AND DISCUSSION
■
Synthesis of Diphosphine 7. Diphosphine 7 was prepared
according to Scheme 1. The reaction of syn-1,3-bis(triflate
ester) 2 with diphenylphosphine oxide in the presence of a
catalytic amount of CuI in DMF gave bis(phosphine oxide) 6
in 24% yield; the reaction was accompanied by side reactions,
Received: December 8, 2015
© XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.5b00999
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Article
a
Scheme 1. Synthesis of Diphosphine 7
Scheme 2. Complexation of Diphosphine 7 with
PdCl2(MeCN)2 and Ligand Exchange of the Resulting
a
Complex 9
a
Reagents and conditions: (a) CuI (10 mol %), HP(O)Ph2 (2.4 mol
equiv), K3PO4 (4.0 mol equiv), DMF, 80 °C, 24 h, 24%; (b) HSiCl3
(10 mol equiv), Et3N (10 mol equiv), xylene, reflux, 4 h; (c) MeI (8.0
mol equiv), NaH (4.0 mol equiv), DMF, room temperature., 4 h, 74%
starting from bis(phosphine oxide) 6.
including hydrogenation, detriflation, and intramolecular
cyclization,11 which could not be suppressed by changing the
reaction conditions, presumably due to the large steric bulk of
the phosphinoylation reagent. Reduction of the phosphinoyl
moieties with HSiCl3, followed by methylation of the hydroxy
1
groups, delivered the desired diphosphine 7. The H NMR
spectrum of diphsophine 7 exhibited two singlets (18H each)
for the tert-butyl protons, a pair of doublets (4H each) for the
bridging methylene protons, a singlet (6H) for the methoxy
protons, and a singlet and a doublet coupled with the
phosphorus atom (4H each) for the aryl protons of the calix
skeleton; the magnetic equivalences suggested a C2v-symmetric
structure. The NOESY spectrum exhibited correlations
between the aryl protons of the calix skeleton and between
the methoxy protons and the aryl protons of the
diphenylphosphino moieties (Figure S2 in the Supporting
Information). These observations indicate that the compound
adopts a cone conformation with a syn arrangement of the two
diphenylphosphino groups. On the other hand, a singlet signal
appeared at −1.4 ppm in the 31P NMR spectrum. The resonant
frequency is close to that of PPh3 (−4.5 ppm), suggesting that
the phosphorus atoms of diphosphine 7 have coordination
ability similar to that of PPh3.
a
Reagents and conditions: (a) PdCl2(MeCN)2 (2.2 molar equiv),
benzonitrile, room temperature, 4.5 h, then 100 °C, 1 h, 64%; (b)
PdCl2(MeCN)2 (1.0 molar equiv), acetonitrile, reflux, 1 h, 67%; (c)
AgBF4 (2.0 molar equiv), acetonitrile, reflux, 1 h, 68% from 7; (d)
AgBF4 (4.0 molar equiv), dichloromethane, room temperature, 1 h,
then acetonitrile, room temperature, 74% from 7; (e) 1,2-dichloro-
ethane, reflux, 1 h, 18% from 7.
Preparation of Pd(II) Complexes of Diphosphine 7.
The complexation ability of diphosphine 7 toward palladium-
(II) ion was investigated (Scheme 2). The reaction of ligand 7
with an equimolar amount of PdCl2(MeCN)2 in benzonitrile
gave a complex mixture. However, increasing the amount of
PdCl2(MeCN)2 to 2.2 molar equiv afforded complex 8 as the
1
sole product. The H NMR spectrum of complex 8 exhibited
two singlets (18H each) for the tert-butyl protons, a pair of
doublets (4H each) for the bridging methylene protons, and
one singlet (6H) for the methoxy protons; the magnetic
equivalences suggested a C2v-symmetric structure. Fortunately,
slow diffusion of hexane into a 1,2-dichloroethane solution of
complex 8 gave single crystals, one of which was subjected to X-
ray analysis (Figure 1). It was revealed that complex 8 is a
dinuclear complex formulated as Pd2(7)Cl4, in which the
calixarene ligand adopts a 1,3-alternate conformation. The
phosphorus atoms coordinate one by one to palladium ions
bridged by two chlorine atoms. Carbon atoms C1 and C23
connecting to the diphenylphosphino groups are highly
distorted out of the calix macrocycle in order to accommodate
the large di-μ-chloro-bridged dipalladium moiety; the dihedral
angles between the least-squares planes defined by C2−C3−
C4−C5−C6 and P1−C1(C2)−C6 and by C24−C25−C26−
C27−C28 and P2−C23(C24)−C28 are 16.65 and 15.52°,
Figure 1. X-ray structure of complex 8. Solvent molecules and
hydrogen atoms are omitted for clarity. Selected bond lengths (Å) and
angles (deg): P1−Pd1 2.2506(7), P2−Pd2 2.2515(7), Pd1−Cl1
2.2907(7), Pd1−Cl2 2.3253(7), Pd1−Cl3 2.3891(7), Pd2−Cl2
2.3281(7), Pd2−Cl3 2.3939(7), Pd2−Cl4 2.2875(7); P1−Pd1−Cl2
95.06(2), Cl2−Pd1−Cl3 84.90(2), P1−Pd1−Cl1 91.53(3), Cl1−
Pd1−Cl3 88.53(2), P2−Pd2−Cl2 95.18(2), Cl2−Pd2−Cl3 84.73(2),
Cl3−Pd2−Cl4 88.18(2), P2−Pd2−Cl4 91.87(3).
