Synthesis of oligo(phenyleneethynylene)s containing central pyromellitdiimide or naphthalenediimide groups and bearing terminal isocyanide groups: molecular components for single-electron transistors

Article abstract of DOI:10.1016/j.tet.2007.05.116

Oligo(phenyleneethynylene)s that are of variable length, contain a central arenediimide unit, either a pyromellitdiimide or a naphthalenediimide group, and are terminated by isocyanide groups have been prepared. The extended frameworks were assembled from appropriately functionalized arenediimide and areneformamide units whose lengths were adjusted by adding phenyleneethynylene units. Final transformation of the formamide groups into isocyanide groups gave the title compounds. Several isocyanide-terminated oligo(phenyleneethynylene)s without an arenediimide unit have also been prepared.

Full text of DOI:10.1016/j.tet.2007.05.116

Tetrahedron 63 (2007) 8206–8217
Synthesis of oligo(phenyleneethynylene)s containing central
pyromellitdiimide or naphthalenediimide groups and bearing
terminal isocyanide groups: molecular components for
single-electron transistors
*
Andreas Mayr, Muthialu Srisailas, Qun Zhao, Yuan Gao, Heidi Hsieh,
Mahsa Hoshmand-Kochi and Natalie St. Fleur
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, NY 11794, USA
Received 15 February 2007; revised 27 April 2007; accepted 29 May 2007
Available online 3 June 2007
Abstract—Oligo(phenyleneethynylene)s that are of variable length, contain a central arenediimide unit, either a pyromellitdiimide or a naph-
thalenediimide group, and are terminated by isocyanide groups have been prepared. The extended frameworks were assembled from appro-
priately functionalized arenediimide and areneformamide units whose lengths were adjusted by adding phenyleneethynylene units. Final
transformation of the formamide groups into isocyanide groups gave the title compounds. Several isocyanide-terminated oligo(phenylenee-
thynylene)s without an arenediimide unit have also been prepared.
Ó 2007 Elsevier Ltd. All rights reserved.
1. Introduction
a central electron acceptor group and terminal surface at-
tachment groups. The title compounds 1–8, shown in
Figure 1, are molecules of this type. In these compounds,
the central electron acceptor is either a pyromellitdiimide or
a naphthalenediimide unit. These arenediimides readily un-
dergo reversible reduction.2 Oligo(phenyleneethynylene)s
(OPEs) are used as moderately conducting tunnel barriers.
OPEs have already been tested as conductors in a variety
of molecular electronic devices.3 Isocyanide groups are at-
tached to the ends of the molecules as surface attachment
groups.4 The length of these molecular single-electron de-
vice components can be adjusted by inserting the appropri-
ate number of phenyleneethynylene units into the linear
chains. In the present series the distance between the termi-
nal isocyanide carbon atoms varies from about 3–9 nm. We
also report the synthesis of several diisocyanides without
a central diimide group and the preparation of corresponding
molecules with only one terminal isocyanide group. The first
molecular electronic devices based on some of the new
diisocyanides have recently been reported.5
The basic devices of single electronics, e.g., the single-
electron box, the single-electron trap, or the single-electron
transistor, consist of simple arrangements of single-electron
islands that are separated from each other and from solid
electrodes by tunnel barriers.1 Single-electron theory spec-
ifies the sizes of the islands and the tunnel barriers as well
as the geometry of their arrangement, but leaves open the
choice of material from which they are made. One possible
means of implementation involves molecular components.
We are developing a building block system for suitable mol-
ecules. Toward this goal, we are using strong electron accep-
tor units as the single-electron islands and linear unsaturated
units as the tunnel junctions. The molecular single-electron
device components also bear terminal surface-binding groups
for the attachment to solid electrode surfaces.
For initial investigations we are preparing molecules that al-
low the placement of just one single-electron island between
two solid electrodes. Such entities may be used as the molec-
ular components in hybrid single-electron transistors. The
general design consists of a linear molecular rod featuring
The chemical synthesis of the title compounds was not ex-
pected to pose any significant challenges, since all molecular
components and chemical transformations involved are well
established. We anticipated that the unusual length of some
of the molecules might give rise to problems concerning
their solubility in common solvents. However, with the in-
troduction of hexyl and isopropyl side chains these potential
Keywords: Oligo(phenyleneethynylene); Isocyanide; Arenediimide; Elec-
tron acceptor.
* Corresponding author. Tel.: +1 631 632 7951; fax: +1 631 632 7960;
e-mail: amayr@notes.cc.sunysb.edu
0040–4020/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2007.05.116

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8207
O
O
Hex
Hex
CN
N
N
NC
Hex
Hex
O
O
n
n
n = 0
n = 1
n = 2
n = 3
1
2
3
4
O
O
Hex
Hex
CN
N
N
NC
Hex
Hex
n
n
O
O
n = 1
n = 2
n = 3
n = 4
5
6
7
8
Figure 1. The title compounds.
problems were effectively eliminated.6 The isopropyl groups
at the arenediimide linkages have the added effect of pre-
venting the coplanar arrangement of the diimide unit and
the OPE chains. This feature adds to the tunnel barrier be-
tween these units. Even the longest products are soluble in
relatively nonpolar solvents or solvent mixtures such as
the toluene/triethylamine mixtures used in the chemical syn-
theses or the hexane/dichloromethane or hexane/ethyl ace-
tate mixtures used in the chromatographic purification
procedures. The isopropyl substituents on the terminal aryl-
isocyanide groups also increase the stability of the final
products. In contrast, unsubstituted arylisocyanides are
known to exhibit a strong tendency toward polymerization.7
in good yields by treatment of 12 and 21 with tetrabutylam-
monium fluoride adsorbed on silica gel. These particular
desilylation procedures did not proceed satisfactorily with
K2CO3 or KOH in methanol. The parent compounds of 13
and 22, bis(4-ethynylphenyl)pyromellitdiimide and bis(4-
ethynylphenyl)naphthalenediimide, have previously been
prepared by the reaction of 10 and 19 with 4-ethynylani-
line.10
The core units 13 and 22 were extended by one or two phe-
nyleneethynylene units. The terminal acetylenes 16 and 24
were obtained by palladium-catalyzed coupling of 13 and
22, respectively, with 4-iodo-2,5-dihexyl-trimethylsilylethy-
nylbenzene, 14, followed by a desilylation step. Compounds
17 and 25 were then obtained by renewed coupling of 16 and
24 with 14.
2. Results and discussion
The arenediimide cores 11 and 20 were prepared from
4-iodo-2,6-diisopropylaniline, 9, and 1,2,4,5-benzenetetra-
carboxylic dianhydride, 10 (Scheme 1a), and from
4-bromo-2,6-diisopropylaniline, 18, and 1,4,5,8-naphthal-
enetetracarboxylic dianhydride, 19 (Scheme 1b). The reac-
tion between 9 and 10 proceeded in hot acetic acid, while
the reaction between 18 and 19 required more forceful con-
ditions. A moderate yield of 20 was obtained by heating a
mixture of 18 and 19 in m-cresol in the presence of a small
amount of isoquinoline to about 210 ꢀC for 20 h.8 Attempts
to prepare the iodo-analogue of 20 were not successful. Only
trace amounts, if any, of the desired compound were ob-
tained when 9 and 19 were allowed to react under the
conditions of the synthesis of 20.
3,5-Diisopropyl-4-formamido-1-ethynylbenzene, 26, was
chosen as the precursor for the terminal isocyanide groups.
