Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone

Article abstract of DOI:10.1021/acscatal.6b01421

Herein, we report an example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for fluoroarylketone: tetrapyrazolyl dipalladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving transfer h

Full text of DOI:10.1021/acscatal.6b01421

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Article
Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting Facile Tandem
Transfer Hydrogenation/Suzuki Coupling Reaction of Fluoroarylketone
Niranjan Dehury, Niladri Maity, Suman Kumar Tripathy, Jean-Marie Basset, and Srikanta Patra
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b01421 • Publication Date (Web): 18 Jul 2016
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ACS Catalysis
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Dinuclear Tetrapyrazolyl Palladium Complexes Exhibiting
Facile Tandem Transfer Hydrogenation/Suzuki Coupling Re-
action of Fluoroarylketone
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Niranjan Dehury,† Niladri Maity,*,‡ Suman Kumar Tripathy,† Jean-Marie Basset*,‡ and Srikanta Patra*,†
†School of Basic Sciences, Indian Institute of Technology Bhubaneswar, Bhubaneswar, Orissa-751007, India.
‡King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900,
Saudi Arabia.
Supporting Information Place holder
ABSTRACT: Herein, we report an example of dinuclear pyrazolyl-based Pd complexes exhibiting facile tandem catalysis for
fluoroarylketone: Tetrapyrazolyl di-palladium complexes with varying Pd-Pd distances efficiently catalyze the tandem reaction involving
transfer hydrogenation of fluoroarylketone to the corresponding alcohol and Suzuki-Miyaura cross coupling reaction of the resulting
fluoroarylalcohol under moderate reaction conditions, to biaryl alcohol. The complex with the shortest Pd-Pd distance exhibits the highest
tandem activity among its di-metallic analogues, and exceeds in terms of activity and selectivity the analogous mononuclear compound.
The kinetics of the reaction indicates clearly that reductive transformation of haloarylketone into haloaryalcohol is the rate determining
step in the tandem reaction. Interestingly while fluoroarylketone undergoes the multistep tandem catalysis, the chloro- and bromo-
arylketones undergo only a single step C-C coupling reaction resulting in biarylketone as the final product. Unlike the pyrazole based Pd
compounds, the precursor PdCl2 and the phosphine based relevant complexes (PPh3)2PdCl2 and (PPh3)4Pd are found to be unable to exhibit
the tandem catalysis.
KEYWORDS: tetrapyrazolyl, dipalladium complex, fluoroarylketone, tandem catalysis, transfer hydrogenation, Suzuki coupling.
INTRODUCTION
ligand framework and the resulting synthesis of the corresponding
polynuclear metal complexes with varying metal-metal distances
is a difficult target.
With the strongest σ-bond among the carbon-hetero atoms,1 the
C-F bond activation of organofluoro compounds followed by
their transformation into new functionalized molecules has been a
great challenge in synthetic organic chemistry.2 In this context, a
significant effort has been put forward for the development of
new and efficient synthetic strategies. Among the various ap-
proaches, catalytic transformations of organofluoro compounds is
one of the most challenging subject. The well-known catalytic
transformations, such as hydrodefluorination,3 Suzuki-Miyaura,4
and Stille5 C-C cross-coupling, amination reaction,5 C–F bond
activations of multi fluorinated compounds,6 nucleophilic substi-
tution of electron deficient fluoroarenes7 and metallofluoroarene
complexes,8 cross-coupling reaction of perfluoro organic com-
pounds,9 etc. are already well documented in literature.
In parallel, there has been a gradual demand for alternate ligands
to replace the existing expensive, toxic and/or unstable phosphine
or carbene based systems.14 In this aspect, N,N donating polypy-
razolyl-based homoscorpionate ligands have been developed and
extensively employed for the preparation of precatalysts or cata-
lysts in studying numerous homogeneous catalytic processeses.15
In contrast, the use of multidentate bis-heteroscorpionate based
multimetallic system is relatively rare.16 Moreover, to the best of
our knowledge, the catalytic tandem transformation of orga-
nofluoro compounds utilizing such heteroscorpionate ligand-
based coordination compound is not known.
