1-(α-Aminobenzyl)-2-naphthol as phosphine-free ligand for Pd-catalyzed Suzuki and one-pot Wittig-Suzuki reaction

Article abstract of DOI:10.1002/aoc.2877

Air stable and easily accessible, 1-(α-aminobenzyl)-2-naphthols are used as efficient phosphine-free ligands in palladium-catalyzed Suzuki reaction for a variety of substrates under conventional heating as well as ultrasonic conditions. Multi-brominated aromatic substrates were successfully converted to corresponding arylated moieties with good conversion and selectivity. A novel one-pot two-step cascade reaction strategy involving Wittig and Suzuki reactions is developed for efficient synthesis of 4-styryl biphenyls (C ₆-C₂-C₆-C₆ unit). Copyright 2012 John Wiley & Sons, Ltd. Phosphine free 1-(α-aminobenzyl)-2- naphthol ligands are used for Pd catalyzed Suzuki and one-pot Wittig-Suzuki reaction to efficiently prepare styryl biphenyls (C₆-C ₂-C₆-C₆ unit). Copyright

Full text of DOI:10.1002/aoc.2877

Full Paper
Received: 21 January 2012
Revised: 3 April 2012
Accepted: 3 April 2012
Published online in Wiley Online Library
(wileyonlinelibrary.com) DOI 10.1002/aoc.2877
1-(a-Aminobenzyl)-2-naphthol as phosphine-
free ligand for Pd-catalyzed Suzuki and
one-pot Wittig-Suzuki reaction
A. R. Chaudhary and A. V. Bedekar*
Air stable and easily accessible, 1-(a-aminobenzyl)-2-naphthols are used as efficient phosphine-free ligands in palladium-
catalyzed Suzuki reaction for a variety of substrates under conventional heating as well as ultrasonic conditions. Multi-
brominated aromatic substrates were successfully converted to corresponding arylated moieties with good conversion and
selectivity. A novel one-pot two-step cascade reaction strategy involving Wittig and Suzuki reactions is developed for efficient
synthesis of 4-styryl biphenyls (C6-C2-C6-C6 unit). Copyright © 2012 John Wiley & Sons, Ltd.
Keywords: 1-(a-aminobenzyl)-2-naphthols; phosphine-free Suzuki reaction; homogeneous palladium catalysis; one-pot Wittig–Suzuki
reaction
Suzuki coupling for the production of biaryls has been
Introduction
applied under microwave[23] or ultrasonic irradiation.[24] Both
Palladium-catalyzed cross-coupling reactions,[1a,b] via Suzuki,[1c-j]
conditions, in general, lead to reduction of reaction time and
Heck,[1k] Stille,[1l,m] Negishi[1n,1o] and Sonogashira[1p,q] protocols are
can offer some advantages.
powerful methods for C-C bond formation. The palladium-catalyzed
Heck and Suzuki reactions have been used extensively for the syn-
thesis of natural products, pharmaceutical intermediates, conduct-
ing polymers, pesticides and liquid crystals.[2–5] The significance of
palladium catalysis and cross-coupling reactions has been acknowl-
edged by the award of a Nobel Prize for Chemistry in 2010 to scien-
tists who carried out pioneering work in this area.
Recently an application of 1-(a-aminobenzyl)-2-naphthols as air-
stable phosphine-free ligands for the palladium-catalyzed
Mizoroki–Heck coupling reaction has been reported.[25] The results
obtained prompted us to extend our studies towards the
palladium-catalyzed Suzuki coupling reactions. To the best of our
knowledge, applications of 1-(a-aminobenzyl)-2-naphthols–Pd
catalyst for Suzuki coupling reaction have not been developed.