respectively, which are considerably larger than those of 1,3-
diphosphonic acid 4 (6.59−8.52°).12 In addition, the P1−Pd1−
Cl2 and P2−Pd2−Cl2 bond angles are obtuse (95.06 and
95.18°, respectively), whereas the Cl2−Pd1−Cl3 and Cl2−
B
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Pd2−Cl3 bond angles are acute (84.90 and 84.73°,
respectively), indicating that Cl2 is shallowly embedded into
the cavity constructed by two calix benzene rings and two
diphenylphosphino groups to avoid steric repulsion with the
benzene rings sandwiching the chlorine atom.
methyl groups of exo- and endo-coordinating acetonitrile
molecules, respectively. The structure of 11 was determined by
X-ray analysis (Figure 3). Complex 11 is a mononuclear
When diphosphine 7 was refluxed with 1.0 molar equiv of
PdCl2(MeCN)2 in acetonitrile, another palladium complex 9
with a C2v-symmetric structure was obtained, as evidenced by
1H NMR analysis. Interestingly, a singlet signal with an
integrated intensity of 3H was observed at −1.56 ppm,
suggesting that an acetonitrile molecule is included into the
cavity of diphosphine 7 with a cone conformation. Crystal-
lization of complex 9 by slow diffusion of hexane vapor into a
solution of this complex in 1,2-dichloroethane gave single
crystals suitable for X-ray analysis (Figure 2). Complex 9 is a
Figure 3. X-ray structure of complex 11. Solvent molecules, hydrogen
atoms, and counteranions are omitted for clarity.
complex, formulated as [Pd(7)(MeCN)2](BF4)2, with a Cs-
symmetric structure in which the palladium center and four
coordinating atoms (P1, P2, N1, and N2) are in the σ plane.
The fact that ligand exchange did not occur in acetonitrile
suggests that the acetonitrile molecule coordinating to the
palladium center has to be eliminated prior to the elimination
of the chloride ligand. This should be assisted by the
coordination of the methoxy groups to the palladium center.
Interestingly, when dichloro complex 9 was refluxed in 1,2-
dichloroethane for 1 h, another dichloro complex 12 was
obtained (Figure 4). The complex has a chemical formula of
Figure 2. X-ray structure of complex 9. Solvent molecules, hydrogen
atoms, and counteranions are omitted for clarity.
cationic mononuclear complex, formulated as [Pd(7)Cl-
(MeCN)]Cl. Diphosphine 7 adopts a pinched-cone conforma-
tion, and the two diphenylphosphino groups coordinate to a
1
palladium ion in a trans fashion. As suggested by the H NMR
analysis, an acetonitrile molecule is deeply embedded in the
cavity of diphosphine 7, directing the nitrogen atom inside so as
to coordinate to the palladium center. The coordination site
trans to the acetonitrile is occupied by a chlorine atom. As
mentioned above, mono- and dinuclear complexes could be
selectively prepared from the same palladium source by simply
changing the solvent.
Next, the displacement of the chlorine atoms of complex 9
was investigated. Treatment of the dichloro complex with 2.0
molar equiv of AgBF4 in acetonitrile resulted in anion exchange
of a chloride ion with BF4− to give complex 10, as evidenced by
X-ray analysis (Scheme 2). Complex 10 has almost the same
cation structure as that of complex 9 (Figure S1 in the
Supporting Information).15 The chlorine atom binding to the
palladium center of 9 was not displaced with acetonitrile, even
upon heating the reaction mixture to reflux. However, this
ligand exchange was achieved when 9 was treated with 4.0
molar equiv of AgBF4 in dichloromethane at room temperature
before the addition of acetonitrile; the reaction mixture
immediately changed from yellow to dark green and further
Figure 4. X-ray structure of complex 12. Solvent molecules and
hydrogen atoms are omitted for clarity.