Tandem catalysis using heterometallic systems are much common
as the metal centers are compatible to conduct mechanistically
diverse reactions.17 Palladium based catalysts are well known for
their efficiency in a wide range of reactions, such as C-C cou-
pling,18 reduction of various organic functionalities,19 dehydro-
genation of alcohols, etc. Combining Pd with other metal centers
a varieties of heterometallic tandem catalysts have been devel-
oped.16-17 Therefore, although a considerable number of reports
comprising heterometallic systems are available,17a-k tandem ca-
talysis using homodimetallic system is rare.20 In particular, ho-
modinuclear Pd complexes catalyzing tandem reactions are not
known.
Nevertheless, one-pot multi-step tandem transformations of orga-
nofluoro compounds comprising C-F activation is rare.10 Such
type of catalysis, owing to their advantage in improving atom
economy, saving chemicals, reduction of waste, energy and time
has emerged as a fascinating tool in the synthesis of complex
organic frameworks.11 Thus, development of single, well-defined
multifunctional catalytic system capable of conducting tandem
reactions is highly demanding, however, challenging due to the
requirement of compatibility between mechanistically diverse
reaction steps.
Besides, combining multiple catalytic metals in close proximity
in order to improve local concentration of the active sites,12 and to
promote cooperativity and/or synergism between the two reaction
centers is also highly challenging.13 Therefore, design of new
In the current contribution we present such examples of new in-
expensive, air-stable bis-heteroscorpionate-di-palladium com-
plexes (Figure 1) and their efficient use towards tandem transfer
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Page 2 of 8
hydrogenation/Suzuki coupling reaction of fluoroarylketone. The
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influence of two metal centers with varying Pd-Pd distances on
the tandem reactivity has also been scrutinized. The advantage of
N-donor pyrazolyl-based complexes over their non-ligated pre-
cursor PdCl2, as well as the phosphine based analogous complex-
es [(PPh3)2PdCl2] and [(PPh3)4Pd] is investigated here. Addition-
ally, kinetics experiments has been carried out to shed light over
the sequence of such multi-step reactions involving both carbonyl
(C=O) reduction and C-F bond activation.
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Cl
PdII
N
N
N
N
Cl
Cl
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N
N
N
PdII
N
N
N
N
N
N
Cl
Cl
N
PdII
Cl
N
N
PdII
Cl
Cl
2
1
Cl
PdII
Cl
Cl
PdII
N
N
Cl
Cl
N
N
N
N
N
N
N
N
PdII
N
N
Cl
4
3
Figure 1. Dimetallic (1-3) and monometallic (4) Pd complexes with
polypyrazolyl framework.
RESULTS AND DISCUSSION
Synthesis and characterization of pyrazolyl Pd complexes 1-4.
The dinuclear tetrapyrazolyl Pd complexes 1-3 have been pre-
pared by reacting Li2[PdCl4] with suitable ligands in appropriate
ratio (2:1, respectively) in methanol followed by repeated washing
of the precipitate using cold methanol (Scheme S1, see in the
Supporting Information (SI)). These resulting neutral complexes
show satisfactory microanalytical data, and display the proton
(1H) and carbon (13C) resonances corresponding to the half of the
molecule (Figures S1 and S2, SI). The mononuclear 4 has been
prepared and characterized by following the reported procedure.21
The formations of complexes 1, 2 and 3 have been further authen-
ticated by their single crystal X-ray structure (Figure 2). Important
crystallographic and bond parameters are depicted in Tables S1
and S2 (SI). These complexes are crystallized out in monoclinic
(1, 2) and triclinic (3) geometry with p21/n, C2/c and p-1 space
group, respectively. The Pd centers in all the compounds display
distorted square planner geometry with pyrazole units, which
forms six membered metallacycle with boat conformation. The
Pd-N and Pd-Cl bond distances are in good agreement with the
structurally similar complexes.16,22 The observed N-Pd-N and Cl-
Pd-Cl bite angles and dihedral angles are also in the range ob-
served with structurally similar compounds.16,22 The intermetallic
Pd-Pd distances for 1, 2 and 3 are 6.479 Å, 6.870 Å and 8.871 Å,
respectively.