This compound was extended by up to three phenyleneethy-
nylene groups to afford compounds 28, 30, and 32 (Scheme
2a). This was accomplished by repeated palladium-cata-
lyzed coupling with 14 and desilylation of the respective in-
termediates 27, 29, and 31 with KOH in CH3OH. The
terminal acetylenes 28, 30, and 32 have a tendency to turn
gradually pink or even brown during storage. For this reason,
they were generated just prior to use. The iodo-terminated
derivatives 34–37 were then obtained from compounds 26,
28, 30, and 32, respectively, by treatment with excess 1,4-
diiodo-2,6-dihexylbenzene, 33, under established coupling
conditions (Scheme 2b). Unused 33 was readily recovered.
These reactions were accompanied by the formation of small
amounts of the extended diformamides 38, 40, 41, and 42.
These compounds as well as diformamide 39, which contains
an even number of phenyleneethynylene groups, can be pre-
pared straightforwardly as shown in Scheme 2c.
Compounds 11 and 20 were then transformed into the corre-
sponding trimethylsilylethynyl derivatives 12 and 21 by
means of palladium-catalyzed coupling with trimethylsilyl-
acetylene.9 The behavior of compound 20 in this reaction
proved to be somewhat erratic. In some attempts of the
synthesis of 21, the formation of a palladium mirror was
observed. In those cases only low yields of 21 were obtained
after the addition of further increments of catalyst and
alkyne. The ethynyl derivatives 13 and 22 were obtained
As an alternative routeto theiodo-terminated compounds34–
37 we also tested the procedure shown in Scheme 3. It
involves the triazene reagent 45, which was prepared from
the diiodobenzene 33 in two steps via the intermediates 43

8208
A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
(a)
O
O
O
O
a
I
NH2
+
O
O
I
N
N
I
O
O
O
O
11
9
10
b
Hex
O
I
SiMe3
14
O
Hex
Hex
d
R
N
R
N
O
Hex
O
n
2
2
15 n = 1 R = SiMe3
16 n = 1 R = H
17 n = 2 R = SiMe3
12 R = SiMe3
13 R = H
c
c
14, d
(b)
O
O
N
O
O
O
O
e
Br
NH2
O
O
Br
N
Br
O
O
18
20
19
f
O
O
N
Hex
15
R
N
R
d
Hex
n
O
O
2
2
21 R = SiMe3
22 R = H
23 n = 1 R = SiMe3
24 n = 1 R = H
25 n = 2 R = SiMe3
c
c
14 d
Scheme 1. Reagents and conditions: (a) acetic acid, 120 ꢀC, 1 h; (b) trimethylsilylacetylene, Pd(PPh3)4, CuI, toluene, NEt3, 2 h, rt; (c) TBAF/THF, silica gel,
CHCl3, rt, 30 min; (d) Pd(PPh3)4, CuI, toluene, Et3N, 12 h, rt; (e) quinoline, m-cresol, 210 ꢀC, 20 h; (f) trimethylsilylacetylene, Pd(PPh3)4, CuI, toluene, NEt3,
65 ꢀC, 7 days.
and 44.11,12 Palladium-catalyzed coupling of 45 with 28 af-
forded the triazene compound 46, which was subsequently
converted into 35 by treatment with methyl iodide at elevated
temperatures. While this triazene route affords the iodo-ter-
minated compound 35 without the byproduct 40, the shorter
procedure shown in Scheme 2a and b is overall more efficient.
group show absorptions in the 3200–3230 cmꢁ1 and 1660–
1690 cmꢁ1 regions for the formamide group. The latter
band is resolved into two peaks in several cases. All com-
pounds containing the pyromellitdiimide group give rise to
an IR band of medium intensity near 1778 cmꢁ1 and a
band of strong intensity near 1730 cmꢁ1. A band of medium
intensity at about 1715 cmꢁ1 and one of strong intensity at
about 1680 cmꢁ1 are characteristic for the naphthalenedi-
imide unit. The trimethylsilylethynyl groups give rise to a
band of medium intensity near 2150 cmꢁ1, the terminal ethy-
The diformamide precursors 47–53 of the isocyanides 1–8
were obtained by palladium-catalyzed coupling of appropri-
ate combinations of the halo- or ethynyl-terminated core
units 11, 13, 16, 22, and 24 and the ethynyl- or iodo-termi-
nated formamide units 26, 34, 35, and 36 (Scheme 4a).
Finally, treatment of these compounds with COCl2 in the
presence of triethylamine13 afforded the isocyanides 1–8.
Furthermore, the monoisocyanides 54–56 and the diisocya-
nides 57–59 were prepared from the monoformamides 27,
29, and 31 and the diformamides 38–40, respectively, under
similar conditions (Scheme 4b).
nyl groups to a band of very low intensity near 2110 cmꢁ1
,
and the internal ethynylene groups to an even weaker band
near 2210 cmꢁ1. The NMR spectra of all compounds con-
taining a formamide group exhibit two sets of signals for
the two conformers that arise due to slow rotation about
the OHC–NH bond. The isocyanides 1–8 exhibit only the
number of signals expected for the symmetry indicated by
the structural formulas. The 13C NMR signals for the iso-
cyanide carbon atoms were found at about d 170 for com-
pounds 54–59. The corresponding signals were not found
for compounds 1–8 since only very small amounts of these
materials were available. The isocyanides 54–59 gave rise
The IR spectra of all isocyanide compounds exhibit a charac-
teristic absorption at about 2110 cmꢁ1. The IR spectra of all
compounds bearing the 2,6-diisopropyl-formamidobenzene

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8209
(a)
Hex
OHC
OHC
H
14
N
R
N
H
a
H
Hex
n
26
27 n = 1 R = SiMe3
28 n = 1 R = H
29 n = 2 R = SiMe3
30 n = 2 R = H
31 n = 3 R = SiMe3
32 n = 3 R = H
b
b
b
a
a
(b)
Hex
34 n = 1
OHC
H
35 n = 2
Hex
I
N
I
36 n = 3
37 n = 4
Hex
n
I
26 or
28 or
30 or
32
Hex
33
+
a
Hex
38 n = 1
40 n = 3
41 n = 5
42 n = 7
OHC
H
H
N
CHO
N
Hex
n
(c)
n = 1, 3
a
2 26 + 33 or
2 28 + 33
Hex
OHC
H
H
N
N
CHO
Hex
n
n = 2
a
28 + 34
38 n = 1
39 n = 2
40 n = 3
Scheme 2. Reagents and conditions: (a) Pd(PPh3)4, CuI, toluene, Et3N, rt, 12 h; (b) KOH/CH3OH, 2 h.
to strong molecular ion peaks in the mass spectra. Attempts
to observe the molecular ion peaks for compounds 1–8 were
not successful. A number of other compounds containing
arenediimide groups, especially those with longer OPE
chains also failed to give rise to molecular ion peaks.
The elemental analyses of the longer molecules consistently
gave lower carbon mass percentages than calculated, while
the hydrogen and nitrogen values stayed within the expected
range. We were not able to identify any impurity, which
might have caused this discrepancy.
Hex
Hex
I
Hex
a
b
c
I
N N
NEt2
NHAc
Hex
I
NH2
Hex
33
Hex
45
28
44
43
d
Hex
OHC
H
e
N
N
2
N
NEt2
35
Hex
46
Scheme 3. Reagents and conditions: (a) N,N0-dimethylethylenediamine, K3PO4, CuI, DMF, 80 ꢀC, 24 h; (b) HCl, EtOH, reflux, 5 h; aq KOH, rt, 1 h; (c)
BF3$Et2O, t-BuNO, CH2Cl2, K2CO3, HNEt2, 0 ꢀC; (d) Pd(PPh3)4, CuI, NEt3, toluene, rt; (e) MeI, 110 ꢀC.