Pd(7)Cl2, in which the two chlorine atoms bind to the
palladium center in a trans fashion, occupying the exo- and
endo-coordination sites. The formation of complex 12 indicates
that the acetonitrile molecule coordinating through the calix
cavity in [Pd(7)Cl(MeCN)]− can be eliminated from the
palladium center in a noncoordinating solvent. This agrees well
with the ligand-exchange mechanism for the formation of
1
to pale orange on the addition of acetonitrile. The H NMR
spectrum of the resulting complex 11 exhibited two singlets
(3H each) at 3.05 and −1.59 ppm, which are assignable to the
C
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Table 1. Selected Bond Lengths, Bite Angles, Benzene Distortion, and Dihedral Angles of Pd Complexes 8−12
8
9
10
11
2.359(2)
12
2.323(2)
2.324(2)
P−Pd distance/Å
2.2506(7)
2.2515(8)
−
2.3427(7)
2.3432(7)
173.18(2)
9.21
2.3563(8)
2.3475(8)
173.10(2)
9.37
2.348(2)
171.76(8)
11.12
P−Pd−P angle/deg
distortion of the benzene rings bearing PPh2 /deg
170.16(6)
13.96
a
16.66
15.22
12.18
9.64
11.02
13.92
b
dihedral angle between the benzene rings bearing PPh2 /deg
3.87
53.38
50.18
54.79
64.51
Pd−OMe distance/Å
2.744(2)
2.933(2)
146.10(4)
26.31
2.796(2)
2.815(2)
147.00(6)
29.99
2.779(4)
2.779(4)
145.50(1)
26.69
2.951(4)
2.976(4)
144.88
O−Pd−O angle/deg
dihedral angle between the benzene rings bearing OMe /deg
c
40.54
9.62
bonding distance/Å
d
Pd−Cl 2.2956(2)
Pd−N 2.001(2)
Pd−Cl 2.2922(6)
Pd−N 1.997(2)
Pd−N1 1.992(7)
Pd−N2 1.975(6)
Pd−Cl1 2.339(2)
Pd−Cl2 2.275(1)
a
The dihedral angle (θ) between the least-squares planes defined by C2−C3−C4−C5−C6 and P−C1(C2)−C6:
b
c
The dihedral angle between the least-squares planes defined by five carbon atoms except the ipso carbon bearing a PPh2 group. The dihedral angle
d
between the least-squares planes defined by six carbon atoms constructing a benzene ring. See Figure 1.
1
complex 11. The H NMR spectrum of complex 12 exhibited
two singlets (18H each) for the tert-butyl protons, a pair of
doublets (4H each) for the bridging methylene protons, a
singlet (6H) for the methoxy protons, and two singlets (4H
each) for the aryl protons of the calix skeleton; the magnetic
equivalences suggested a C2v-symmetric structure. The NOESY
spectrum exhibited correlations between the aryl protons of the
calix skeleton and between the methoxy protons and the aryl
protons of the diphenylphosphino moieties (Figure S3 in the
Supporting Information). These observations indicate that the
compound adopts a cone conformation also in solution,
similarly to the other mononuclear complexes.
reactions, including this reaction.4b,c,e−g,j However, the Suzuki−
Miyaura coupling catalyzed by calixarene complexes often
encounters difficulties in using aryl chlorides as substrates, even
if they are activated by electron-withdrawing groups. Tsuji and
co-workers reported that bulky triarylphosphine ligands
promoted the Suzuki−Miyaura coupling of aryl chlorides.17,18
We were interested in the catalytic activity of complexes 8−12
toward the Suzuki−Miyaura coupling between aryl chlorides
and phenylboronic acid because of their bulkiness and unique
stereostructures. The reaction of 4-chloroacetophenone (13a)
with phenylboronic acid was conducted in the presence of 1
mol % of a complex (8−12) in dioxane at 100 °C for 1 h using
NaH as a base to give biphenyl 14a; the product yield varied
depending on the complex employed (Table 2, entries 1−5).
Since the reaction requires a palladium complex with two
ligand-exchangeable coordination sites in a cis relationship,19
this observation indicates that one of the two Pd−P bonds in
mononuclear complexes 9−12 is dissociated during catalysis. In
other words, diphosphine 7 can serve as a bulky monodentate
phosphine ligand with a calixarene skeleton. Dicationic complex
11 exhibited the highest catalytic activity among complexes 8−
12 (entry 4); this observation suggested that complex 11 can be
converted into an active Pd(0) species more readily than the
others via the replacement of the two acetonitrile ligands with
phenyl anions generated from the boronic acid with the aid of
NaH, followed by the reductive elimination of biphenyl.
Reducing the amount of complex 11 to 0.01 mol % made the
reaction sluggish, but the turnover number reached 2500 after
prolonged heating (48 h) (entry 6). It should be noted that the
cationic palladium complex [Pd(PPh3)2(PhCN)2](BF4)2 did
not catalyze the reaction (entry 7) in spite of the fact that the
phosphine constitutes a structural element of ligand 7. In
addition, cationic palladium complexes with the bidentate
ligands BINAP, dppp, and dppf gave no coupling product
(entries 8−10). These observations indicate that the catalytic
activity of complexes 9−12 toward the aryl chloride was
realized by incorporating the phosphine structure into the
calix[4]arene framework. The attempt to generate an in situ
catalyst from [Pd(MeCN)4](BF4)2 and ligand 7 was
unsuccessful, giving biphenyl 14a in a poor yield (entry 11).