The Suzuki reaction is proving to be an increasingly popular
tool for the construction of unsymmetrical biaryls. It represents
an attractive alternative to other methods using organometallic
reagents as organoboranes are air and moisture stable and
with relatively low toxicity.[1d,g,3a] These reactions, normally per-
formed with 1–5 mol% of Pd catalyst along with equal or
higher molar amounts of phosphine ligands, still suffer from
two significant problems.[6a] Firstly, palladium is expensive
and its contamination has to be particularly regulated in the
case of consumption for biological systems. Secondly, many
phosphine ligands are not readily available, and are not simple
to work with owing to their poisonous character, air sensitivity
and ease of degradation. However, most of these catalysts con-
taining phosphines are generally sensitive to moisture and air,
and require air-free conditions to minimize oxidation. More-
over, their large-scale application is limited in industry owing
Result and Discussion
A series of 1-(a-aminobenzyl)-2-naphthols 1 were prepared from
2-naphthols by aromatic Mannich reaction[25,26] and screened as
a ligand for Suzuki reaction. The product 1 (Scheme 1), a derivative
of Betti base,[27] and some analogous molecules have been investi-
gated from different aspects of stereoselective transformations.[28]
The amino phenol of type 1 has a suitable arrangement of
heteroatoms to form a six-membered stable chelate, a prerequisite
for application as a ligand in metal-catalyzed reactions. Some
examples of the applications of 1 as a ligand in catalytic reactions
are available in the literature.[25,29–34] One of the basic types of
reactivity in palladium-driven catalytic cycles is due to the ability
of Pd(0) species to undergo oxidative addition to various C-X bonds.
The ligand 1 stabilizes the Pd catalysts via formation of Pd(0) species
and thus accelerates coupling in the reaction.
to their high cost and toxic nature[6b]
.
These reasons offer an option to develop Pd catalysts that can
utilize inexpensive phosphine-free ligands. In this endeavor, a
number of nitrogen donor ligands such as imine,[7a] oxime,[7b–d]
diazabutadiene derivatives,[7e] bis(pyrimidine),[8] N-heterocyclic carbenes
(NHC),[9] oxazolines,[10] amines,[11] Schiff bases,[12] pyridines,[13] hydra-
zones,[14] guanidines,[15] pyrazoles,[16] tetrazoles,[17] quinolines,[18]
carbazones,[19] imidazoles,[20] thioureas,[21] and 1,3-dicarbonyl com-
pounds[22] have been examined for palladium-catalyzed reactions.
*
Correspondence to: Ashutosh V. Bedekar, Department of Chemistry, Faculty
of Science, M. S. University of Baroda, Vadodara 390 002, Gujarat, India.
E-mail: avbedekar@yahoo.co.in
Department of Chemistry, Faculty of Science, M. S. University of Baroda,
Vadodara 390 002, Gujarat, India
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.

A. R. Chaudhary and A. V. Bedekar
R
NR'2
OH
Pd(OAc)2 - 1
Ar Ar'
Ar
X
+ Ar' B(OH)2
see Table-1
for conditions
2
3
4
1
Scheme 2. Typical Suzuki–Miyaura reaction
Scheme 1. General structure of the ligand for the present study
cascade reaction reduces the consumption of reagents, number
of purifications and shortens reaction time, contributing to better
economy of the chemical process. Many combinations of different
bond-making processes are combined for cascade reactions
with reasonable success.[35] One-pot synthesis of stilbenes by
dehydrohalogenation–Heck olefination and multi-component
Wittig–Heck reaction was recently accomplished by the present
authors.[10d] Cascade reactions involving Suzuki reaction as one of
A small group of these ligands 1a–d were prepared with
corresponding 2o amine, benzaldehyde and 2-naphthol for this
study (Fig. 1).
The ligands were screened to determine standard reaction
conditions for the Suzuki–Miyaura reaction with aryl halides and
aryl boronic acids in the presence of a suitable base (Scheme 2).
The results are presented in Table 1.
the steps have been reported in the literature, although almost
36–50]
all involve phosphine-based catalyst systems.[2e,
A few
The results of the study of Suzuki–Miyaura coupling indicate very
efficient conversion with aryl iodides and aryl bromides with a
small quantity of tetra-n-butylammonium bromide (TBAB) when
aqueous dioxane was used as solvent. Chlorobenzene was consid-
erably less reactive after a long reaction time but iodobenzene
gave biphenyls with good conversion amounts even with very
low catalyst quantity. Variation of the amount of catalyst to as
low as 0.01 mol% of Pd resulted in the formation of biphenyl in high
yield and turnover number (TON).
The efficacy of different ligands was ascertained by separate
experiments (Table 1, entries 1, 2, 4 and 5). It was found that in
the absence of any ligand, only Pd(OAc)2 (Table 1, entry 3) could
catalyze the Suzuki reaction, but the yield of biphenyl was low
(20%). The reaction with ligand 1c under controlled conditions
increased the yield to 96% (Table 1, entry 4), clearly indicating
the role of the ligand. Similarly, reaction carried out at room
temperature (with neither heating nor sonication) gave the
biphenyl in very poor yield (Table 1, entry 9), indicating the effect
of ultrasonic irradiation.