8210
A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
(a)
O
Hex
1
2
3
4
11 + 26
13 + 34
16 + 34
16 + 35
OHC
H
b
a
N
N
Hex
n
O
2
47 n = 1
48 n = 2
49 n = 3
O
Hex
5
6
7
8
22 + 34
22 + 35
24 + 35
24 + 36
OHC
b
a
N
N
H
Hex
n
O
2
50 n = 1
51 n = 2
52 n = 3
53 n = 4
(b)
Hex
54 n = 1
55 n = 2
56 n = 3
27
29
31
b
CN
SiMe3
Hex
n
Hex
38
39
40
57 n = 1
58 n = 2
59 n = 3
b
CN
NC
Hex
n
Scheme 4. Reagents and conditions: (a) Pd(PPh3)4, CuI, toluene, Et3N, rt, 12 h; (b) COCl2, Et3N, CH2Cl2, ꢁ78 ꢀC to rt.
Compounds 1–8 are readily soluble in methylene chloride
and toluene or other moderately polar solvents or solvent
mixtures. The solubility of these compounds in highly polar
solvents such as dimethylformamide or dimethylsulfoxide
decreases strongly with increasing length of the OPE chain.
solvents and reagents were used as received from commer-
cial sources. All coupling reactions were performed under
an atmosphere of nitrogen gas. The IR spectra were recorded
1
on a Mattson Galaxy FTIR 3000 instrument. The H NMR
spectra (CDCl3) were recorded using a Varian Gemini
2300 spectrometer at 300 MHz and 13C NMR spectra
(CDCl3) were recorded using Varian Inova 400 spectrometer
at 100 MHz. Mass spectrometric measurements were per-
formed by the Stony Brook Mass Spectrometry Facility.
Column chromatographies were performed using silica gel
(45–60 mm). Elemental analyses were obtained from QTI
laboratories.
3. Summary
A building block system for the synthesis of unsaturated lin-
ear molecules containing a central pyromellitdiimide and
naphthalenediimide units as electron acceptors and terminal
isocyanide groups as surface-binding groups has been devel-
oped. The individual building blocks for the central and ter-
minal portions of the molecules can be prepared from readily
available starting materials. The lengths of these molecules
can be adjusted by attaching phenyleneethynylene units to
the basic building blocks prior to the assembly of the com-
plete extended structures.
4.2. Synthetic procedures
4.2.1. Typical procedure for the preparation of com-
pounds 1–8 and 55–59. Compound 2: compound 47
(50 mg, 0.033 mmol) was dissolved in CH2Cl2 (10 mL) and
NEt3 (0.3 mL). The stirred mixture was cooled to ꢁ78 ꢀC
and a 1.9 M solution of COCl2 in toluene (0.3 mL) was
added. After 30 min, the reaction mixture was allowed
to warm to room temperature. A solution of KHCO3 (10%,
50 mL) was introduced into the mixture and stirred for a fur-
ther 30 min. The mixture was then extracted with CH2Cl2
(50 mL), washed with water (2ꢂ50 mL), and dried over an-
hydrous MgSO4. Evaporation of the solvent under vacuum
gave a residue, which was purified by column chromato-
graphy on silica gel (hexane/CH2Cl2 5:1). Pale yellow solid.
Yield: 46 mg, 94%.
4. Experimental
4.1. General information
The compounds 9,14 14,15 18,14 26,14b and 3316 were pre-
pared as described in the literature. The solvents toluene,
triethylamine, CH2Cl2, and THF were dried using appropri-
ate drying agents under an atmosphere of nitrogen. All other

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8211
4.2.2. Typical procedure for the preparation of com-
pounds 15, 17, 23, 25, 27, 29, and 31. Compound 15: a mix-
ture of 13 (0.200 g, 0.34 mmol), 14 (0.400 g, 0.85 mmol),
and Pd(PPh3)4 (0.050 g) in toluene (30 mL) and NEt3
(15 mL) was stirred for 10 min. Then CuI (0.025 g) was
added and the mixture was stirred for a further 2 h. The
salt formed was filtered off. Evaporation of the solvent under
vacuum gave a residue, which was purified by column chro-
matography (silica gel, hexane/CH2Cl2 4:1). Pale yellow
solid. Yield: 0.35 g, 81%.
was stirred for a further 16 h. The salt formed was removed
by filtration. The solvent was removed from the filtered so-
lution under vacuum. Evaporation of the solvent under vac-
uum gave a residue, which was purified by column
chromatography on silica gel (hexane/EtOAc 2:1). Pale yel-
low solid. Yield: 0.537 g, 63%.
4.2.7. Compound 1. Yield: 0.110 g, 86%; IR (KBr, cmꢁ1):
2965, 2934, 2872, 2111, 1778, 1730, 1602, 1468, 1366,
1116; H NMR: d 8.56 (s, 2H), 7.50 (s, 4H), 7.38 (s, 4H),
1
3.39 (septet, J¼6.9 Hz, 4H), 2.67 (septet, J¼6.9 Hz, 4H),
1.32 (d, J¼6.9 Hz, 24H), 1.20 (d, J¼6.9 Hz, 24H); 13C
NMR (75 MHz): d 170.1, 165.8, 147.5, 145.3, 137.3,
127.6, 126.8, 126.6, 125.2, 124.0, 119.8, 90.6, 89.6, 31.6,
29.8, 23.8, 22.5.
4.2.3. Typical procedure for the preparation of com-
pounds 13, 16, 22, and 24. Compound 13: tetrabutylammo-
nium fluoride (TBAF, 1.05 g, 4 mmol) and silica gel (5 g)
were added to THF (10 mL). The mixture was stirred for
10 min and then dried. A solution of 12 (0.730 g, 1 mmol)
in CHCl3 (20 mL) was added to a stirred suspension of
TBAF adsorbed on silica gel in CHCl3 (20 mL). The mixture
was stirred for 30 min. The silica gel was filtered off and
washed with CHCl3 (5ꢂ5 mL). The combined solutions
were washed with a saturated aqueous solution of KHCO3
(50 mL) and water (2ꢂ50 mL) and then dried over an-
hydrous MgSO4. Evaporation of the solvent under vacuum
gave a residue, which was purified by column chromato-
graphy on silica gel (hexane/CH2Cl2 3:1). Colorless solid.
Yield: 0.510 g, 85%.
4.2.8. Compound 2. IR (KBr, cmꢁ1): 2957, 2922, 2854,
2112, 1779, 1732, 1597, 1462, 1367; H NMR: d 8.57 (s,
1
2H), 7.48 (s, 4H), 7.44 (s, 2H), 7.42 (s, 2H), 7.33 (s, 4H),
3.40 (septet, 4H), 2.88–2.81 (m, 8H), 2.70 (septet, 4H),
1.76–1.70 (m, 8H), 1.46–1.26 (m, 24H), 1.32 (d,
J¼6.9 Hz, 24H), 1.22 (d, J¼6.9 Hz, 24H), 0.92–0.89 (m,
12H); 13C NMR (75 MHz): d 170.0, 165.8, 147.4, 145.3,
142.5, 137.3, 132.4, 127.4, 126.5, 126.3, 125.9, 124.6,
124.0, 122.7, 122.3, 119.8, 93.8, 93.4, 90.1, 89.1, 34.4,
34.3, 31.8, 31.7, 30.8, 29.8, 29.5, 29.4, 23.8, 22.7, 22.7,
22.5, 14.1.
4.2.4. Typical procedure for the preparation of com-
pounds 28, 30, and 32. Compound 28: potassium hydroxide
(1 M, 15 mL) was added to a methanol solution of 27 (1.3 g,
2.28 mmol). The mixture was stirred for 2 h. Then the sol-
vent was removed under vacuum and the residue was ex-
tracted with CH2Cl2 (2ꢂ50 mL). The combined extracts
were washed with water (2ꢂ50 mL) and dried over an-
hydrous magnesium sulfate. Evaporation of the solvent
gave a residue, which was used as such for further reactions.