The structural data for complexes 8−12 are summarized in
Table 1. The P−Pd distances of mononuclear complexes 9−12
are similar to each other and longer than the P−Pd distance of
dinuclear complex 8 by ca. 0.1 Å, indicating that the
phosphorus atoms of the mononuclear complexes coordinate
to palladium less strongly than those of the dinuclear complex.
The distances between the methoxy oxygen atoms and the
palladium centers in mononuclear complexes 9−12 fall within a
range that allows for Pd−O interaction (2.744−2.976 Å).
However, such an interaction does not seem to be present in
these complexes, judging from the directions of the oxygen lone
pairs. Mononuclear complexes 9−12 adopt pinched-cone
conformations, in which the facing benzene rings bearing
methoxy groups have a dihedral angle (9.62−29.99°) smaller
than those bearing diphenylphosphino groups (50.18−64.51°).
Complex 12 exhibits the largest difference in dihedral angle
(54.89°) among these complexes. In addition, this complex has
longer Pd−O distances and shows greater distortion of the calix
benzene rings bearing diphenylphosphino groups in compar-
ison to the other mononuclear complexes. These seem to be
caused by the steric and electrostatic repulsion between the
chlorine atom embedded in the calix cavity and the
methoxybenzene units.
Application to Catalytic Reactions. Suzuki−Miyaura
coupling is one of the most useful cross-coupling reactions
for the construction of unsymmetrical biaryls from aryl halides
and arylboronic acids.16 To date, a number of phosphine
ligands with calixarene skeletons have been applied to coupling
D
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The reaction of 1,2-epoxyoctane with thiophenol was then
investigated using 0.25 mol % of complex 11 as a catalyst in
various solvents (entries 1−6 in Table 3). Interestingly, the
Table 2. Suzuki−Miyaura Coupling Reaction of Aryl
Chlorides 13 with Phenylboronic Acid Catalyzed by
a
Palladium Complexes
Table 3. Ring-Opening Reaction of 1,2-Epoxyoctane with
a
Thiophenol
product, yield
b
entry
13
R
catalyst
(%)
b
entry
catalyst
solvent
yield (%)
1
2
3
4
5
13a
13a
13a
13a
13a
13a
13a
4-Ac
8
14a, 6
14a, 11
14a, 56
14a, 85
14a, 9
14a, 25
n.d.
4-Ac
4-Ac
4-Ac
4-Ac
4-Ac
4-Ac
9
1
2
3
4
5
6
11
11
11
11
11
11
11
CH2Cl2
CHCl3
THF
7
10
11
12
11
6
4
toluene
hexane
DMF
DMF
DMF
DMF
DMF
DMF
DMF
6
c
e
6
5
7
8
9
[Pd(PPh3)2(PhCN)2]
(BF4)2
60
80
n.d.
n.d.
n.d.
n.d.
n.d.
c
7
13a
13a
4-Ac
4-Ac
[Pd(binap)(MeCN)2]
(BF4)2
n.d.
n.d.
8
[Pd(PPh3)2(PhCN)2](BF4)2
[Pd(binap)(MeCN)2](BF4)2
[Pd(dppp)(MeCN)2](BF4)2
[Pd(dppf)(PhCN)2](BF4)2
[Pd(MeCN)4](BF4)2/7
9
[Pd(dppp)(MeCN)2]
(BF4)2
10
11
12
10
11
13a
13a
13b
13c
13d
13e
13f
4-Ac
4-Ac
[Pd(dppf)(PhCN)2](BF4)2
n.d.
[Pd(MeCN)4](BF4)2/7
14a, 5
14b, 75
14c, 69
14d, 59
n.r.
d
a
12
4-CO2Et 11
Reagents and conditions: 1,2-epoxyoctane (0.40 mmol), thiophenol
(0.80 mmol), catalyst (0.25 mol %), solvent (1.0 mL), 40 °C, 12 h.
13
14
15
4-CF3
4-F
11
11
11
11
11
11
b
1H NMR yield determined using CH2Br2 as an internal standard.
c
Catalyst (0.5 mol %) was used.
4-NO2
4-Me
2-Ac
d
f
16
14f, 53
14g, 64
14h, 82
17
18
13g
13h
reaction proceeded with the low catalyst loading to give the
corresponding β-hydroxysulfide regioselectively. Among the
solvents tested, DMF was the most effective (entry 6). A good
yield (80%) was achieved when the catalyst loading was slightly
increased (0.5 mol %) (entry 7), indicating that complex 11 is a
potent Lewis acid. It should be noted that dicationic palladium
complexes bearing PPh3, BINAP, dppp, and dppf did not
promote the reaction (entries 8−11). In addition, the reaction
did not proceed when Pd(MeCN)4(BF4)2 and ligand 7 were
added instead of complex 11 (entry 12), indicating that the
desired complexation did not take place.