The method of using readily accessible ligands was further
extended for a number of examples (Table 2). A series of different
biaryls 5–13 were prepared by using a ligand–Pd ratio (1/Pd(OAc)2)
of 0.12/0.10 mol%), while for dibromo, tribromo and tetrabromo
substrates a higher ratio of phenylboronic acid and catalyst
was needed. The method worked well for a series of compounds,
establishing the generality of the present ligand system for the
Suzuki–Miyaura coupling reaction.
The present reaction system was then investigated under
ultrasonic/sonication conditions. The reaction was conducted in a
normal cleaning immersion sonication bath and the reaction
medium was agitated by a mechanical stirrer. Care was taken to
maintain the bath temperature below 40ꢀC by careful water
circulation. A wide variety of substrates and boronic acids were
used for Suzuki–Miyaura coupling under sonication and the results
are summarized in Table 3.
examples of double Suzuki reactions have been reported in which
excellent control for two different reagents was achieved.[51] In this
paper, the present authors report the initial efforts to apply this
phosphine-free Pd catalyst system for a one-pot combination of
Wittig and Suzuki–Miyaura coupling reactions. Very few references
are reported in the literature describing an organophosphine-
catalyzed one-pot Wittig–Suzuki reaction sequence with
formylareneboronic acid[52] where the formyl group undergoes
an olefination reaction. A case of one-pot Wittig–Suzuki reaction
utilizing a phosphine-free catalyst system has not been reported.
The essential requirement of planning any one-pot multi-step
reaction is the compatibility of the reagent system and reaction
conditions. The stability of the phosphonium salt, while still reactive
towards carbonyl groups, under a number of different reaction
conditions offers the opportunity to combine the Wittig olefination
reaction with another transformation in a one-pot procedure.
Phosphonium salt 28 was prepared from 4-bromobenzyl bromide
and triphenyl phosphine as the component which can undergo
Suzuki coupling at its Ar-Br site. A separate aldehyde has
been chosen to receive its carbanion/ylide for the olefination
reaction. This approach is outlined in Scheme 3 considering the
Br
Br
-
+
BrPh3P
Wittig
29
R
28
Suzuki
(HO) B
2
R'
R'
The strategy for cascade reactions involved carrying out a
sequence of transformations in which the product of the first step
serves as the substrate for the second step. The process involved
a number of steps until finally a stable product was formed. The
30
R
Scheme 3. One-pot approach for synthesis of styryl biphenyls
O
Me
Ph
Ph
Ph
N
Ph
N
Ph
N
Me
OH
N
N
OH
OH
OH HO
1a
1b
1c
1d
Figure 1. List of ligands for the present study
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Appl. Organometal. Chem. (2012)

1-(a-Aminobenzyl)-2-naphthol as phosphine-free ligand
Table 1. Search for suitable conditions for Suzuki reaction with 1-(a-aminobenzyl)-2-naphthols 1 as ligand
Entry
PhX, X
(mol eq.)
1
Temperature (ꢀC)
[Time (h)]
Yield (%
of Ph–Ph)
[TON]
(Pd(OAc)2/ligand
mol% ratio)
1
2c, I
(1.0)
2c
1a
(0.1/0.12)
1b
95
92
[920]
89
[4]
2
95
(1.0)
2c
(0.1/0.12)
1c
[4]
[890]
20
3
95
(1.0)
2c
(0.1/0.00)
1c
[4]
[200]
96
4
95
(1.0)
2c
(0.1/0.12)
1d
[4]
[964]
85
5
95
(1.0)
2b, Br
(1.0)
2a, Cl
(1.0)
2c
(0.1/0.12)
1c
[4]
[854]
82a
6
95
(0.1/0.12)
1c
[20]
[629]
26a
7
95
(0.1/0.12)
1c
[30]
[146]
93
8
95
[24]
(1.0)
2c
[0.01:0.012]
1c
[9390]
10
9
r.t.