Off-white solid.
4.2.9. Compound 3. Yield: 0.112 g, 83%; IR (KBr, cmꢁ1):
2961, 2926, 2855, 2109, 1778, 1730, 1596, 1460, 1365; 1H
NMR: d 8.57 (s, 2H), 7.47 (s, 4H), 7.43 (s, 2H), 7.40 (s,
2H), 7.39 (s, 2H), 7.38 (s, 2H), 7.32 (s, 4H), 3.39 (septet,
J¼6.9 Hz, 4H), 2.87–2.80 (m, 16H), 2.68 (septet,
J¼6.9 Hz, 4H), 1.78–1.68 (m, 16H), 1.48–1.28 (m, 48H),
1.31 (d, J¼6.9 Hz, 24H), 1.21 (d, J¼6.9 Hz, 24H), 0.91–
0.86 (m, 24H); 13C NMR: d 165.8, 147.4, 145.3, 142.5,
142.0, 137.3, 132.5, 132.4, 127.4, 126.5, 124.6, 123.0,
119.8, 93.8, 93.3, 90.2, 85.9, 34.2, 31.8, 31.8, 31.7, 30.8,
30.7, 29.8, 29.5, 29.4, 29.3, 23.9, 22.7, 22.5, 14.1.
4.2.5. Typical procedure for the preparation of com-
pounds 34–37. Compound 34: a mixture of 26 (1.15 g,
5 mmol), 33 (20.0 g, 32 mmol), and Pd(PPh3)4 (0.100 g)
in NEt3 (70 mL) was stirred for 10 min. Then CuI
(0.050 g) was added and the mixture was stirred for a fur-
ther 16 h. The salt formed was removed by filtration. The
solvent was removed from the filtered solution under vac-
uum. The residue was redissolved in CH2Cl2 and 50 g of
silica gel was added with stirring. The solvent was slowly
removed under vacuum and the residue dried. The solid
residue was added to the top of a silica gel column
(5ꢂ30 cm), which had been prepared with hexane. Excess
33 was eluted with hexane. Compound 34 was eluted with
hexane/EtOAc (1:1). The product thus obtained was
contaminated with a small amount of compound 38. Com-
pounds 34 (2.24 g, 75%) and 38 (0.274 g, 8%) were sepa-
rated by a second chromatography on silica gel (hexane/
EtOAc 1:1). Both compounds were obtained as off-white
solids.
4.2.10. Compound 4. Yield: 0.044 g, 98%; IR (KBr, cmꢁ1):
2959, 2924, 2855, 2108, 1778, 1729, 1596, 1463, 1366; 1H
NMR (300 MHz): d 8.57 (s, 2H), 7.48 (s, 4H), 7.43–7.39
(m, 12H), 7.32 (s, 4H), 3.39 (septet, J¼9.6 Hz, 4H), 2.85–
2.80 (m, 24H), 2.69 (septet, J¼ 6.9 Hz, 4H), 1.78–1.69 (m,
24H), 1.47–1.31 (m, 96H), 1.22 (d, J¼6.9 Hz, 24H), 0.90–
0.89 (m, 36H); 13C NMR (75 MHz): d 170.0, 165.8, 147.4,
145.3, 142.5, 142.0, 141.9, 137.3, 132.5, 132.5, 132.3,
127.4, 126.5, 126.3, 126.0, 124.6, 123.3, 123.1, 122.8,
122.7, 122.2, 121.9, 119.8, 93.6, 93.3, 93.1, 93.0, 92.9,
90.2, 89.3, 34.4, 34.3, 31.8, 31.8, 31.7, 30.8, 30.7, 29.8,
29.7, 29.5, 29.4, 29.3, 23.8, 22.7, 22.5, 14.1.
4.2.11. Compound 5. Yield: 0.029 g, 60%; IR (cmꢁ1): 2964,
2929, 2858, 2111, 1718, 1682, 1599, 1581, 1460, 1448,
1337, 1249; H NMR (300 MHz): d 8.91 (s, 4H), 7.51 (s,
1
4H), 7.44 (s, 2H), 7.41 (s, 2H), 7.32 (s, 4H), 3.39 (septet,
4H), 2.88–2.81 (m, 8H), 2.72 (septet, 4H), 1.78–1.68 (m,
8H), 1.48–1.26 (m, 24H), 1.31 (d, 24H), 1.20 (d, 24H),
0.92–0.87 (m, 12H); 13C NMR (100 MHz): d 162.8, 146.0,
145.3, 141.8, 140.2, 139.4, 135.9, 132.2, 131.7, 127.6,
126.8, 126.5, 34.4, 31.7, 30.7, 29.5, 25.1, 23.8, 22.6, 22.5,
14.1.
4.2.6. Typical procedure for the preparation of com-
pounds 38–40, 46, and 47–53. Compound 52: a mixture
of 24 (0.377 g, 0.32 mmol), 35 (0.608 g, 0.70 mmol),
Pd(PPh3)4 (0.025 g) in NEt3 (40 mL) was stirred for
10 min. Then CuI (0.012 g) was added and the mixture

8212
A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
4.2.12. Compound 6. Yield: 0.016, 72%; IR (cmꢁ1): 2961,
2928, 2856, 2111, 1717, 1682, 1598, 1581, 1460, 1446,
1337, 1248; H NMR (400 MHz): d 8.92 (s, 4H), 7.52 (s,
off. Evaporation of the solvent under vacuum gave a residue,
which was purified by column chromatography on silica gel
(hexane/CH2Cl2 1:3). Yield: 0.73 g, 50%; IR (KBr, cmꢁ1):
1
1
4H), 7.44–7.39 (m, 8H), 7.32 (s, 4H), 3.39 (septet, 4H),
2.88–2.81 (m, 16H), 2.72 (septet, 4H), 1.78–1.68 (m,
16H), 1.46–1.26 (m, 48H), 1.32 (d, 24H), 1.20 (d, 24H),
0.96–0.84 (m, 24H); 13C NMR (100 MHz): d 169.7, 162.8,
146.0, 145.3, 143.7, 142.4, 142.0, 133.3, 132.5, 132.4,
131.7, 130.3, 127.7, 126.9, 126.5, 125.2, 124.6, 123.3,
122.8, 122.5, 121.9, 93.9, 93.3, 92.9, 90.2, 88.7, 34.4,
34.3, 34.1, 33.9, 31.8, 31.8, 31.7, 30.8, 30.7, 30.7, 29.8,
29.7, 29.5, 29.4, 29.3, 29.1, 23.8, 22.7, 22.6, 22.5, 21.9, 14.1.
2964, 2159, 1778, 1729; H NMR (300 MHz): d 8.52 (s,
2H), 7.40 (s, 4H), 2.62 (septet, J¼6.9 Hz, 4H), 1.17 (d,
J¼6.9 Hz, 24H), 0.29 (s, 18H); 13C NMR (100 MHz):
d 165.7, 147.2, 137.2, 127.9, 126.5, 125.5, 119.7, 104.7,
95.2, 29.5, 23.8, ꢁ0.1; FABMS: m/z 729.42 ((M+1)+).