3-Ac
a
Reagents and conditions: aryl chloride 13 (0.20 mmol), phenyl-
boronic acid (0.40 mmol), catalyst (1.0 mol %), NaH (2.0 molar
b
equiv), dioxane (1.0 mL), 100 °C, 1 h. 1H NMR yield determined
c
using CH2Br2 as an internal standard. The reaction time was
prolonged to 48 h. The reaction was carried out at 130 °C. Catalyst
(0.01 mol %) was used. Catalyst (5 mol %) was used.
d
e
f
Aryl chlorides 13b−d bearing electron-withdrawing ester,
trifluoromethyl, and fluoro groups also gave the corresponding
biphenyls in good yields (entries 12−14). On the other hand,
no coupling product was obtained in the reaction of 1-chloro-4-
nitrobenzene (13e) (entry 15), probably due to the strong
coordination of the nitro group to the palladium center. The
reaction of aryl chloride 13f bearing an electron-donating
methyl group gave the corresponding biphenyl 14f in a
moderate yield (entry 16). However, this required a higher
catalyst loading (5 mol %) in addition to a higher temperature
(130 °C) in comparison to those used in the reaction of aryl
chlorides 13a−d bearing electron-withdrawing groups. Aryl
chlorides 13g,h bearing acetyl groups at the ortho and meta
positions, respectively, were also converted to the correspond-
ing biaryls in moderate to good yields (entries 17 and 18).
The ring-opening reaction of epoxides with thiophenols
affords β-hydroxysulfides, which are important synthetic
intermediates for natural products as well as pharmaceuticals.20
Among methods hitherto reported for this transformation,21
the Lewis acid catalyzed strategy is of particular interest, as it
can be carried out under mild reaction conditions.22 However,
the method has a drawback of requiring a high catalyst loading
(5−10 mol %). As mentioned above, complex 11 exhibited the
highest performance as a catalyst for the Suzuki−Miyaura
coupling of aryl chlorides. Since the complex is dicationic, it
was expected that it would also serve as a Lewis acid catalyst.
CONCLUSION
■
We prepared calix[4]arene-based diphosphine 7 via an
Ullmann-type phosphinoylation. The diphosphine formed
palladium(II) complexes 8−12, the structures of which were
determined by X-ray analysis. The dicationic complex 11
exhibited good catalytic activity for the Suzuki−Miyaura
coupling between aryl chlorides and phenylboronic acid. The
complex also served as an efficient Lewis acid catalyst for the
ring-opening reaction of an epoxide with thiophenol.
EXPERIMENTAL SECTION
■
General. Melting points were taken with a micro melting point
apparatus and are uncorrected. 1H and 13C NMR spectra were
measured with tetramethylsilane as an internal standard and CDCl3 as
a solvent unless otherwise noted. Silica gel (63−200 μm) was used for
column chromatography and TLC. Water- and air-sensitive reactions
were routinely carried out under nitrogen. DMF, dichloromethane,
and 1,2-dichloroethane were distilled from calcium hydride. Xylene
was distilled from sodium diphenyl ketyl. Triethylamine was distilled
after drying over calcium chloride and molecular sieves 4A.
Acetonitrile and benzonitrile were distilled after drying over K2CO3.
Preparation of Bis(phosphine oxide) 6. A suspension of
bis(triflate ester) 2 (50.0 mg, 54.8 μmol), CuI (1.00 mg, 5.25
μmol), diphenylphosphine oxide (26.6 mg, 132 μmol), and K3PO4
E
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Article
(46.5 mg, 219 μmol) in dry DMF (3.0 mL) was stirred at 80 °C for 24
h. After cooling, the mixture was dissolved by the addition of saturated
aqueous NH4Cl (20 mL) and chloroform (15 mL). After the two
layers were separated, the aqueous layer was extracted with
chloroform. The combined organic layer was washed successively
with 2 M HCl and then water, dried over MgSO4, and evaporated. The
residue was purified by thin-layer chromatography with hexane/ethyl
acetate (2/1) as a developer to give bis(phosphine oxide) 6 (13.3 mg,
24%) as a colorless powder: mp 365−367 °C dec; IR (KBr) 2962,
1486, 1438, 1211, 1148, 1112, 719, 697 cm−1; 1H NMR (500 MHz) δ
0.86 (s, 18H), 1.20 (s, 18H), 2.81 (d, 4H, J = 13.5 Hz), 4.12 (d, 4H, J
= 13.5 Hz), 6.74 (d, 4H, J = 3.7 Hz), 6.82 (s, 4H), 7.37−7.45 (m,
12H), 7.79 (br, 8H), 9.85 (s, 2H); 13C NMR (125 MHz) δ 30.5, 31.7,
33.6, 34.1, 37.2 (d, J = 5.0 Hz), 125.3, 126.0 (d, J = 11.0 Hz), 127.9,
128.3 (d, J = 12.0 Hz), 130.8 (d, J = 2.0 Hz), 132.0 (d, J = 9.5 Hz),
136.8, 137.6, 139.3, 144.1 (d, J = 10.8 Hz), 151.5, 152.6; 31P NMR
(162 MHz) δ 28.7; MS (FAB) m/z 1017 (M)+; HR-MS (ESI-FTICR)
calcd for C68H74O4P2Na (M + Na)+ 1039.4960, found 1039.4955.