(1.0)
2c
(0.1/0.12)
1c
[2]
[100]
60
10
11
Sonication
Temp. ≤ 40 ꢀC [2]
Sonication
Temp. ≤ 40 ꢀC [2]
(1.0)
2c
(0.1/0.12)
1c
[603]
70
(1.0)
(0.5/0.60)
[140]
All reactions in dioxane–water (1:1) with phenyl boronic acid (1.2 equiv.), K2CO3 (2.0 equiv.).
aWith TBAB (20 mol%).
example of the in situ Wittig synthesis of stilbene and then the Suzuki
reaction to form 4-styryl biphenyl. A similar class of molecules was
synthesized by one-pot Heck–Suzuki sequence by Gruber et al.[36e]
In order to effectively carry out our practical one-pot strategy it
was necessary to establish the efficacy of the solvent for both steps.
It was also important to check whether the ratio of Z and E isomers
was affected in the second step. To confirm this aspect an experi-
ment was conducted in which the product 4-bromo stilbene 29
was separated and characterized. The ratio of Z:E isomer of 29
of stilbene derivatives 30 were obtained in excess in Wittig
olefination.[53] The Z:E isomer ratios were close to ~55:45, except
for product 4-nitrostyryl biphenyl 34, where the nitro group
controls the ratio in favor of the E isomer.
Experimental
Reagents were purchased from Sigma-Aldrich Chemicals Ltd, SD
Fine, Qualigens Limited, etc. Thin-layer chromatography (TLC) was
performed on Merck 60 F254 aluminium-coated plates. The spots
were visualized under UV light or with iodine vapor. All the
compounds were purified by column chromatography using silica
gel (60–120 mesh). The ligands 1 were prepared by the general
process[25] and characterized by usual spectral analysis before
being used for the present work. All the products were characterized
1
was established by H-NMR analysis to be 48:52 and the isolated
yield was 72%. The product 29 was then subjected to a separate
step under Suzuki reaction conditions and the final product 30
was isolated in 67% yield, with a Z:E ratio of 50:50. Both steps were
carried out in same solvent (anhydrous DMA) and the ratio of
isomers was almost the same, indicating the compatibility of
solvent and also establishing that negligible isomerization occurred
in the second step of the one-pot sequence.
The overall reaction sequence involved three components or
variables, although presently 28 has been used as the common
element. By varying the other two components a series of
styryl biphenyls were synthesized and the results are presented
in Table 4.
The Wittig olefination reaction of aromatic aldehyde with
phosphonium salt 28 took place even in the presence of a weak
base like potassium carbonate (3 equiv.) in DMA under inert
atmosphere at 130ꢀC initially to form 29, an intermediate
4-bromostilbene. Boronic acid (1.2 equiv.), potassium carbonate (2
equiv.), a catalytic quantity of Pd(OAc)2–ligand 1c, and TBAB as
phase transfer catalyst were added after 6 h and the reaction
mixture was continued to completion. In all cases, the Z isomer
1
by H-NMR IR, mass spectroscopy and by comparison of melting
1
point with the reported values. H-NMR spectra were recorded on
a Bruker Avance 400 Spectrometer and were run in CDCl3. Mass
spectra were recorded on a Thermo Fisher DSQ II GCMS instrument.
IR spectra were recorded on a PerkinElmer FTIR RXI spectrometer
as KBr pallets. Melting points were recorded in Thiele’s tube using
paraffin oil and are uncorrected.
Typical Experimental Procedure for the Suzuki Reaction
under Conventional Conditions (in Thermal Condition)
To an oven-dried two-necked round-bottom flask equipped with a
stirrer bar was charged 4-iodoanisole (0.25 g, 1.07 mmol), potassium
carbonate (0.295 g, 2.14 mmol), palladium acetate (0.24 mg,
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.
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A. R. Chaudhary and A. V. Bedekar
Table 2. Application of 1-(a-aminobenzyl)-2-naphthols 1 as ligand for palladium-catalyzed Suzuki–Miyaura reaction with phenylboronic acid,*with
o-tolylboronic acid.