4.2.17. Compound 13. IR (KBr, cmꢁ1): 3270, 2965, 2120,
1778, 1725; H NMR (400 MHz): d 8.54 (s, 2H), 7.44 (s,
1
4H), 3.16 (s, 2H), 2.64 (septet, 4H), 1.17 (d, J¼9.2 Hz,
24H); 13C NMR (100 MHz): d 165.7, 147.4, 137.3, 128.1,
126.8, 124.6, 119.8, 83.3, 78.0, 29.5, 23.8; FABMS: m/z
585.16 ((M+1)+). Analysis: C38H36N2O4 requires C, 78.06;
H, 6.21; N, 4.79. Found: C, 76.68; H, 6.11; N, 4.69.
4.2.13. Compound 7. Yield: 0.034 g, 76%; IR (cmꢁ1): 2958,
2926, 2856, 2110, 1716, 1681, 1597, 1581; 1H NMR: d 8.93
(s, 4H), 7.53 (s, 4H), 7.45 (s, 2H), 7.41–7.39 (m, 10H), 7.32
(s, 4H), 3.39 (septet, J¼6.9 Hz, 4H), 2.90–2.81 (m, 24H),
2.72 (septet, J¼6.9 Hz, 4H), 1.78–1.68 (m, 24H), 1.44–
1.30 (m, 96H), 1.21 (d, J¼6.9 Hz, 24H), 0.91–0.89 (m,
36H); 13C NMR: d 169.8, 162.8, 146.0, 145.3, 142.5,
142.0, 132.5, 132.4, 131.7, 130.2, 128.8, 127.7, 126.9,
126.5, 125.2, 124.6, 123.3, 122.9, 122.7, 122.5, 121.9,
94.0, 93.3, 93.1, 92.9, 90.2, 88.8, 34.4, 34.3, 34.2, 31.8,
31.8, 31.7, 30.8, 30.7, 29.8, 29.5, 29.4, 29.3, 23.8, 22.9,
22.7, 22.6, 22.5, 14.1, 14.1.
4.2.18. Compound 15. IR (KBr, cmꢁ1): 2959, 2926, 2148,
1779, 1729; H NMR (300 MHz): d 8.56 (s, 2H), 7.44 (s,
1
4H), 7.36 (s, 2H), 7.32 (s, 2H), 2.78–2.64 (m, 12H), 1.65–
1.60 (m, 8H), 1.42–1.30 (m, 24H), 1.19 (d, J¼6.9 Hz,
24H), 0.89 (m, 12H), 0.27 (s, 18H); 13C NMR (75 MHz):
d 165.8, 147.4, 142.8, 142.3, 137.3, 132.6, 132.3, 127.4,
126.3, 126.0, 122.7, 122.4, 119.8, 103.9, 99.1, 93.5, 89.2,
34.3, 34.2, 31.7, 30.8, 30.6, 29.5, 29.4, 29.3, 23.8, 22.7,
22.6, 14.1, 14.0, 0.0; FABMS: m/z 1265.60 ((M+1)+).
4.2.14. Compound 8. Yield: 0.043 g, 84%; IR (cmꢁ1): 2111,
1718, 1681; 1H NMR: d 8.92 (s, 4H), 7.52 (s, 4H), 7.44–7.32
(m, 20H), 3.39 (septet, 4H), 2.90–2.80 (m, 24H), 2.72 (sep-
tet, 4H), 1.77–1.20 (m, 144H), 0.91–0.88 (m, 48H); 13C
NMR: d 171.1, 164.8, 146.9, 146.5, 143.7, 142.8, 142.4,
141.9, 141.9, 139.4, 132.4, 132.3, 132.3, 130.0, 129.8,
127.0, 126.8, 124.0, 123.8, 123.0, 122.9, 122.8, 122.7,
122.6, 122.4, 122.2, 94.0, 93.6, 93.1, 93.0, 92.5, 92.3,
88.9, 88.4, 34.3, 34.2, 33.8, 31.8, 31.7, 31.7, 31.6, 30.8,
30.7, 30.2, 29.4, 29.4, 29.3, 29.2, 29.0, 28.4, 23.5, 22.6,
22.6, 14.0.
4.2.19. Compound 16. Yield: 0.158 g, 94%; IR (KBr,
cmꢁ1): 3274, 2961, 2926, 2855, 2215, 2108, 1777, 1728;
1H NMR (400 MHz): d 8.56 (s, 2H), 7.45 (s, 4H), 7.38 (s,
2H), 7.35 (s, 2H), 3.31 (s, 2H), 2.80–2.60 (m, 12H), 1.71–
1.64 (m, 8H), 1.44–1.32 (m, 24H), 1.20 (d, J¼8 Hz, 24H),
0.93–0.85 (m, 12H); 13C NMR (100 MHz): d 165.8, 147.4,
142.8, 142.3, 137.2, 133.0, 132.3, 127.4, 126.3, 125.8,
122.7, 121.7, 119.7, 93.5, 89.0, 82.4, 81.5, 34.2, 33.8,
31.7, 31.6, 30.7, 30.5, 29.5, 29.4, 29.1, 23.8, 22.6, 22.6,
14.1; FABMS: m/z 1121.64 ((M+1)+).
4.2.15. Compound 11. To a suspension of 1,2,4,5-benz-
enetetracarboxylic dianhydride, 10 (1.30 g, 6 mmol), in ace-
tic acid (30 mL) at 100 ꢀC was added 9 (3.20 g, 9.6 mmol)
in acetic acid (30 mL). The reaction mixture was heated to
120 ꢀC for 1 h and then allowed to cool gradually to room
temperature. The precipitate formed was filtered off, washed
with acetic acid (2ꢂ50 mL) and water (2ꢂ50 mL), and then
dried under vacuum. The crude product was redissolved in
CH2Cl2 and filtered through a short bed of silica gel (hex-
ane/CH2Cl2 1:1) to give 11 as a colorless solid. Yield:
4.7 g, 50%; IR (KBr, cmꢁ1): 2960, 2929, 2870, 1778,
4.2.20. Compound 17. Yield: 0.120 g, 61%; IR (KBr,
cmꢁ1): 2959, 2926, 2856, 2148, 1779, 1729; 1H NMR
(400 MHz): d 8.59 (s, 2H), 7.50 (s, 4H), 7.45 (s, 2H), 7.41
(s, 2H), 7.35 (s, 2H), 7.34 (s, 2H), 2.90–2.62 (m, 20H),
1.82–1.62 (m, 16H), 1.44–1.34 (m, 48H), 1.23 (d,
J¼7.2 Hz, 24H), 0.94–0.89 (m, 24H), 0.29 (s, 18H);
13C NMR (100 MHz): d 165.8, 147.4, 142.8, 142.4,
141.9, 141.8, 137.3, 132.5, 132.4, 127.4, 126.3, 126.0,
123.1, 123.0, 122.4, 122.2, 119.7, 104.0, 98.9, 93.5,
93.1, 93.0, 89.3, 34.4, 34.2, 34.2, 34.1, 31.8, 31.7, 31.7,
30.8, 30.7, 30.6, 29.5, 29.4, 29.3, 29.2, 23.8, 22.7, 22.6,
14.1, 0.0.
1
1727, 1567, 1455, 1364, 1244, 861, 847, 730; H NMR
(400 MHz): d 8.53 (s, 2H), 7.62 (s, 4H), 2.59 (septet,
J¼9.2 Hz, 1H), 1.15 (d, J¼9.2 Hz, 24H); 13C NMR
(100 MHz): d 165.2, 149.0, 136.8, 133.3, 125.9, 119.5,
97.2, 29.0, 23.4; FABMS: m/z 789.26 ((M+1)+). Analysis:
C34H34I2N2O4 requires C, 51.79; H, 4.35; N, 3.55. Found:
C, 51.89; H, 4.16; N, 3.47.
