Kryptofix 5 as an inexpensive and efficient ligand for the palladium-catalyzed Mizoroki-Heck reaction

Article abstract of DOI:10.1002/aoc.4224

A novel complex of PdCl₂ with a multidentate cryptand ligand, Kryptofix 5, has been prepared and characterized by various techniques including ¹H- and ¹³C NMR spectroscopy, Fourier transform infrared (FT-IR), Raman, ultraviolet and visible (UV-VIS) spectroscopy, inductively coupled plasma (ICP), CHN elemental and energy dispersive X-ray analysis (EDX). This heat- and air-stable complex was utilized as a highly active catalyst for the Mizoroki-Heck reaction of aryl halides with various olefins. Interestingly, it was found that aryl bromides as well as aryl iodides were efficiently cross-coupled with terminal alkenes at 130?°C in 10?min. Furthermore, the least reactive aryl chlorides reacted with styrene to obtain the desired products in acceptable yields.

Full text of DOI:10.1002/aoc.4224

Received: 18 October 2017
DOI: 10.1002/aoc.4224
Accepted: 14 November 2017
F U L L P A P E R
Kryptofix 5 as an inexpensive and efficient ligand for the
palladium‐catalyzed Mizoroki‐Heck reaction
Barahman Movassagh
| Shabnam Ranjbari
Department of Chemistry, K.N. Toosi
A novel complex of PdCl with a multidentate cryptand ligand, Kryptofix 5, has
University of Technology, P.O. Box 16315‐
618, Tehran, Iran
2
1
13
1
been prepared and characterized by various techniques including H‐ and
C
NMR spectroscopy, Fourier transform infrared (FT‐IR), Raman, ultraviolet
and visible (UV‐VIS) spectroscopy, inductively coupled plasma (ICP), CHN ele-
mental and energy dispersive X‐ray analysis (EDX). This heat‐ and air‐stable
complex was utilized as a highly active catalyst for the Mizoroki‐Heck reaction
of aryl halides with various olefins. Interestingly, it was found that aryl bro-
mides as well as aryl iodides were efficiently cross‐coupled with terminal
alkenes at 130 °C in 10 min. Furthermore, the least reactive aryl chlorides
reacted with styrene to obtain the desired products in acceptable yields.
Correspondence
Barahman Movassagh, Department of
Chemistry, K.N. Toosi University of
Technology, P.O. Box 16315‐1618, Tehran,
Iran
Email: bmovass1178@yahoo.com
KEYWORDS
2
aryl halides, cross‐coupling, Heck reaction, Kryptofix 5, PdCl –K 5 complex
1
| INTRODUCTION
turnover numbers (TON's) with less reactive aryl bromides
and chlorides. The catalytic system for an efficient Heck
reaction consists of a palladium source, ligand, base and
solvent. Usually, suitable ligand is required to stabilize pal-
ladium catalyst precursor. Many catalytic systems have
been developed for this reaction using different palladium
Transition metal‐catalyzed cross‐coupling reaction to cre-
ate a new carbon‐carbon (Csp2–Csp2) bond have played a
crucial role in contemporary organic synthesis. The pal-
ladium‐catalyzed coupling of aryl halides and terminal
alkenes, the Mizoroki‐Heck reaction, is a versatile and
powerful tool for the preparation of various substituted ole-
[1]
[
8]
catalysts together with phosphane and phosphorous
[
9]
ligands, as they play an important role in stabilization
and in situ generation of Pd(0) species from Pd(II) com-
plexes. However, due to the high cost, toxicity and thermal
[
2,3]
fins, dienes, and precursors of conjugated polymers.
The Mizoroki‐Heck reaction has received considerable
attention due to its functional group tolerance and its wide-
instability of phosphine ligands, various phosphane‐free
[
4]
[10]
spread application in the synthesis of agrochemicals,
catalytic systems
have been developed as less compli-
[5]
pharmaceuticals, and in enantioselective synthesis of
cated and environmentally more desirable alternatives to
the original Pd‐phosphane catalysts. Therefore, the design
of new ligands and their palladium complexes that can cat-
alyze the Mizoroki‐Heck reaction of less reactive aryl bro-
mides and chlorides with high efficiency is in high demand.
[6]
natural products.
Unlike other carbon‐carbon bond
forming reactions that involve a polar addition, the
Mizoroki‐Heck reaction can be performed in the presence
of sensitive functional groups such as aldehyde, ketone,
hydroxyl, amino, cyano, ester, carboxy, or nitro groups,
thus avoiding the need for protection and deprotection of
[7]
functional groups during organic transformation. There-
fore, to find industrial application, several goals have to be
met, such as the use of stable and inexpensive ligands, the
use of cheap starting materials, and achievement of high
2 | RESULTS AND DISCUSSION
Palladium catalysts are known to aggregate easily and
form palladium black, which may lead to a considerable
Appl Organometal Chem. 2018;e4224.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
1 of 6
https://doi.org/10.1002/aoc.4224

