First catenane-containing phosphino groups: A step toward a catenane ligand

Article abstract of DOI:10.1080/00397910701797814

A novel [2] catenane containing a diphenylphosphino group on each ring was prepared. Synthesis of the new catenane involved the use of tetraamide rings to form an efficient pseudorotaxane intermediate. The catenane was found to be applicable as a ligand for metal-catalyzed reactions such as Suzuki-Miyaura coupling. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910701797814

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First Catenane‐Containing Phosphino Groups:
A Step toward a Catenane Ligand
a
a
a
Manabu Yamazaki , Toshiki Hagiwara , Masahiro Sekiguchi , Takashi
a
a
Sawaguchi & Shoichiro Yano
a
Department of Materials and Applied Chemistry , College of Science and
Technology, Nihon University , Chiyoda-ku, Tokyo, Japan
Published online: 27 Feb 2008.
To cite this article: Manabu Yamazaki , Toshiki Hagiwara , Masahiro Sekiguchi , Takashi Sawaguchi & Shoichiro
Yano (2008) First Catenane‐Containing Phosphino Groups: A Step toward a Catenane Ligand, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 38:4,
553-558, DOI: 10.1080/00397910701797814
To link to this article: http://dx.doi.org/10.1080/00397910701797814
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Synthetic Communications , 38: 553–558, 2008
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910701797814
First Catenane Containing Phosphino
Groups: A Step toward a Catenane Ligand
Manabu Yamazaki, Toshiki Hagiwara, Masahiro Sekiguchi,
Takashi Sawaguchi, and Shoichiro Yano
Department of Materials and Applied Chemistry, College of Science and
Technology, Nihon University, Chiyoda-ku, Tokyo, Japan
Abstract: A novel [2] catenane containing a diphenylphosphino group on each ring
was prepared. Synthesis of the new catenane involved the use of tetraamide rings to
form an efficient pseudorotaxane intermediate. The catenane was found to be appli-
cable as a ligand for metal-catalyzed reactions such as Suzuki-Miyaura coupling.
Keywords: amides, catenane, hydrogen bonding, ligand, phosphino group
INTRODUCTION
Over the past decade, catenanes have been the subject of much attention because
[1]
of their unique structure. Therehave been manyreportsconcerningthe synthesis
and structural analysis of catenanes, but fewer on their application as functional
[
2]
molecules. Balzani et al. have investigated functional catenanes for use in
[2a–c]
such applications as switching devices
[2d]
and color-switchable dyes.
We have investigated the preparation of catenanes containing phosphorous
functions for use as novel ligands in metal complex catalysis. Because catenane
rings show rigidity and high mobility, catenane-based ligands may be expected
to show high selectivity and wide applicability. There are examples of catenane
0
[3]
ligands containing 2,2 -bipyridyl moieties as coordination sites; however, to
the best of our knowledge, there have not yet been any reports of a [2]catenane
Received December 8, 2006
Address correspondence to Toshiki Hagiwara, Department of Materials and
Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14,
Kanda-Surugadal, Chiyoda-ku, Tokyo 101-8308, Japan. E-mail: hagiwara@chem.
cst.nihon-u.ac.jp
5
53

5
54
M. Yamazaki et al.
with coordination sites on each ring. Very recently, phosphorous - containing
catenane that is an other type reported. That has phosphineoxide moieties in
[
4]
thier ring structures. In this communication, we report the preparation of a
novel [2]catenane possessing diphenylphosphino-group coordination sites and
the application of this catenane as a ligand for metal catalysis.
RESULTS AND DISCUSSION
Amide-based [2]catenanes, studied in detail by several researchers, were
selected as the mother catenane onto which phosphino groups were intro-
[
5]
duced. These can be prepared relatively easily and contain no other
metal-coordination sites and no electric charges; the amide group can be
[6]
inactivated by reduction and methylation if necessary.
-(Diphenylphosphino)isophthalic acid (1) was prepared in good yield from
5
-aminoisophthalic acid via diazonium salt iodination followed by palladium-
[7]
5
catalyzed coupling with diphenylphosphine (Scheme 1). Compound 1 was
[8]
allowed to react with SOCl to form an acid chloride, which then underwent
2
amidation with 4-hydroxybenzylamine to form phosphorous-containing
diphenol 2a, with oxidation of the phosphino group. (In the process of
amidation of 1 and 4-hydroxybenzylamine, the phosphino group was oxidized
and phosphinoxide 2a was obtained. The air oxidation was supposed, but
details have not been revealed.) From 2a, catenane preparation was attempted
[
5e]
according to the reported procedure,
and no interlocked compounds were obtained. It has been reported that
but only macrocycle 3a was formed,
[9]
catenane structures may be assembled via ring closure of pseudorotaxane, but
in this case, it was thought that the pseudorotaxane structure could not be
formed because of the bulkiness of the diphenylphosphino groups (Fig. 1a).
To avoid this steric hindrance, the preparation of a tetraamide ring catenane
was investigated. The use of a tetraamide ring, which contains many hydrogen
bonding sites (Fig. 1b), allows the formation of less hindered pseudorotaxane inter-
mediates. Diamine 2b was prepared from 1and 4-aminobenzylamine by amidation
Scheme 1. Catenane preparation from phosphorous-containing diphenol 2a.