According to this procedure, compound 6 was prepared on a large
scale. Starting from bis(triflate ester) 2 (4.00 g, 4.38 mmol), CuI (83.4
mg, 0.438 mmol), diphenylphosphine oxide (2.13 g, 10.5 mmol),
K3PO4 (3.72 g, 17.5 mmol), and dry DMF (200 mL), compound 6
(949 mg, 21%) was obtained after column chromatography with
chloroform/ethyl acetate (4/1) as an eluent, followed by crystallization
from chloroform/methanol.
Preparation of Mononuclear Cationic Complex 9. A mixture
of diphosphine 7 (40.0 mg, 39.5 μmol) and PdCl2(MeCN)2 (10.2 mg,
39.5 μmol) in dry acetonitrile (4.0 mL) was refluxed for 1 h. After the
mixture was cooled, the solvent was evaporated to leave a residue,
which was dissolved by the addition of dichloromethane. After the
insoluble part was filtered off, the filtrate was evaporated to leave a
residue, which was crystallized from dichloromethane/hexane to give
complex 9 (32.5 mg, 67%) as a yellow powder: mp 276−278 °C dec;
IR (KBr) 2957, 1480, 1437, 1197, 1000, 745, 701 cm−1; 1H NMR (400
MHz) δ −1.56 (s, 3H), 1.05 (s, 18H), 1.33 (s, 18H), 3.24 (d, 4H, J =
13.6 Hz), 3.47 (s, 6H), 3.87 (d, 4H, J = 13.6 Hz), 7.14 (s, 4H), 7.46
(br, 8H), 7.53 (t, 8H, J = 7.0 Hz), 7.65 (br, 4H), 9.45 (br, 4H); 13C
NMR (100 MHz) δ −3.8, 31.0, 31.2, 34.2, 34.7, 34.8, 62.6, 126.5,
128.1 (t, J = 3.1 Hz), 129.0, 129.8, 130.7, 130.8, 131.5, 133.81, 133.85
(t, J = 24.4 Hz), 134.8, 146.4, 147.3 (t, J = 4.3 Hz), 153.1, 155.1; 31P
NMR (162 MHz) δ 1.8; HR-MS (ESI-FTICR) calcd for
C72H81ClNO2P2Pd (M − Cl)+ 1194.4466, found 1194.4464.
Preparation of Mononuclear Cationic Complex 10. A mixture
of diphosphine 7 (20.0 mg, 19.7 μmol) and PdCl2(MeCN)2 (5.1 mg,
19.7 μmol) in dry acetonitrile (4.0 mL) was refluxed for 1 h. After the
mixture was cooled, AgBF4 (7.7 mg, 39.4 μmol) was added, and the
mixture was stirred at room temperature for 12 h. After the insoluble
part was filtered off, the filtrate was evaporated to leave a residue,
which was crystallized from dichloromethane/hexane to give complex
10 (32.5 mg, 67%) as a yellow powder: mp 153−155 °C dec; IR
1
(KBr) 2960, 1479, 1437, 1196, 1084, 1000, 701 cm−1; H NMR (400
Preparation of Diphosphine 7. To a solution of bis(phosphine
oxide) 6 (50.0 mg, 49.1 μmol) and trimethylamine (d 0.726; 68.5 μL,
491 μmol) in dry xylene (3.0 mL) was added trichlorosilane (d 1.34;
49.7 μL, 491 μmol) at 0 °C, and the mixture was refluxed for 4 h. After
cooling, the reaction was quenched with 1 M NaOH and the mixture
was extracted with chloroform. The extract was washed successively
with 2 M HCl and water, dried over MgSO4, and evaporated to leave a
residue, which was dissolved by the addition of dry DMF. To the
solution was added NaH (60% suspension in mineral oil; 7.9 mg, 196
μmol), and the mixture was stirred at room temperature for 1 h. To
the mixture was added iodomethane (d = 2.29; 12.2 μL, 196 μmol),
and the mixture was stirred at room temperature for 3 h. The reaction
was quenched with 2 M HCl and the mixture was extracted with
chloroform. The organic layer was washed with water, dried over
MgSO4, and evaporated. The residue was purified by column
chromatography with hexane/ethyl acetate (2/1) as an eluent to
give diphosphine 7 (36.7 mg, 74%) as a colorless powder: mp 296−
299 °C dec; IR (KBr) 2961, 1481, 1461, 1435, 1361, 1209, 1017, 867,
MHz) δ −1.55 (s, 3H), 1.05 (s, 18H), 1.31 (s, 18H), 3.22 (d, 4H, J =
13.8 Hz), 3.47 (s, 6H), 3.87 (d, 4H, J = 13.8 Hz), 7.14 (s, 4H), 7.37−
7.56 (m, 16H), 7.65 (br, 4H), 9.45 (br, 4H); 13C NMR (100 MHz) δ
−3.7, 31.0, 31.2, 34.2, 34.7, 34.8, 62.6, 126.5, 128.0 (t, J = 3.6 Hz),
129.0, 129.7, 130.68, 130.71, 131.54, 133.8, 133.9 (t, J = 24.1 Hz),
134.9, 146.5, 147.3 (t, J = 4.4 Hz), 153.3, 155.1; 31P NMR (162 MHz)
δ 2.1; HR-MS (ESI-FTICR) calcd for C72H81ClNO2P2Pd (M − BF4)+
1194.4466, found 1194.4464.