Figure 2. ORTEP diagram of complexes (a) 1, (b) 2 and (c) 3. Ellipsoids
are drawn at 20% probability level. Hydrogen atoms are eliminated for
clarity.
Employing alcohols as the source of hydrogen via transition met-
als catalyzing the dehydrogenation process are well known in the
literature.23 It appears from the screening results in Table 1 that
complex 1 exhibits the best catalytic efficiency for the transfer
hydrogenation of A for the combination of KOtBu and iPrOH
(entry 1). It is also observed that under such conditions reduction
occurs only to the carbonyl group to produce 1-(4-
fluorophenyl)ethanol (B) barring the hydrodehalogenation process
of either the reagent or the product.
Reaction conditions could thus be identified to achieve the trans-
fer hydrogenation before the tandem reaction (Pd/4-
fluoroacetophenone/KOtBu = 1/1000/2500 (molar ratio), catalyst
(0.1 mol% Pd), 4-fluoroacetophenone (0.5 mmol), KOtBu (1.25
mmol), iPrOH (1 mL), 80 °C).
Evaluation of transfer hydrogenation activities of pyrazolyl
Pd complexes. The present set of complexes 1-4 were evaluated
for their activity in tandem transfer hydrogenation and Suzuki-
Miyaura C-C cross coupling reaction for fluoroarylketone. Initial-
ly, the reduction of 4-fluoroacetophenone (A), comprising C-F
and C=O functionalities, was monitored in the presence of 1 (Ta-
ble 1, entries 1-6). The reaction conditions were screened for a
range of bases and solvents (as the source of hydrogen) at 80 °C.
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Table 1. Catalytic transfer hydrogenation of 4-fluoroacetophenonea
Table 2. Tandem transfer hydrogenation/Suzuki coupling of 4-
fluoroacetophenonea
1
2
3
4
5
6
7
8
Yield (%)b
B
Yield (%)b
Entry
Catalyst
ROH
Base
Entry
Catalyst
B
C
1
2
1
iPrOH
iPrOH
iPrOH
nPrOH
MeOH
PhCH2OH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
iPrOH
KOtBu
98
21
16
12
1
2
3
4
5
6
1
6
92
80
73
58
0
9
KOH
2
15
22
22
12
0
1
10
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12
13
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3
4
3
1
Na2CO3
KOtBu
4
1
PdCl2
5
1
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
KOtBu
0
0
(PPh3)2PdCl2
(PPh3)4Pd
0
6
1
7
0
0
7
2
95
92
67
13
0
a
Reaction conditions: Pd/4-fluoroacetophenone/PhB(OH)2/ KOtBu =
1/1000/1200/2500 (molar ratio), catalyst (0.1 mol% Pd), 4-
fluoroacetophenone (0.5 mmol), PhB(OH)2 (0.6 mmol), KOtBu (1.25
mmol), iPrOH (1 mL), 80 °C, reaction time = 20 h. b Isolated yields after
preparatory thin layered chromatography.
8
3
9
4
PdCl2
10
11
12
13
(PPh3)2PdCl2
(PPh3)4Pd
-
In order to get more insight into the pyrazolyl Pd complex medi-
ated tandem catalysis, time monitored reaction profile was stud-
ied for the reaction between 4-fluoroacetophenone (A) and phe-
nylboronic acid in the presence of KOtBu and iPrOH at 80 °C
(Figure 3). It is evident from the figure that in this multistep cata-
lytic process hydrogenation of the carbonyl group of the substrate
(line through the red points) precedes the reactions to produce 1-
(4-fluorophenyl)ethanol (B, line through the blue points). Next,
the C–C coupling occurs between B and phenylboronic acid to
yield the tandem product 1-(4-biphenylyl)ethanol (C, line through
the green points). In fact, the coupling reaction follows an induc-
tion period of 2h, which suggests that the hydrogenation of the
carbonyl group of 4-fluoroacetophenone is more facile than C-F
activation. Indeed, the coupling product 4-acetylbiphenyl could
not be detected, which would arise if direct C-C coupling be-
tween 4-fluoroacetophenone and phenylboronic acid would pro-
ceed. These results clearly suggest a consecutive nature of the
two reactions mechanistically independent, where the hydrogena-
tion of carbonyl group leads the tandem process in step I with
subsequent coupling occurring between the corresponding fluoro-
arylalcohol and phenylboronic acid in step II (Scheme S2, SI).