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MOVASSAGH AND RANJBARI
[11]
loss of catalytic activity.
To overcome this intrinsic
problem of homogeneous Pd catalysis, we explored a new
class of palladium catalyst system based on cryptands. In
cross‐coupling reactions, amines are generally used as
bases, but they can also serve to stabilize the reactive
[12]
palladium intermediates.
Because of their stronger
σ‐donation, which favors both the oxidative addition step
and the slow reductive elimination step in the catalytic
cycle, ligands of the N,N‐type show superior properties to
P,P‐type ligands in terms of both palladium complexation
[13]
and catalysis of cross‐coupling reactions. Many N‐based
ligands are stable and have been reported to be efficient
ligands for the Pd‐catalyzed Heck and Suzuki coupling
2
FIGURE 2 The EDX spectrum of PdCl –K 5 complex
[14]
reactions.
Among these, the N– and O–donor
cryptands represent an important family of multidentate
the stretching bands of the nitrogen‐palladium and palla-
dium‐chlorine bonds, respectively (Figure 3).
ligands which forms a three‐dimentional cavity for metal
[15]
cations.
A rather intriguing ligand of this type is
The UV‐visible spectra of Kryptofix 5 and its Pd(II)
complex were carried out in CH Cl at room temperature
Kryptofix 5. As part of our ongoing investigation to find a
2
2
robust and easily prepared system to catalyze C–C bond
(Figure 4); The spectrum of ligand, Kryptofix 5, displayed
a strong absorption band (π→π ) at 239 and a weak
[10d, e, 16]
*
forming reactions,
system based on a commercially available Kryptofix 5
1,13‐bis(8‐quinolyl)‐1,4,7,10,13‐pentaoxatridecane, here
we found that a Pd(II) catalyst
absorption at 304 nm. The absorption spectrum of the
complex, Pd(II)‐K 5, showed its first band at 244 nm and
the weak band in the range 310‐320 nm which might be
due to metal to ligand charge transfer (MLCT) bands from
[
abbreviated with K 5] is a very active homogeneous
catalyst under aerobic condition. This ligand consist of a
crown ether moiety and two quinoline substituent. The
*
the d‐orbitals of the palladium metal to the π of the aryl
2+
[17]
metal cation (Pd ) can be coordinated to the crown ether
unit as well as to the quinoline chromophores (Figure 1).
This catalyst was prepared in our laboratory for the first
time by an easy method.
group.
The Pd(II)‐Kryptofix 5 complex has been fully
characterized by elemental analysis, NMR, FT‐IR,
Raman, UV‐VIS, inductively coupled plasma (ICP), and
energy dispersive X‐ray analysis (EDX) techniques. The
loading value of Pd(II) in the catalyst, as determined by
‐1
ICP analysis, was found to be 16.61% (1.56 mmol.g ) which
is in good agreement with the calculated value (17.00%).
The elemental composition of the complex was confirmed
using EDX and elemental analyses (Figure 2); it revealed
the presence of C, N, O, Cl, and Pd elements. Also, the ratio
of N/Pd in the catalyst was found to be 2.03.
2
FIGURE 3 Raman spectrum of PdCl –K 5 complex
The IR spectrum of the K 5 ligand shows a strong
‐
1
C‐O‐C stretching frequency at 1101 cm ; this band
appears at 1112 cm‐ for the PdCl –K 5 complex. Also,
1
2
Raman spectroscopy of the complex showed two promi-
nent bands at 478 and 361 cm‐ which are attributed to
1
N
N
O
O
Cl Pd Cl
O
.H O
2
O
O
FIGURE 4 Absorption spectra of Kryptofix 5 and its Pd(II)
FIGURE 1 PdCl
2
–K 5 catalyst
complex