Preparation of Mononuclear Dicationic Complex 11. A
mixture of diphosphine 7 (20.0 mg, 19.7 μmol) and PdCl2(MeCN)2
(5.1 mg, 19.7 μmol) in dry acetonitrile (4.0 mL) was refluxed for 1 h.
After the mixture was cooled, the solvent was evaporated to leave a
residue, which was dried under vacuum for 30 min. To the dried
residue were added AgBF4 (15.3 mg, 78.8 μmol) and dichloromethane
(4.0 mL), and the mixture was stirred at room temperature for 1 h.
After the addition of acetonitrile (0.40 mL), the insoluble part was
filtered off. The filtrate was evaporated to leave a residue, which was
crystallized from dichloromethane/hexane to give complex 11 (20.1
mg, 74%) as a pale yellow powder: mp 179−181 °C dec; IR (KBr)
1
738, 701 cm−1; H NMR (400 MHz) δ 0.85 (s, 18H), 1.23 (s, 18H),
2959, 1479, 1436, 1197, 1084, 1038, 998, 704 cm−1; H NMR (400
2.67 (d, 4H, J = 13.6 Hz), 3.62 (d, 4H, J = 13.6 Hz), 4.06 (s, 6H), 6.47
(d, 4H, J = 2.6 Hz), 6.90 (s, 4H), 7.15−7.25 (m, 12H), 7.54−7.69 (m,
8H); 13C NMR (100 MHz) δ 30.9, 31.6, 33.7, 34.0, 38.6 (d, J = 8.2
Hz), 61.6 (t, J = 7.7 Hz), 124.0, 125.9, 128.1, 128.4 (d, J = 8.6 Hz),
133.0 (d, J = 22.9 Hz), 134.0 (d, J = 16.8 Hz), 135.4 (d, J = 1.8 Hz),
142.4 (d, J = 9.3 Hz), 144.2 (d, J = 14.1 Hz), 144.9, 147.5, 155.0; 31P
NMR (162 MHz) δ −1.5; HR-MS (ESI-FTICR) calcd for
C70H78O2P2Na (M + Na)+ 1035.5375, found 1035.5369.
1
MHz; CDCl3/DMSO-d6 (5/1)) δ −1.59 (s, 3H), 1.05 (s, 18H), 1.33
(s, 18H), 3.04 (s, 3H), 3.28 (d, 4H, J = 13.8 Hz), 3.52 (s, 6H), 3.78 (d,
4H, J = 13.8 Hz), 7.54 (s, 4H), 7.37−7.71 (m, 16H), 8.09 (br, 4H),
8.82 (br, 4H); 13C NMR (100 MHz; CDCl3/DMSO-d6 (5/1)) δ −4.2,
5.2, 30.8, 31.0, 34.16, 34.23, 34.8, 63.6, 126.9, 128.4 (t, J = 3.1 Hz),
130.2, 130.9, 131.9 (t, J = 26.2 Hz), 132.5, 133.4, 134.0, 146.8, 147.6
(t, J = 4.4 Hz), 154.5, 154.6; 31P NMR (162 MHz) δ 13.1; HR-MS
(ESI-FTICR) calcd for C74H84BF4N2O2P2Pd (M − BF4)+ 1287.5072,
found 1287.5067.