4.2.21. Compound 20. A mixture of 18 (5.9 g, 22 mmol), 19
(2.7 g, 10 mmol), m-cresol (50 mL), and isoquinoline
(1 mL) was heated to 210 ꢀC for 20 h. Then the mixture
was poured into a solution of MeOH/water (1:1, 200 mL)
and allowed to settle for 1 h. The precipitate was filtered
off, washed with MeOH/water (1:1, 2ꢂ100 mL), and dried.
The residue was purified by column chromatography over
silica gel (hexane/CH2Cl2 1:1) to give 20 as a pale yellow
solid. Pure samples are colorless. Yield: 1.7 g, 23%; IR
(KBr, cmꢁ1): 3021, 2932, 2872, 2968, 1714, 1677, 1581,
4.2.16. Compound 12. A mixture of 11 (1.60 g, 2 mmol),
trimethylsilylacetylene (1.28 mL, 9 mmol), Pd(PPh3)4
(0.075 g) in toluene (10 mL) and Et3N (25 mL) was stirred
for 10 min. Then CuI (0.030 g) was added and the reaction
mixture was stirred at room temperature for a further 2 h
and then at 50 ꢀC for 15 min. The salt formed was filtered
1
1467, 1445, 1343, 1250, 1222, 856, 788, 736; H NMR
(300 MHz): d 8.89 (s, 4H), 7.47 (s, 4H), 2.66 (septet,

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8213
J¼6.9 Hz, 4H), 1.15 (d, J¼6.9 Hz, 24H); 13C NMR
(100 MHz): d 162.7, 147.9, 131.7, 129.1, 127.8, 127.6,
126.8, 124.4, 29.4, 23.7; ES-MS (m/z): 743.40 ((M+1)+).
4.2.27. Compound 27. Yield: 2.24 g, 75%; IR (KBr, cmꢁ1):
3249, 3009, 2962, 2929, 2859, 2147, 1690, 1490, 1467; 1H
NMR (300 MHz): d 8.45 (s) and 8.03 (d) (1H), 7.64 and
7.04 (1H), 7.40–7.30 (4H), 3.21 (m) and 3.10 (m, 2H),
2.74 (m, 4H), 1.57 (m, 4H), 1.22 (m, 4H), 1.17 (d) and
1.12 (d) (6H), 0.88 (m, 6H), 0.26 (s, 9H); 13C NMR
(100 MHz): d 165.1, 160.5, 146.9, 146.4, 142.9, 142.8,
142.2, 132.6, 132.5, 132.2, 130.2, 129.8, 127.0, 126.8,
124.0, 123.8, 122.6, 122.4, 104.0, 103.9, 99.1, 98.9, 94.0,
93.5, 88.8, 88.3, 34.3, 34.2, 34.1, 31.7, 30.7, 30.6, 29.4,
29.3, 29.2, 28.8, 28.4, 23.5, 23.4, 22.6, 14.1, 0.1; FABMS:
m/z 570.88 ((M+1)+).
4.2.22. Compound 21. A mixture of 20 (0.500 g,
0.67 mmol), trimethylsilylacetylene (0.6 mL, 4 mmol), and
Pd(PPh3)4 (0.050 g) in toluene (40 mL) and Et3N (10 mL)
was stirred for 10 min. Then CuI (0.025 g) was added and
the reaction mixture was stirred for a further 4 days at
65 ꢀC. Then, additional amounts of Pd(PPh3)4 (0.050 g), tri-
methylsilylacetylene (0.5 mL), and CuI (0.025 g) were
added to the reaction mixture, which was stirred for a further
2 days at 75 ꢀC. The salt formed was filtered off and washed
with toluene (2ꢂ20 mL). Evaporation of the solvent under
vacuum gave a residue, which was purified by column chro-
matography on silica gel (hexane/CH2Cl2 1:3). Yield: 0.40 g,
77%, pale yellow solid; IR (KBr, cmꢁ1): 2964, 2935, 2873,
4.2.28. Compound 28. Yield: 2.49 g, 93%; IR (KBr, cmꢁ1):
3302, 3019, 2964, 2929, 2870, 2859, 2108, 1691; 1H NMR
(300 MHz): d 8.49 (s) and 8.03 (d, J¼11.7 Hz) (1H), 7.36–
7.34 (4H), 7.12 (d, J¼11.7 Hz) and 6.76 (s) (1H), 3.30 and
3.29 (1H), 3.29–3.17 (m, 2H), 2.82–2.72 (m, 4H), 1.72–1.60
(m, 4H), 1.44–1.29 (m, 12H), 1.24 (d, 12H), 0.92–0.87 (m,
6H); FABMS: m/z 498.65 ((M+1)+). Analysis: C35H47NO
requires C, 84.45; H, 9.52; N, 2.81. Found: C, 84.11; H,
9.36; N, 2.84.
1
2155, 1716, 1678, 1580; H NMR (400 MHz): d 8.90 (s,
4H), 7.49 (s, 4H), 7.37 (s, 2H), 7.32 (s, 2H), 2.84–2.64 (m,
12H), 1.74–1.60 (m, 8H), 1.45–1.29 (m, 24H), 1.18 (d,
J¼6.9 Hz, 24H), 0.93–0.87 (m, 12H), 0.27 (s, 18H); 13C
NMR (100 MHz): d 162.7, 145.8, 131.6, 130.4, 128.0,
127.6, 126.8, 124.7, 105.1, 94.5, 29.3, 23.8, 0.02.
4.2.29. Compound 29. Yield: 1.53 g, 89%; IR (KBr, cmꢁ1):
3250, 2962, 2929, 2859, 2157, 1690, 1490, 1467; 1H NMR
(250 MHz): d 8.46 (d, J¼1 Hz) and 8.04 (d, J¼11 Hz)
(1H), 7.42–7.32 (m, 6H), 7.73 (d, J¼11 Hz) and 7.06 (s)
(1H), 3.24 (m) and 3.11 (m) (2H), 2.84–2.70 (m, 8H),
1.78–1.22 (m, 36H), 0.89 (m, 12H), 0.27 (s, 9H); 13C
NMR (100 MHz): d 165.2, 160.6, 146.9, 146.4, 142.7,
142.3, 141.9, 141.9, 141.7, 132.4, 132.3, 132.2, 130.2,
129.9, 127.0, 126.8, 124.0, 123.8, 123.0, 122.9, 122.9,
122.8, 122.4, 122.4, 122.3, 122.2, 104.0, 104.0, 99.0, 98.9,
94.0, 93.6, 93.1, 93.0, 92.9, 88.8, 88.4, 34.3, 34.2, 34.1,
31.8, 31.7, 30.7, 30.6, 30.5, 29.4, 29.4, 29.3, 29.2,
28.8, 28.4, 23.5, 23.4, 22.6, 14.1, ꢁ0.1; FABMS: m/z
837.11 (M+).
4.2.23. Compound 22. Yield: 0.230 g, 71%; 1H NMR
(400 MHz): d 8.89 (s, 4H), 7.49 (s, 4H), 3.15 (s, 2H), 2.68
(septet, J¼6.9 Hz, 4H), 1.58 (d, J¼6.9 Hz, 24H); 13C
NMR (100 MHz): d 162.7, 146.0, 131.7, 130.7, 128.4,
127.6, 126.8, 123.8, 83.6, 29.2, 23.8.