Entry
ArX
Pd(OAc)2–1
[mol% ratio]
Temp. (ꢀC)
[Time (h)]
Ar–Ar′
[Yield (%)]
1
2
3
4
5
6
7
8
C6H5I
1c
[0.1/0.12]
1c
95
[4]
C6H5-C6H5 4 [96]
4-MeOC6H4I
AcHNC6H4I
95
4-MeOC6H4–C6H5 5 [98]
AcHNC6H4–C6H5 6 [98]a
4-NO2C6H4–C6H5 7 [89]
3-NO2C6H4–C6H5 8 [81]
4-CH3COC6H4–C6H5 9 [90]
[0.1:0.12]
1c
[4]
95
[0.1:0.12]
1c
[8]
4-NO2C6H4Br
3-NO2C6H4Br
4-CH3COC6H4Br
1,2-Br2C6H4
95
[0.1:0.12]
1a
[15]
95
[0.1:0.12]
1a
[15]
95
[0.1:0.12]
1c
[15]
95
2-BrC6H4–C6H5 10 [24]
1,2-Ph2C6H4 11 [68]
[0.1:0.12]
1c
[15]
95
Br
Br
X
Ph
[0.1:0.12]
[15]
12, X = Br [20]
13, X = Ph [77]
9
2-MeC6H4I
2-MeC6H4I
1,2-Br2C6H4
1c
[0.5:0.6]
1c
95
[15]
95
2-MeC6H4–C6H5 14 [94]
10
11
2-MeC6H4–2′-MeC6H4 15 [96]*
[0.5:0.6]
1c
[15]
95
2-BrC6H4–Ar 16 [24]a,c
*
[2:2.2]
[24]
1,2-Ar2–C6H4 17 [74]a,c
*
Ar = 2-MeC6H4
12
13
14
1,3,5-Br3C6H3
1,3,5-Br3C6H3
1,2,4,5-Br4C6H2
1c
[3:3.3]
1c
95
[15]
95
1,3,5-Ph3C6H3 18 [89]a,c
1,3,5-Ar3C6H3 19 [86]a,c
Ar = 2-MeC6H4
*
[3:3.3]
1c
[15]
95
1,2,4,5-Ph4C6H2 20 [90]a,a
[4:4.4]
[40]
All reactions in dioxane-water (1:1) with K2CO3 (2.0 eq); aWith TBAB (20% per halogen atom);
aDioxane-H2O (2:1); cDioxane-H2O (3:1).
0.001 mmol) and 1c (0.356 mg, 0.0013 mmol) in dioxane–water (1:1).
To this reaction mixture phenylboronic acid (0.156 g, 1.28 mmol)
was added. The reaction mixture was heated at 95 ꢀC for 4 h. Follow-
ing confirmation of consumption of the starting material by TLC, the
reaction mixture was quenched with water and extracted with ethyl
acetate (3 Â 25 ml). The combined organic phase was washed with
water and dried over anhydrous sodium sulfate. Solvent was re-
moved under vacuum and the crude product was purified by col-
by TLC. After completion of the reaction, the reaction mixture
was quenched with water and extracted with ethyl acetate (3 Â
25 ml). The combined organic phase was washed with water and
dried over anhydrous sodium sulfate. Solvent was removed under
vacuum and the crude product was purified by column chromatog-
raphy on silica gel to afford 3-(hydroxymethyl)biphenyl 27 (0.078 g,
95%) (Table 3, entry 13).
umn chromatography on silica gel to afford
nyl 5 (0.194 g, 98%) (Table 2, entry 2).
4-methoxybiphe-
Representative Procedure for the One-Pot Wittig–Suzuki
Reaction
4-(Chlorostyryl)biphenyl (32) (Table 4)
General Procedure for the Suzuki Reaction under Sonochemical
Conditions (in Ultrasonication)
In a dry N2-flushed two-necked round-bottom flask a mixture of
4-chlorobenzaldehyde (0.2 g, 1.423 mmol), (4-bromobenzyl)triphe-
nylphosphonium bromide 28 (0.729 g, 1.423 mmol) and dry potas-
sium carbonate (0.59 g, 4.268 mmol) in dry N,N-dimethylacetamide
(5 ml) was placed and kept under N2 atmosphere. The reaction
was heated to 130ꢀC for 6 h and then phenylboronic acid
(0.208 g, 1.707 mmol), potassium carbonate (0.393 g, 2.845 mmol),
TBAB (0.092 g, 0.284 mmol), palladium acetate (3.19 mg,
To the mixture of iodobenzene (0.05 ml, 0.447mmol), palladium
acetate (0.5mg, 0.002 mmol), 1c (0.74 mg, 0.002 mmol), and
potassium carbonate (0.185 mg, 1.34 mmol) in dioxane–water
(1:1) was added 3-(hydroxymethyl)phenyl boronic acid (0.082 g,
0.536mmol). The reaction mixture was then sonicated for the time
mentioned in Table 3. The progress of the reaction was monitored
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Appl. Organometal. Chem. (2012)

1-(a-Aminobenzyl)-2-naphthol as phosphine-free ligand
Table 3. Application of 1c as ligand for palladium-catalyzed Suzuki–Miyaura reaction under sonication
Entry
Ar-X
Ar-B(OH)2
Pd(OAc)2–1c
Temp. ≤ 40 ꢀC
Ar–Ph
(mol. equiv.)