MOVASSAGH AND RANJBARI
3 of 6
To evaluate the usefulness of this multidentate, phos-
phine‐free Pd(II) complex in C–C bond forming reaction,
we investigated its application to the Heck reaction of aryl
halides. To optimize the reaction conditions with respect
to base, solvent, temperature, and the catalyst loading,
the coupling reaction between iodobenzene (1 equiv) with
styrene (1.1 equiv), and a base (1.1 equiv) was performed
as a model reaction under aerobic condition (Table 1).
Specifically, five bases and five solvents were surveyed
where they were compatible.
different amounts, 0.9 mol% of the catalyst is found to
be the best (Table 1, entry 5). Therefore, it was decided
to use Et N as the base and DMF as solvent at 130 °C in
3
the presence of 0.9 mol% of the catalyst as the optimal
condition in further studies. To find out if the in situ for-
mation of PdCl /K 5 in the reaction vessel would drive
2
the reaction, the process was also conducted under the
same reaction conditions, by adding a mixture of
iodobenzene and styrene in DMF, to a test tube contain-
ing PdCl (0.9 mol%), Kryptofix 5 (0.9 mol%), and Et N;
2
3
Various organic and inorganic bases such as, Et N,
stirring the reaction mixture for 1.5 h produced the corre-
sponding product in 68% yield.
3
diisopropylethylamine (DIPEA), K CO , Na CO and
2
3
2
3,
t
KO Bu were screened. The yield of the Heck product
was reduced when inorganic bases were used (Table 1,
entries 1‐4). A considerable increase in product formation
is observed in the presence of triethylamine, in DMF at a
high temperature, 130 °C (Table 1, entry 5). Several other
solvents, including dimethylsulfoxide (DMSO), N‐
To examine the general scope of this coupling reac-
tion, the catalyst was then applied to other cross‐coupling
reactions of aryl halides carrying either electron‐with-
drawing or electron‐donating substituents in aromatic
rings with various vinylic substrates (styrenes, acrylates,
acrylonitrile, and acrylamide) (Table 2). Only trans prod-
ucts were obtained selectively in all the cases. The results
methylpyrrolidin‐2‐one
(NMP),
dimethylacetamide
(DMAc), and toluene were also surveyed under similar
clearly show that the PdCl ‐K 5 catalytic system is highly
2
conditions, but compared with DMF all gave inferior
results (Table 1, entries 6‐9). Also, reducing the tempera-
ture to 120 °C and 110 °C resulted in the formation of
the target product in 76% and 51% yields, respectively
active and tolerates a wide range of functional groups. As
expected, the reaction of aryl iodides with terminal olefins
all proceeded smoothly within 10 min to give the desired
products in 71‐95% isolated yields (Table 2, entries 1‐14).
However, the reaction of sterically hindered 2‐
iodotoluene with styrene and methyl acrylate gave lower
yields (Table 2, entries 8 and 9). Electron‐donating
(Table 1, entries 10 and 11). Then, various amounts of cat-
alyst between 0.6 and 0.9 mol% were investigated for the
reaction (Table 1, entries 5 and 12‐14). Among the
a
TABLE 1 Screening of the reaction conditions
b
Entry
Base
CO
Solvent
Temp (°C)
Catalyst (mol%)
Yield (%)
1
K
2
3
DMF
130
0.9
56
2
3
4
5
6
7
8
9
Na
2
CO
3
DMF
DMF
DMF
DMF
DMSO
NMP
DMAc
130
130
130
130
130
130
130
130
120
110
130
130
130
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.9
0.8
0.7
0.6
42
33
63
95
77
64
53
48
76
51
83
74
65
t
KO Bu
DIPEA
Et
3
Et
3
Et
3
Et
3
Et
3
Et
3
Et
3
Et
3
Et
3
Et
3
N
N
N
N
N
N
N
N
N
N
PhCH
DMF
DMF
DMF
DMF
DMF
3
10
11
12
13
14
a
Reaction conditions: iodobenzene (1 mmol), styrene (1.1 mmol), base (1.1 mmol), solvent (1 ml), 10 min, under air.
b
Isolated yields.