4.2.24. Compound 23. Yield: 0.478 g, 73%; IR (KBr,
cmꢁ1): 2959, 2926, 2856, 2148, 1716, 1680, 1580; 1H
NMR (400 MHz): d 8.90 (s, 4H), 7.34 (s, 2H), 7.32 (s,
1H), 7.33 (s, 2H), 2.81 (m, 4H), 2.72 (m, 8H), 1.64 (m,
8H), 1.42–1.32 (m, 24H), 1.19 (d, J¼6.9 Hz, 24H), 0.91
(m, 12H), 0.28 (s, 18H); 13C NMR (100 MHz): d 162.8,
146.0, 142.8, 142.3, 134.3, 134.2, 132.5, 132.3, 131.7,
130.2, 129.5, 128.4, 128.3, 127.7, 127.6, 126.9, 125.2,
122.6, 122.5, 104.0, 99.0, 93.8, 88.7, 34.3, 34.2,
31.8, 31.7, 30.8, 30.6, 29.4, 29.3, 23.8, 22.7, 22.6, 14.1,
14.0, 0.0.
4.2.30. Compound 30. Yield: 1.32 g, 98%; 1H NMR
(300 MHz): d 8.50 (d, J¼1 Hz) and 8.04 (d, J¼11 Hz)
(1H), 7.39–7.33 (6H), 6.90 (d, J¼11 Hz) and 6.70 (s)
(1H), 3.30 (s, 1H), 3.24–3.09 (m, 2H), 2.84–2.72 (m, 8H),
1.70–1.59 (m, 8H), 1.40–1.30 (m, 24H), 1.24 (d, 12H),
0.90–0.85 (m, 12H).
4.2.25. Compound 24. Yield: 0.377 g, 87%; IR (KBr,
cmꢁ1): 3266, 2958, 2926, 2855, 2108, 1715, 1679, 1580;
1H NMR (400 MHz): d 8.91 (s, 4H), 7.51 (s, 4H), 7.40 (s,
2H), 7.36 (s, 2H), 3.32 (s, 2H), 2.86–2.67 (m, 12H), 1.77–
1.62 (m, 8H), 1.48–1.32 (m, 24H), 1.20 (d, J¼6.9 Hz,
24H), 0.91 (m, 12H); 13C NMR (100 MHz): d 162.8,
146.0, 142.8, 142.3, 134.3, 134.2, 132.5, 132.3, 131.7,
130.2, 129.5, 127.7, 127.6, 126.9, 125.2, 122.6, 122.5,
104.0, 99.0, 93.8, 88.7, 34.3, 33.9, 31.7, 30.7, 30.5, 29.4,
29.3, 23.8, 22.7, 22.6, 14.1.
4.2.31. Compound 31. Yield: 0.130 g, 73%; 1H NMR
(400 MHz): d 8.49 (s) and 8.04 (d, J¼11 Hz) (1H), 7.41–
7.30 (8H), 7.17 (d, J¼11 Hz) and 6.79 (s) (1H), 3.28–3.08
(m, 2H), 2.88–2.71 (m, 12H), 1.78–1.60 (m, 12H), 1.48–
1.30 (m, 36H), 1.26–1.24 (m, 12H), 0.9 (m, 18H), 0.24 (s,
9H); 13C NMR (100 MHz): d 164.9, 160.5, 146.9, 146.5,
142.8, 142.4, 142.0, 141.9, 141.8, 132.5, 132.4, 132.4,
132.3, 130.1, 129.8, 127.1, 126.9, 124.0, 123.9, 123.1,
123.0, 122.9, 122.8, 122.7, 122.4, 122.3, 122.2, 104.0,
99.0, 94.1, 93.6, 93.2, 93.0, 92.9, 88.9, 88.4, 34.3, 34.2,
34.1, 31.8, 31.7, 30.8, 30.7, 30.7, 30.6, 29.4, 29.3, 28.8,
28.4, 23.5, 23.5, 22.6, 14.1, 0.0; FABMS: m/z 1106.37
((M+1)+).
4.2.26. Compound 25. Yield: 0.286 g, 76%; IR (KBr,
cmꢁ1): 2959, 2926, 2856, 2149, 1716, 1679, 1580; 1H
NMR (400 MHz): d 8.90 (s, 4H), 7.49–7.29 (m, 12H),
2.80–2.68 (m, 12H), 1.72–1.64 (m, 16H), 1.41–1.33 (m,
48H), 1.18 (d, J¼12 Hz, 24H), 0.93–0.87 (m, 24H), 0.27
(s, 18H); 13C NMR (100 MHz): d 162.8, 146.0, 142.8,
142.3, 134.3, 134.2, 132.5, 132.3, 131.7, 130.2, 129.5,
128.4, 128.3, 127.7, 127.6, 126.9, 125.2, 122.6, 104.0,
98.9, 93.8, 88.8, 34.3, 34.2, 31.8, 31.7, 30.8, 30.6, 29.4,
29.3, 23.8, 22.7, 22.6, 14.1, 14.1, 0.0.
4.2.32. Compound 32. Yield: 0.045 g, 89%; 1H NMR
(300 MHz): d 8.67 (d, J¼1 Hz) and 8.22 (d, J¼11 Hz)
(1H), 7.58–7.43 (8H), 7.19 (d, J¼11 Hz) and 6.94 (1H),
3.48 (s, 1H), 3.44–3.24 (m, 2H), 3.03–2.71 (m, 12H),

8214
A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
1.91–1.72 (m, 12H), 1.51–1.48 (m, 36H), 1.43–1.41 (m,
12H), 1.10–1.03 (m, 18H).
4.2.37. Compound 38. IR (KBr, cmꢁ1): 3228, 2960, 2926,
2857, 1679, 1666, 1597, 1511; 1H NMR (300 MHz):
d 8.49 (s) and 8.04 (d, J¼11 Hz) (1H), 7.40–7.35 (6H),
7.11 (d, J¼11 Hz) and 6.78 (s) (1H), 3.26–3.07 (m, 4H),
2.82 (m, 4H), 1.72–1.64 (m, 4H), 1.44–1.23 (m, 36H),
0.89–0.86 (m, 6H); 13C NMR (100 MHz): d 165.0, 160.5,
146.9, 146.5, 142.4, 132.3, 130.1, 129.8, 127.1, 126.9,
124.0, 122.45, 94.1, 93.7, 88.8, 88.3, 34.3, 31.7, 30.7,
29.4, 28.8, 28.4, 23.5, 22.6, 14.1; Analysis: C48H64N2O2 re-
quires C, 82.24; N, 9.20; N, 4.00. Found: C, 81.20; H, 9.11;
N, 3.85.
4.2.33. Compound 34. IR (KBr, cmꢁ1): 3201, 2962, 2925,
2860, 1687, 1669, 1524, 1459, 1387, 879; 1H NMR
(300 MHz): d 8.48 (s) and 8.03 (d, J¼11 Hz) (1H), 7.68
(s) and 7.67 (s) (1H), 7.38–7.33 (3H), 7.11 (d, J¼11 Hz)
and 6.80 (s) (1H), 3.23–3.10 (m, 2H), 2.77–2.63 (m, 4H),
1.72–1.54 (m, 4H), 1.41–1.28 (m, 12), 1.23 (d, J¼6.9 Hz,
12H), 0.88 (m, 6H); 13C NMR (100 MHz): d 164.9, 160.4,
146.9, 146.5, 144.2, 142.8, 142.7, 139.5, 139.4, 132.2, 130.1,
129.8, 127.0, 126.8, 123.9, 123.8, 123.7, 122.6, 122.4, 101.1,
100.9, 93.5, 93.1, 88.2, 87.6, 40.2, 34.0, 33.9, 31.6, 30.7,
30.2, 29.4, 29.3, 29.0, 28.8, 28.4, 23.6, 23.4, 23.5, 22.6,
22.5, 14.1, 14.0; FABMS: m/z 600.54 ((M+1)+). Analysis:
C33H46INO requires C, 66.10; H, 7.73; N, 2.34. Found: C,
66.41; H, 7.94; N, 2.27.