[mol % ratio]
[Time (h)]
[Yield (%)]
1
4-NO2C6H4Br
3-NO2C6H4Br
4-CH3COC6H4Br
C6H5I
C6H5B(OH)2
(1.2 equiv.)
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
[1:1.2]
[5]
[5]
[4]
[5]
[5]
[5]
[7]
[5]
[5]
[5]
[4]
[4]
[4]
4-NO2C6H4–C6H5 7 [89]
3-NO2C6H4–C6H5 8 [86]
4-CH3COC6H4–C6H5 9 [84]
2-Me-C6H4–C6H5 14 [66]
2
C6H5B(OH)2
(1.2 equiv.)
3
C6H5B(OH)2
(1.2 equiv.)
4
2-Me-C6H4B(OH)2
(1.2 equiv.)
5
4-NO2C6H4Br
4-CH3COC6H4Br
4-CHOC6H4Br
1,2-Br2C6H4
1,4-Br2C6H4
1,3,5-Br3C6H3
C6H5I
2-Me-C6H4B(OH)2
(1.2 equiv.)
4-NO2C6H4–Ar 21 [90]
Ar = 2-MeC6H4
6
2-Me-C6H4B(OH)2
(1.2 eq.)
4-CH3COC6H4–Ar 22 [94]
Ar = 2-MeC6H4
7
C6H5B(OH)2
4-CHOC6H4–C6H5 23 [89]
(1.2 equiv.)
8
C6H5B(OH)2
2-BrC6H4–C6H5 10 [10]a
1,2-Ph2C6H4 11 [87]a
4-BrC6H4–C6H5 24 [27]a
1,4-Ph2C6H4 25 [52]a
1,3,5-Ph3C6H3 18 [91]a
(4.0 equiv.)
9
C6H5B(OH)2
[1:1.2]
(4.0 equiv.)
10
11
12
13
C6H5B(OH)2
[3:3.3]
(6.0 eqiov.)
4-CHOC6H4B(OH)2
(1.2 equiv.)
[0.5:0.6]
[0.5:0.6]
[0.5:0.6]
4-CHOC6H4–C6H5 23 [57]
3-HOC6H4–C6H5 26 [92]b
3-HOCH2C6H4–C6H5 27 [95]b
C6H5I
3-HOC6H4B(OH)2
(1.2 equiv.)
C6H5I
3-HOCH2C6H4B(OH)2
(1.2 equiv.)
All reactions run in dioxane–water (1:1) with K2CO3 (2.0 equiv.).
aWith TBAB (20% per halogen atom).
bWith K2CO3 (3.0 equiv.).
0.014 mmol) and 1c (4.71 mg, 0.017 mmol) were added and again
heated to 130ꢀC for 24 h. The reaction mixture was added to
20 ml of water and extracted with ethyl acetate (3 Â 25 ml). The
combined organic layer was washed with water (2 Â 20 ml), dried
with anhydrous sodium sulfate and concentrated under vacuum.
The residue was purified by flash chromatography on silica gel to
give the desired product 4-(chlorostyryl)biphenyl 32 (0.33 g, 80%)
(Table 4, entry 2).
129.65, 129.8, 130.01, 130.36, 130.45, 130.49, 135.36, 135.42,
135.7, 135.91, 137.42, 140.77, 141.35, 141.56, 141.6 (for mixture
of Z and E). Mass (EI): 271.1 (21), 270.07 (100), 255.05 (12), 179
(12), 178 (14), 152.01 (3), 91 (3).
4-[2-(4-Nitrophenyl)vinyl]biphenyl (34) (Table 4, entry 4). Yield
0.307 g (77%); Z:E = 9 : 91; m.p. 212–214ꢀC (lit.[57,58] 216–218ꢀC).