4
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MOVASSAGH AND RANJBARI
a
TABLE 2 Palladium(II) chloride‐Kryptofix 5‐catalyzed Mizoroki‐Heck reaction of aryl halides with olefins
b
Entry
Aryl halide
R
Product
Time
Yield (%)
1
PhI
Ph
3a
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
10 min
24 h
95
81
91
86
91
90
87
76
71
82
86
94
81
91
16
70
74
74
90
87
91
88
8
2
3
4
5
6
7
8
9
PhI
PhI
PhI
PhI
4‐MeOC
6
H
4
3b
3c
3d
3e
3f
CN
CONH
2
CO
Ph
CO
Ph
CO
CO
Ph
CO
Ph
CO
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
CO
Ph
2
Me
4‐MeC
4‐MeC
2‐MeC
6
6
6
H
H
H
4
4
4
I
I
I
2
Me
3g
3h
3i
2‐MeOC
2‐MeC
1‐iodonaphthalene
4‐MeCOC
4‐BrC
6
H
4
I
2
2
Me
Me
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
6
H
4
I
3j
3k
3l
6
H
4
I
2
2
Me
Bu
6
H
4
I
3m
3n
3a
2‐iodothiophene
PhBr
c
PhBr
3a
10 min
10 min
10 min
10 min
10 min
10 min
10 min
36 h
d
PhBr
3a
c
4‐MeOC
6
H
4
Br
Br
CHO
3b
c
4‐MeCOC
6
H
4
3o
c
4‐BrC
4‐BrC
4‐BrC
PhCl
PhCl
PhCl
6
6
6
H
H
H
4
4
4
3p
c
NO
2
3q
c
CN
3r
3a
c
3a
6 h
45
49
54
51
58
c
3a
24 h
c
4‐MeCOC
6
H
4
Cl
3o
4 h
c
4‐ClC
4‐ClC
6
6
H
H
4
4
CHO
CN
2
Me
3s
1 h
c
3r
2 h
a
3
Reaction conditions: aryl halide (1 mmol), olefin (1.1 mmol), Et N (1.1 mmol), catalyst (0.9 mol%), in DMF (1 ml) at 130 °C.
b
Isolated yields.
c
TBAB (1 mmol) and catalyst (0.9 mol%) were used.
d
TBAB (1 mmol) and catalyst (1.5 mol%) were used.
substituent (4‐methoxy) on styrene gave lower yield when
compared to that of styrene (Table 2, entries 1 and 2). It
was also observed that for a particular olefin, activated
electron‐deficient aryl iodide (4‐iodo acetophenone) could
effectively couple with the olefin (methyl acrylate) provid-
ing the corresponding product in excellent yield after
substrates (4‐iodotoluene and 4‐iodoanisol) gave lower
yields when coupling with methyl acrylate (91, 87, and
82%, respectively) (Table 2, entries 5, 7, and 10).
Chemoselectivity of the procedure was also studied
using 4‐bromo‐1‐iodobenzene (Table 2, entry 13). In this
reaction, iodine acted as a better leaving group. Under
the same reaction conditions, coupling of bromobenzene
and chlorobenzene with styrene gave very poor yields
1
0 min (Table 2, entry 12). The non‐activated electron‐
neutral iodobenzene and deactivated electron‐rich