Catenane-Containing Phosphino Groups
555
Figure 1. Plausible pseudorotaxane intermediates from diamide macrocycle (a) and
tetraamide macrocycle (b).
Scheme 2. Preparation of tetraamide catenane ligand 4b.
1
Figure 2. H NMR spectra of catenane ligand 4b and macrocycle 3b (400 MHz,
DMSO-d ; signals indicated by “E” represent ethanol used for PLC isolation).
6

5
56
M. Yamazaki et al.
0
using N,N -dicyclohexylcarbodiimide/1-hydroxybenzotriazole (DCC/HOBt) as
[10]
a coupling reagent, and cyclization of 2b with sebacoyl chloride was carried
out under dilution conditions (Scheme 2). The desired diphenylphosphinated
[2]catenane 4b was isolated from the product by preparative thin layer chromato-
graphy (PLC), along with macrocycle 3b. The H NMR spectra of catenane 4b and
1
macrocycle 3b are shown in Fig. 2. In 4b, the signals of the 1,4-disubstituted
aromatic rings are shifted to higher field compared to those of 3b, suggesting
1
that a catenane structure was formed. These high field shifts of the H NMR
signals are characteristic of catenanes. The same results have been reported by
[5e]
Leigh et al. The MALDI-TOF MS spectrum of 4b is shown in Fig. 3. The
þ
molecular ion of the [2]catenane (M , m/z ¼ 1449.8), along with some cationized
þ
þ
molecular ions ([M þ Na] , m/z ¼ 1472.7 and [M þ K] , m/z ¼ 1488.7), were
observed clearly, showing that the required phosphinated catenane had been
obtained.
To investigate the activity of catenane 4b as a ligand, a Suzuki–Miyaura
[
11]
coupling reaction was carried out.
acetate, bromobenzene was coupled with phenylboronic acid to give biphenyl in
9% yield (Scheme 3). This is the first report about preparation of catenane
In the presence of 4b and palladium(II)
6
containing phosphino groups and using the catenane as a ligand of metal
catalyst. Further investigations of the catenane ligand such as applications for
other catalytic reactions and structure analysis of the metal–ligand complex are
now in progress.
EXPERIMENTAL
Preparation of Diamine 2b
To a solution of 5-diphenylphosphinoisophthalic acid (0.70 g) and 1-hydroxy-
0
benzotriazole monohydrate (0.64 g) in DMF (6.0 mL), N,N -dicyclohexylcar-
bodiimide (0.87 g) was added at 08C and stirred for 24 h. The formed
precipitate was filtered off, and the filtrate was added dropwise to a solution
of 4-aminobenzylamine (0.51 g) in DMF (20 mL) and stirred for 24 h at
Figure 3. Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF)
MS spectrum of catenane ligand 4b.

Catenane-Containing Phosphino Groups
557
Scheme 3. Suzuki–Miyaura coupling reaction with catenane 4b as a ligand.
08C. After the solvent was distilled off, the residue was dissolved in chloro-
form and washed with 2 M NaOH. The organic layer was washed with
water, dried over MgSO , and evaporated. Diamine 2b was obtained in 60%
4
yield, and the purity was high enough to use a catenane preparation.
Preparation of [2]Catenane 4b
Because of low solubility in chloroform, diamine 2b (0.173 g) was dissolved in
acetonitrile (4.0 mL) by heating and diluted by chloroform (150 mL). After
adding triethylamine (0.063 g) to the diamine solution, sebacoyl chloride
(0.074 g) in chloroform (50 mL) was added dropwise for 2 h. Precipitate was
removed by filtration. The filtrate was washed with 1 M HCl, dried over
MgSO , and the solvent was removed by evaporation. The residue was
4
dissolved in a few milliliters of chloroform and allowed to stand for overnight.
After filtration, [2]catenane 4b was isolated from the filtrate by PLC in 7% yield.
ACKNOWLEDGMENT
We acknowledge financial support bythe High-TechResearch Center Project from
the Ministry of Education, Culture, Sports, Science, and Technology of Japan.
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