4-[2-(4-Methoxyphenyl)vinyl]biphenyl (35) (Table 4, entry 5). Yield
for compound 35 is = 0.30 g (64%) ; Z:E = 55:45; m.p. 234–236 ꢀC
(lit.[59,60] 236–236.5ꢀC).
Analytical and spectral data for new compounds are reported
in Table 4.
5-(2-Biphenyl-4-ylvinyl)benzo[1, 3]dioxole (36) (Table 4, entry 6).
Yield 0.29 g (73%); Z:E = 55:45; m.p. 176–178ꢀC (lit.[60]
188–189ꢀC).
4-Styrylbiphenyl (31) (Table 4, entry 1). Yield 0.34 g (56%); Z:
E = 55:45; m.p. 64–66 ꢀC (Z isomer), 216–218ꢀC (E isomer)
(lit.[54,55] 209ꢀC).
4-[2-(4-Chlorophenyl)vinyl]biphenyl (32) (Table 4, Entry 2). Yield:
0.33 g (80%); Z:E = 57:43; m.p. 100–102ꢀC (Z isomer), 242–244ꢀC
(E isomer).[56]
2’-(2-Biphenyl-4-ylvinyl)furan (37) (Table 4, entry 7). Yield 0.28 g
(55%); Z:E = 38:62 (tentatively established by 1H-NMR compound
was unstable); m.p. 134–136ꢀC. IR (KBr): n 3028, 2922, 1951,
1776, 1749, 1698, 1599, 1556, 1485, 1408, 1326, 1257, 963, 735,
693 cmÀ1. Anal. Calcd for C18H14O.1/4H2O: C, 86.2; H, 5.63. Found:
C, 86.3; H, 4.95%. 1H-NMR (400 MHz, CDCl3) d 6.36–6.54 (m, 2 H),
6.97 and 7.10 (two d, J = 16 Hz), 7.36–7.67 (m, 10 H). 13 C NMR
(CDCl3) d 108.76, 111.74, 116.55, 126.63, 126.78, 126.93, 127.01,
127.36, 127.39, 128.85, 129.25, 136.09, 140.27, 140.66, 142.24,
153.31 (for mixture of Z and E). Mass (EI): 247.05 (19), 246.04
(100), 245.05 (16), 217.04 (30), 202.02 (22), 169.01 (4), 152.02 (3).
5-[2-(2′-Methylbiphenyl-4-yl)vinyl]benzo[1,3]dioxole (38) (Table 4,
entry 8). Yield 0.28 g (67%); Z:E = 56:44; m.p. 94–96ꢀC. IR (KBr):
n 3018, 2952, 1926, 1630, 1600, 1503, 1487, 1444, 1356, 1313,
2-Methyl-4′-styrylbiphenyl (33) (Table 4, entry 3). Yield 0.42 g
(63%); Z:E = 59:41; m.p. 74–76 ꢀC. IR (KBr): n 3054, 3020, 2951,
2922, 1950, 1915, 1598, 1574, 1510, 1481, 1447, 1409, 1379,
1326, 1305, 966, 762, 729, 692 cmÀ1. Anal. Calcd for C21H18:
1
C, 93.29; H, 6.73. Found: C, 93.39; H, 6.79%. H-NMR (400 MHz,
CDCl3) d 2.35 (s, 3 H), 7.20 (s, 2 H), 7.28–7.32 (m, 5 H), 7.36–7.43
(m, 4 H), 7.57–7.62 (m, 4 H) (for E isomer). 13 C NMR ( CDCl3) d
20.6, 20.63, 125.86, 125.92, 126.31, 126.6, 127.21, 127.3, 127.39,
127.71, 128.33, 128.4, 128.67, 128.74, 128.78, 128.94, 129.13,
Appl. Organometal. Chem. (2012)
Copyright © 2012 John Wiley & Sons, Ltd.
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A. R. Chaudhary and A. V. Bedekar
Table 4. One-pot Wittig olefination–Suzuki coupling reaction variation of boronic acid and aldehyde components
No
Aldehyde
(1.0 equiv.)
Boronic acid
(1.2 equiv.)
Product
Yielda (%)
(Z:E ratio)
m.p.c (ꢀC)
(lit. m.p.)[ref.]