MOVASSAGH AND RANJBARI
5 of 6
nd
(
16% and 8%, respectively) after 24 h and 36 h (Table 2,
Dispersive Raman Spectrometer with 2
@532 nm of a Nd:YLF laser.
harmonic
entries 15 and 23). Changing the amount of the catalyst
from 0.9 mol% to 1.5 mol% in the case of bromobenzene,
or increasing reaction time to 24 h in the case of
chlorobenzene had little effect on the product yields
4
.1 | Preparation of PdCl ‐K 5 complex
2
(Table 2, entries 17 and 25); therefore, tetra‐n‐
A RB‐flask was charged with Kryptofix 5 (0.137 g,
butylammonium bromide (TBAB, 1 equiv) was used
as an additive for the cross‐coupling of aryl bromides
or chlorides with olefins. Several aryl bromides,
possessing electron‐rich (deactivated) or electron‐
deficient (activated) substituents, worked well with
styrene to give the corresponding stilbenes. The reactivity
of aryl bromides with electron‐deficient substituent was
higher than that of aryl bromides with electron‐rich
substituent (Table 2, entries 18‐22). Compared with the
corresponding bromo analogues, the reaction of the
chloro derivatives gave lower yields and required longer
times (Table 2, entries 23‐28).
0.31 mmol), PdCl (0.054 g, 0.31 mmol), and CH CN
2
3
(10 ml). The mixture was refluxed for 2 h, during which
time the color of the mixture was turned from colorless
to brown, and all the materials dissolved thoroughly.
Then, the solvent was removed under reduced pressure,
and to the resulting residue was added dichloromethane
(25 ml), and filtered; diethyl ether (25 ml) was added to
the filterate, and a light yellow precipitate formed. The
precipitate was washed with Et O and air‐dried to give
2
the PdCl ‐K 5 complex (140 mg, 73 %). Mp 138‐140 °C.
2
1
H NMR (300 MHz, CDCl ): δ 9.96‐10.09 (m, 2H), 8.00‐
3
1
3
8.19 (m, 2H), 7.01‐7.61 (m, 8H), 3.52‐5.64 (m, 16H);
C
NMR (75 MHz, CDCl ): δ 155.0, 151.9, 139.1, 138.3,
3
131.0, 127.9, 121.7, 121.2, 112.9, 70.6, 70.3, 69.9. Anal.
3
| CONCLUSION
Calcd. for C H N O Pd.H O: C, 48.50; H, 4.69; N, 4.35.
Found: C, 48.82; H, 4.61; N, 4.44.
26
28
2
5
2
In conclusion, Pd(II) complex bearing Kryptofix 5
ligand has been synthesized with a simple method and
characterized by various methods. Furthermore, the
4
.2 | General procedure for the Mizoroki‐
Heck coupling reaction
PdCl –K 5 complex was found to be highly efficient
2
homogeneous catalyst for the Mizoroki‐Heck reactions
of aryl halides with various terminal olefins. This new
catalyst has the advantages of being thermally stable,
readily prepared, inexpensive, easily handled, and
operating under air. In addition, Kryptofix 5 might act
as a ligand to stabilizing the Pd(0) species in the
Mizoroki‐Heck reaction.
A test tube was charged with aryl halide (1.0 mmol),
olefin (1.1 mmol), PdCl ‐K 5 (5.6 mg, 0.9 mol%), Et N
2
3
(1.1 mmol), DMF (1 ml). [For aryl bromides or chlorides,
TBAB (1.0 mmol) was also added]. The mixture was then
stirred at 130 °C under air for appropriate time. The prog-
ress of the reaction was monitored using TLC. Upon com-
pletion of the reaction, the mixture was cooled to room
temperature, poured into H O (12 ml), and extracted with
2
CH Cl (3×8 ml). The combined organic extracts were
2
2
4
| EXPERIMENTAL
dried (Na SO ) and concentrated in vacuo to give the
2 4
crude product, which was further purified by prep. TLC
[silica gel; n‐hexane or n‐hexane‐EtOAc (9:1)] to afford
the desired pure product. The products were character-
ized using FT‐IR, 1H‐ and 13C NMR spectroscopies (see
supporting information).
All chemicals were purchased from Merck, Sigma and
Acros chemical companies. Melting points were deter-
mined on a Büchi melting point B‐540 apparatus. FT‐IR
spectra were recorded on an ABB Bomem model FTLA
2
000 spectrophotometer. Nuclear magnetic resonance
1
13
(NMR) spectra were recorded at 300 ( H) and 75.4 ( C)
ACKNOWLEDGMENTS
MHz, on a commercial Bruker AQS‐300 instrument using
CDCl as solvent. The ICP analyses were carried out on a
Financial support from K.N. Toosi University of Technol-
ogy Research Council is gratefully acknowledged. The
authors also wish to express their gratitude to Dr. Elmira
Mohammadi for her assistance throughout this work.
3
Varian vista‐MPX instrument. Elemental analyses for C,
H and N were performed using a Perkin Elmer 2400 series
Rapid analyzer. The EDX for the elements’ valuation
was performed using Vega, TESCAN‐Model instrument.
UV‐VIS spectra of the ligand and complex were carried
ORCID
‐
5
out (10 M in DCM) using a 4802 UNICO UV/VIS double
beam spectrophotometer. Raman spectrum of the com-
plex was recorded on a Thermo Nicolet Almega
Barahman Movassagh
http://orcid.org/0000-0001-8489-
9962

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MOVASSAGH AND RANJBARI
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