0
0
a Reaction conditions: Pd/4-fluoroacetophenone/Base = 1/1000/2500 (mo-
lar ratio), catalyst (0.1 mol% Pd), 4-fluoroacetophenone (0.5 mmol), base
(1.25 mmol), ROH (1 mL), 80 °C, reaction time = 8 h. b Isolated yields
after preparatory thin layered chromatography.
The other dinuclear Pd complexes (2, 3) as well as the analogous
mononuclear 4 also showed good catalytic efficiencies (entries 7-
9) under the identical conditions. Catalytic activities were also
monitored for the precursor PdCl2 (entry 10), and the phosphine
based palladium complexes (PPh3)2PdCl2 and (PPh3)4Pd (entries
11 and 12). Notably, the reaction did not proceed at all in the
presence of phosphine based complexes, or under blank condition
(entry 13). A much lower yield (13%) of B was obtained using
PdCl2 as compared to its pyrazolyl analogues 1-4 (98-67%).
Evaluation of tandem activities of pyrazolyl Pd complexes.
Next, we extended our study to examine whether 1-4 can initiate
tandem transfer hydrogenation/Suzuki-Miyaura cross coupling
reaction. Substrate 4-fluoroacetophenone (A, having C=O and C-
F functionalities) was reacted with phenylboronic acid in pres-
ence of the complexes under the conditions given in Table 2. A
high yield (92%) of the tandem product, 1-(4-biphenylyl)ethanol
(C), was obtained using the dinuclear Pd complex 1 (entry 1)
after a reaction period of 20 h. The analogous 2 (80%), 3 (73 %)
with higher internuclear Pd-Pd distances (6.870 and 8.871 Å,
respectively), or mononuclear 4 (58 %) showed lower activities
(entries 2-4) than 1 (Pd-Pd distance 6.479 Å, see Table S2 in the
SI). This is very likely due to the proximity among the dinuclear
centers in the set of complexes 1-3 and the assistance of proximal
metallic centers for a stepwise mechanism (vide infra).
Expectedly, the precursor PdCl2 resulted in a very low yield
(12%, entry 5) of transfer hydrogenation product (B), however
devoid of further C-C coupling to produce C. Reaction did not
proceed at all with the phosphine based complexes (entries 6 and
7). Therefore, neither PdCl2 nor (PPh3)2PdCl2 and (PPh3)4Pd were
able to conduct the desired tandem catalysis. It should be men-
tioned that none of the complexes listed in Table 2 was active to
catalyze direct C-C coupling between 4-fluoroacetophenone (A)
and phenylboronic acid to produce 4-acetylbiphenyl.
100
4-Fluoroacetophenone (A)
1-(4-Fluorophenyl)ethanol (B)
80
1-(4-biphenylyl)ethanol (C)
60
40
20
0
0
2
4
6
8 10 12 14 16 18 20
t (h)
Figure 3. Reaction kinetics for tandem transfer hydrogenation/Suzuki
coupling of 4-fluorocetophenones. Reaction conditions: 4-
fluoroacetophenone (A, 0.5 mmol), PhB(OH)2 (0.6 mmol), KOtBu (1.25
mmol), iPrOH (1 mL), 1 (0.1 mol% Pd) at 80 °C.