1
C6H5CHO
4-ClC6H4CHO
C6H5CHO
C6H5B(OH)2
C6H5B(OH)2
56
216–218
(55 : 45)
(209)[54]
31
2
3
80
242–244
(NA)[56]
Cl
(57 : 43)
32
2-MeC6H4B(OH)2
63
74–76
(59 : 41)
(NA)
33
Me
4
5
4-NO2C6H4CHO
4-MeOC6H4CHO
C6H5B(OH)2
C6H5B(OH)2
77
212–314
O2N
(9 : 91)
(216–218)[57,58]
34
64
234–236
(236–236.5)[59]
MeO
(55 : 45)
35
36
6
7
8
Piperonal
Furfural
C6H5B(OH)2
C6H5B(OH)2
73
176–178
O
O
(55:45)
(188)[60]
55
(38:62)b
134–136
O
(NA)
37
Piperonal
2-MeC6H4B(OH)2
67
94–96
O
O
(56:44)
(NA)
38
Me
9
4-MeC6H4CHO
C6H5B(OH)2
77
214–216
(219–220)[61]
Me
(55:45)
39
All reactions run with aldehyde (1 equiv.), phosphonium salt 28 (1 equiv.), boronic acid (1.2 equiv.), K2CO3 (5.0 equiv.), TBAB (20%), Pd(OAc)2 (1%), 1c
(1.2%) in DMA at 130 ꢀC for 30 h.
aIsolated. cis:trans ratio determined by 1H-NMR.
bTentatively established by 1H-NMR; compound was unstable.
cFor E isomer.
1260, 1100, 1042, 968, 941, 851, 735, 612 cmÀ1. Anal. Calcd For
C22H18O2.1/4(H2O): C, 82.86; H, 5.69. Found: C, 83.02; H, 5.3%.
1H-NMR (400MHz, CDCl3) d 2.32 and 2.33 (two s, 3 H, –CH3 of Z
and E isomers), 5.96 and 6.01 (two s, 2 H, –CH2– of Z and E isomer),
6.55 and 6.56 (two d, J = 12.4 Hz, 2 H), 6.69–6.85 (m, 1 H), 6.98–7.63
(m, 10 H). 13 C NMR (CDCl3) d 20.57, 29.75, 100.97, 101.18,
105.56, 108.26, 108.48, 108.95, 121.54, 122.97, 125.82, 125.86,
126.05,126.27, 126.67, 127.26, 127.31, 128.37, 128.58, 128.63,
128.99, 129.15, 129.59, 129.63, 129.76, 129.78, 129.89, 130.4,
130.43, 131.27, 131.94, 135.35, 135.39, 135.73, 135.95, 140.66,
141.04, 141.54, 141.57, 146.69, 147.36, 147.43, 148.2 (for mixture
of Z and E). Mass (EI): 315.09 (24), 314.07 (100), 239.04 (15),
165.01 (12).
4-[2-(4-Methylphenyl)vinyl]biphenyl (39) (Table 4, entry 9). Yield
0.52 g (77%), Z:E = 55:45; m.p. of pure E isomer 214–216ꢀC
(lit.[61,62] 219 ꢀC).
Conclusion
In this communication we have reported applications of
1-(a-aminobenzyl)-2-naphthols as air-stable phosphine-free
wileyonlinelibrary.com/journal/aoc
Copyright © 2012 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. (2012)

1-(a-Aminobenzyl)-2-naphthol as phosphine-free ligand
A. V. Bedekar, Tetrahedron Lett. 2010, 51, 6227; e) A. S. Saiyed,
R. S. Joshi, A. V. Bedekar, J. Chem. Res. 2011, 408.
ligands for palladium-catalyzed Suzuki–Miyaura reaction and
extended the study with development of a one-pot strategy for
the combination of Wittig olefination and Suzuki–Miyaura coupling
reaction to offer easy access to styryl biphenyls (C6-C2-C6-C6 unit).
Such reactions carried out in one-pot or under cascade conditions
reduce consumption of reagents such as solvent, save energy and
offer many advantages which can make this a greener process.
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Acknowledgements
We thank the Council of Scientific and Industrial Research (CSIR)
New Delhi for the award of a Research Fellowship (JRF) to A.R.C.
We are grateful to Prof. B. V. Kamath for his support and
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