Preparation of Mononuclear Complex 12. A mixture of
diphosphine 7 (20.0 mg, 19.7 μmol) and PdCl2(MeCN)2 (5.1 mg,
19.7 μmol) in dry acetonitrile (4.0 mL) was refluxed for 1 h. After the
mixture was cooled, the solvent was evaporated to leave a residue,
which was dried under vacuum for 30 min. The dried residue was
dissolved by the addition of 1,2-dichloroethane (4.0 mL), and the
solution was refluxed for 2 h. After this solution was cooled, the
solvent was evaporated to leave a residue, which was crystallized from
dichloromethane/hexane to give complex 12 (5.7 mg, 18%) as a
yellow powder: mp 280−282 °C dec; IR (KBr) 2963, 1480, 1436,
1361, 1197, 1019, 860, 741, 698 cm−1; 1H NMR (400 MHz) δ 0.90 (s,
18H), 1.39 (s, 18H), 2.80 (d, 4H, J = 14.0 Hz), 3.30 (s, 6H), 3.62 (d,
4H, J = 14.0 Hz), 6.65 (s, 4H), 7.16 (s, 4H), 7.40 (t, 4H, J = 7.0 Hz),
7.42 (br, 12H), 9.71 (br, 4H); 13C NMR (100 MHz) δ 31.5, 31.5,
33.8, 34.3, 34.3, 61.1, 123.9, 126.3, 128.2, 129.9, 131.6, 133.7, 136.8,
Preparation of Dinuclear Complex 8. A mixture of diphosphine
7 (18.9 mg, 18.7 μmol) and PdCl2(MeCN)2 (10.6 mg, 40.9 μmol) in
dry benzonitrile (4.0 mL) was stirred at room temperature for 4.5 h
and then at 100 °C for 1 h. After the mixture was cooled, the solvent
was evaporated to leave a residue, which was crystallized from
dichloromethane/hexane to give complex 8 (15.0 mg, 64%) as a
yellow powder: mp 242−245 °C dec; IR (KBr) 2954, 1592, 1485,
1
1436, 1210, 1019, 743, 699 cm−1; H NMR (400 MHz) δ 1.34 (s,
18H), 1.76 (s, 18H), 2.68 (d, 4H, J = 16.0 Hz), 3.28 (s, 6H), 3.41 (d,
4H, J = 16.0 Hz), 7.12 (d, 4H, J = 3.6 Hz), 7.22 (s, 4H), 7.17−7.25
(m, 8H), 7.41−7.47 (m, 4H), 7.55−7.61 (m, 4H), 9.50 (dd, 4H, J =
14.8, 7.6 Hz); 13C NMR (100 MHz) δ 31.1, 32.2, 34.2, 35.2, 41.1,
57.0, 124.4 (d, J = 46.7 Hz), 127.8 (d, J = 15.1 Hz), 128.3, 128.6, 130.5
(d, J = 10.2 Hz), 130.9, 131.4, 131.6, 132.8 (d, J = 54.7 Hz), 140.3 (d, J
= 21.1 Hz), 146.7 (d, J = 6.6 Hz), 146.9, 151.4, 158.2; 31P NMR (162
MHz) δ 27.2; HR-MS (ESI-FTICR) calcd for C70H78Cl4NaO2P2Pd2
(M + Na)+ 1387.2199, found 1387.2197.
F
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Article
137.0, 143.6, 147.0, 149.1, 157.2; 31P NMR (162 MHz) δ 19.3; HR-
MS (ESI-FTICR) calcd for C70H78Cl2NaO2P2Pd (M + Na)+
1211.3787, found 1211.3781.
X-ray crystallographic data for 12 (CIF)
AUTHOR INFORMATION
Typical Procedure for Suzuki−Miyaura Coupling Reaction
(Entry 4 in Table 2). In a 5 mL vial reactor equipped with a septum
cap and a stirrer bar were charged phenylboronic acid (48.8 mg, 0.40
mmol) and NaH (60% suspension in mineral oil; 9.6 mg, 0.40 mmol),
and the vial was purged with nitrogen. To the mixture was added 1,4-
dioxane (1.0 mL) with a syringe, and the mixture was stirred at room
temperature for 10 min. To the mixture were added 4-
chloroacetophenone (13a; 28.1 mg, 0.20 mmol) and complex 11
(2.8 mg, 2.04 μmol) under a nitrogen stream, and the resulting
mixture was stirred at 100 °C for 1 h. After it was cooled, the mixture
was dissolved by the addition of water (1 mL) and ethyl acetate (2
mL), and the two layers were separated. The aqueous layer was
extracted with ethyl acetate and the combined organic layers were
evaporated to leave a residue, which was dried in vacuo and analyzed
by 1H NMR spectroscopy to determine the yield of biphenyl 14, using
CH2Br2 as an internal standard.
■
Corresponding Authors
*E-mail for S.T.: tanaka@orgsynth.che.tohoku.ac.jp.
*E-mail for T.H.: hattori@orgsynth.che.tohoku.ac.jp.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was supported in part by a Grant-in-Aid for Scientific
Research (C) (no. 15K05466) from the Japan Society for the
Promotion of Science (JSPS).
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ASSOCIATED CONTENT
* Supporting Information
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Sem
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The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.organo-
met.5b00999.
Supplemental figures and Table S1, characteristic data of
compounds synthesized by catalytic reactions, crystal
structures for complexes 8−12, and NMR spectral charts
for compounds and complexes synthesized (PDF)
X-ray crystallographic data for 8 (CIF)
X-ray crystallographic data for 9 (CIF)
X-ray crystallographic data for 10 (CIF)
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Bull. Chem. Soc. Jpn. 2009, 82, 1187−1193. (d) Marson, A.; Ernsting, J.
X-ray crystallographic data for 11 (CIF)
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H
DOI: 10.1021/acs.organomet.5b00999
Organometallics XXXX, XXX, XXX−XXX