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To explore whether this tandem catalysis is effective on other
Finally, to check the homogeneous nature of the catalytic hydro-
1
2
3
4
5
6
7
8
haloderivatives, we followed the reactions of 4-chloro- and 4-
bromoacetophenone (A/ and A//, respectively) with phenylboronic
acid in the presence of 1 under identical conditions (Scheme 1).
Interestingly, for both the substrates 4-acetylbiphenyl (B/) was
obtained as the sole product in high yield (99 %, Table 3, entries
2 and 3). Reduction of keto group did not proceed at all to pro-
duce the desired tandem product C even after prolonging the
reaction time. It therefore appears that reductive transformation of
haloarylketone into haloaryalcohol is the first key step to proceed
the reaction to C. To prove this, a control reaction between (4-
halophenyl)ethanol (i.e. (4-chloro-) and (4-bromophenyl)ethanol)
and phenylboronic acid was examined in the presence of 1 (Table
S3, SI). Indeed, the reactions led to the formation of tandem
product C in high yield (≥ 92 %) for both reagents within 12 h.
Additionally, an attempt towards transfer hydrogenation of 4-
acetylbiphenyl (B/) on 1 resulted in no hydrogenation of the keto
group (Table S3, SI) even after a longer period of time (20 h).
Overall, these experimental results suggest that no tandem reac-
tion could be achieved for 4-haloacetophenones with weaker
electron withdrawing Cl and Br substituents than F, using the
present Pd based catalytic systems. The weaker C-halide (halide =
Cl and Br) bond in the substrates favors C-C cross coupling with
phenylboronic acid involving oxidative addition, σ-bond metathe-
sis with KOtBu, trans-metalation and reductive elimination
(Scheme S2, SI) to produce 4-acetylbiphenyl (Scheme 1). In con-
trast, with F once the alcohol is formed the oxidative addition of
the C-F on Pd is kinetically favored because the transfer hydro-
genation is slower than the C-C coupling.
genation or tandem reactions mercury drop test was conducted
(SI) for 1 (as representative complex).25 However, no significant
change in the yield of the final product (C) was observed (Table
S4) from that of the normal reaction. This suggests the homoge-
neous nature of the present catalytic systems.
Table 3. Scope of tandem transfer hydrogenation/Suzuki coupling for 4-
haloarylketonesa
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10
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12
13
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16
17
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Product
% Conversion
of ArX
/
Entry
ArX
Ar/B(OH)2
(B/B /C)
% Yieldb
1
2
3
100
100
100
6/0/92
0/99/0
0/99/0
4c
5c
6c
7
-
-
-
100
68
98/0/0
65/0/0
0/0/0
<1
100
50/0/47
8
9
100
100
100
52/0/43
35/0/61
41/0/52
10
Scheme 1. Reaction sequence of 4-chloro- and 4-bromoacetophenone
under identical reaction conditions for fluoro-analogue.
a
Reaction conditions: Pd/ArX/Ar/B(OH)2/KOtBu = 1/1000/1200/1500
(molar ratio), 1 (0.1 mol% Pd), ArX (0.5 mmol), Ar/B(OH)2 (0.6 mmol),
KOtBu (1.25 mmol), iPrOH (1 mL), 80 °C, reaction time = 20 h. b Isolated
c
To further support these hypotheses, we investigated the electron-
ic effect of the halo groups (-F, -Cl and -Br) on to the reduction of
carbonyl functionality in the substrates 4-haloacetophenones. The
transfer hydrogenation reaction was conducted in the absence of
phenylboronic acid (Table 3, entries 4-6). It is observed that the
fluoro-substituted substrate is the most active (98% yield) to pro-
duce the corresponding alcohol, followed by the chloro-
substituted substrate (65% yield). The bromo-substituted com-
pound remained unreactive. Indeed, a similar order of reactivity
was reported with higher transfer hydrogenation activity for 4-
fluoroacetophenone compared to its bromo-analogues.24 These
results suggest that fluoro substituent in 4-haloacetophenone in-
duces highest activity in reductive hydrogenation of its carbonyl
group into alcohol.
We, therefore, suggest that the productive tandem reaction for 4-
fluoroacetophenone, unlike its chloro- and bromo-analogues, is
due to the result of a facile reductive transformation of keto group
into alcohol, which undergo a subsequent C-C coupling reaction
with phenylboronic acid (see the reaction sequence under caption
of Table 2). On the other hand, with weaker C-halide bond, both
chloro- and bromo-substrates favor C-C coupling over reduction
of ketone, which result in 4-acetylbiphenyl as the end product
(Scheme 1).
yields after preparatory thin layered chromatography. Reaction time = 8
h.
CONCLUSIONS
In summary, the results of this work emphasize that we have de-
veloped tetrapyrazolyl based air-stable dinuclear Pd complexes 1-
3 with gradual increase in intermetallic distances. The structures
of 1, 2 and 3 have been authenticated by single crystal X-ray
diffraction. Superior catalytic activity (tandem transfer hydro-
genation/Suzuki coupling of 4-fluoroacetophenone as model sub-
strate) of 1 as compared to other dinuclear Pd complexes (2 and
3) is anticipated due to the shortest inter Pd-Pd distance. Activi-
ties of all the dinuclear complexes (1-3) are higher than those of
the mononuclear compound 4, suggesting that a well-defined
multinuclear catalytic system is more efficient compared to its
analogous mononuclear complex. While the pyrazolyl based
complexes exhibit tandem catalysis, the precursor complex PdCl2
(without any ligand) and the palladium phosphine complexes
(PPh3)2PdCl2 and (PPh3)4Pd were found to be inactive. These
results suggest the significance of pyrazole-based ligand frame-
works for achieving sustainable active catalytic system. Time
monitored reaction profile and controlled reactions inicate that
reductive transformation of haloarylketone into haloaryalcohol is
the rate determining step to proceed desired tandem reaction. The
productive tandem reaction of fluoroarylketone over chloro- and
bromo-analogues may open new avenues for the development of
desired one-pot multi-step reactions utilizing varieties of orga-
nofluoro compounds as starting reagents.
Furthermore, the tandem reaction has been extended for the com-
bination of 4-fluoroacetophenone and varieties of arylboronic
acids (Table 3, entries 7–10). Under the moderate reaction condi-
tions 1 is active towards all the reactants with good yields of the
tandem products.
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13. (a) Bratko, I.; Gómez, M. Dalton Trans. 2013, 42, 10664-10681; (b) van
ASSOCIATED CONTENT
den Beuken, E. K.; Feringa, B. L. Tetrahedron 1998, 54, 12985-13011;
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A. E.; MacMillan, D. W. Chem. Sci. 2012, 3, 633-658; (e) van der
Vlugt, J. I. Eur. J. Inorg. Chem. 2012, 363-375.
1
2
3
4
5
6
7
8
Supporting Information
Experimental procedures, characterization data of all new com-
plexes and catalysis products, crystallographic details of com-
plexes 1, 2 and 3. This material is available free of charge via the
Internet at http://pubs.acs.org.
14. Srinivas, P.; Srinivas, K.; Likhar, P. R.; Sridhar, B.; Mohan, K. V.;
Bhargava, S.; Kantam, M. L. J. Organomet. Chem. 2011, 696, 795-801.
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AUTHOR INFORMATION
Corresponding Authors
16. (a) Morin, T. J.; Wanniarachchi, S.; Gwengo, C.; Makura, V.; Tatlock,
H. M.; Lindeman, S. V.; Bennett, B.; Long, G. J.; Grandjean, F.;
Gardinier, J. R. Dalton Trans. 2011, 40, 8024-8034; (b) Dehury, N.;
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work has been supported by DST (EMR/2015/002219), New
Delhi, India. ND and SKT are grateful to the University Grant
Commission (UGC) and the Council of Scientific and Industrial
Research (CSIR), New Delhi, India, respectively, for their fellow-
ship. N. M. acknowledges the King Abdullah University of Sci-
ence and Technology (KAUST) for the postdoctoral fellowship.
The authors are grateful to the reviewers’ for their valuable com-
ments and suggestions to improve the manuscript.
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