4.2.38. Compound 39. Yield: 0.720 g, 77%; IR (KBr,
cmꢁ1): 3233, 2959, 2926, 2855, 1688, 1667, 1597, 1499,
1
1464; H NMR (300 MHz): d 8.45 (d, J¼1 Hz) and 8.04
(d, J¼11 Hz) (1H), 7.41–7.36 (8H), 7.71 (d, J¼11 Hz) and
7.03 (s) (1H), 3.27–3.08 (m, 4H), 2.86–2.81 (m, 8H),
1.77–1.69 (m, 8H), 1.44–1.20 (m, 48H), 0.91–0.86 (m,
12H); 13C NMR (100 MHz): d 165.2, 160.6, 146.9, 146.4,
142.4, 141.9, 141.9, 132.5, 132.3, 130.2, 129.8, 127.0,
126.8, 123.9, 123.8, 123.8, 123.0, 122.9, 122.8, 122.7,
122.5, 122.4, 122.2, 122.2, 94.1, 94.0, 93.6, 93.6, 93.1,
93.0, 93.0, 92.9, 88.9, 88.8, 88.4, 88.3, 34.4, 34.3, 31.8,
31.7, 30.8, 30.7, 29.4, 29.2, 23.5, 22.3, 14.1, 14.0.
4.2.34. Compound 35. Yield: 3.85 g, 65%; IR (KBr, cmꢁ1):
3200, 2960, 2924, 2856, 1685, 1597, 1524, 1464, 1385, 879;
1H NMR (300 MHz): d 8.50 (s) and 8.04 (d) (1H), 7.69 (s,
1H), 7.39–7.30 (5H), 6.98 (d) and 6.75 (s) (1H), 3.30–3.08
(m, 2H), 2.84–2.63 (m, 8H), 1.74–1.55 (m, 8H), 1.44–1.25
(m, 24H), 1.23 (d, 12H), 0.88 (m, 12H); 13C NMR
(100 MHz): d 164.8, 160.4, 146.9, 146.5, 143.7, 142.8,
142.4, 142.0, 139.5, 132.4, 132.3, 132.3, 130.0, 129.7,
127.1, 126.9, 124.1, 123.9, 123.0, 122.9, 122.9, 122.8,
122.7, 122.6, 122.5, 122.2, 100.8, 94.1, 93.6, 93.1, 93.0,
92.5, 92.3, 88.9, 88.4, 40.2, 34.4, 34.2, 33.9, 31.7, 31.7,
30.8, 30.7, 30.2, 29.4, 29.3, 29.2, 28.8, 28.4, 23.5, 22.6,
22.6, 14.1; FABMS: m/z 867.0 (M+). Analysis: C53H74INO
requires C, 73.33; H, 8.59; N, 1.61. Found: C, 74.16; H,
8.88; N, 1.80.
4.2.39. Compound 40. Yield: 0.176 g, 11% (Scheme 2b); IR
(KBr, cmꢁ1): 3233, 2957, 2924, 2854, 1687, 1666, 1596,
1499, 1464, 1383, 1363, 1244, 892, 879, 723; H NMR
1
(300 MHz): d 8.50 (d, J¼1 Hz) and 8.04 (d, J¼11 Hz)
(1H), 7.40–7.35 (10H), 6.98 (d, J¼11 Hz) and 6.76 (s)
(1H), 3.26–3.07 (m, 4H), 2.86–2.78 (m, 12H), 1.76–1.65
(m, 12H), 1.44–1.20 (m, 60H), 0.91–0.86 (m, 18H); 13C
NMR (100 MHz): d 164.9, 160.5, 146.9, 146.5, 142.4,
142.0, 141.9, 133.3, 132.4, 132.3, 131.1, 132.0, 130.0,
129.8, 128.9, 128.6, 128.4, 127.1, 126.9, 124.0, 123.8,
123.6, 123.0, 122.8, 122.2, 94.1, 93.6, 93.0, 88.9, 88.4,
34.3, 34.2, 31.8, 31.7, 31.7, 30.8, 30.7, 29.4, 29.3, 29.0,
28.9, 28.4, 23.6, 23.5, 22.6, 14.1. Analysis: C88H120N2O2 re-
quires C, 85.38; N, 9.77; N, 2.26. Found: C, 82.99; H, 9.44;
N, 2.53.
4.2.35. Compound 36. Yield: 1.75 g, 88%; IR (KBr, cmꢁ1):
3329, 2954, 2922, 2852, 1658, 1595, 1497, 1458, 1381, 878;
1H NMR (250 MHz): d 8.47 (s) and 8.07 (d) (1H), 7.70 (s,
1H), 7.42–7.33 (7H), 7.65 (d) and 7.02 (s) (1H), 3.25–3.22
(m, 2H), 2.90–2.62 (m, 12H), 1.80–1.55 (m, 12H), 1.50–
1.20 (m, 48H), 0.90 (m, 18H); 13C NMR (75 MHz):
d 165.2, 146.9, 146.4, 143.7, 142.8, 142.4, 141.9, 139.4,
132.4, 130.2, 129.8, 127.0, 126.8, 124.0, 123.8, 123.0,
122.9, 122.8, 122.7, 122.6, 122.2, 100.8, 94.1, 93.6, 93.1,
93.0, 92.5, 92.3, 88.9, 88.4, 40.2, 34.3, 34.2, 33.9, 31.8,
31.7, 31.6, 30.8, 30.6, 30.2, 29.4, 29.3, 29.0, 28.8, 28.4,
23.5, 22.6, 14.1; ES-MS: m/z 1135.05 (M+). Analysis:
C73H102INO requires C, 77.15; H, 9.05; N, 1.23. Found: C,
76.46; H, 8.99; N, 1.24.
4.2.40. Compound 41. Yield: 0.098 g, 9%; 1H NMR
(300 MHz): d 8.51 and 8.04 (2H), 7.40–7.26 (14H), 7.03
and 6.78 (2H), 3.25–3.01 (m, 4H), 2.86–2.84 (m, 20H),
1.74–1.72 (m, 20H), 1.43–1.24 (m, 84H), 0.91–0.89 (m,
30H); 13C NMR (100 MHz): d 164.8, 160.4, 146.9, 146.5,
142.4, 141.9, 132.4, 132.3, 130.0, 129.7, 128.4, 127.1,
126.9, 124.1, 123.1, 122.8, 122.4, 122.2, 94.0, 93.6, 93.1,
88.9, 88.4, 34.3, 34.2, 31.8, 31.7, 30.8, 30.7, 29.4, 29.3,
28.8, 28.4, 23.5, 22.7, 14.1. Analysis: C128H176N2O2 re-
quires C, 86.62; N, 10.00; N, 1.58. Found: C, 84.64; H,
9.86; N, 1.53.
4.2.36. Compound 37. Yield: 0.042 g, 72%; IR (KBr, cmꢁ1):
2954, 2925, 2852, 1685, 1669, 1498, 1460, 1384, 879;
1H NMR (300 MHz): d 8.50 (d, J¼1 Hz) and 8.04 (d,
J¼11 Hz) (1H), 7.69 (s, 1H), 7.41–7.32 (9H), 6.94 (d,
J¼11 Hz) and 6.73 (d, J¼1 Hz) (1H), 3.29–3.02 (m, 2H),
2.87–2.64 (m, 16H), 1.76–1.62 (m, 16H), 1.45–1.30 (m,
48H), 1.25 (d, 12H), 0.94–0.87 (m, 24H); 13C NMR
(100 MHz): d 162.8, 148.6, 146.0, 145.2, 142.4, 141.9,
132.4, 132.3, 131.7, 130.2, 129.0, 128.2, 127.5, 126.8, 126.4,
125.2, 125.2, 124.6, 123.3, 122.8, 122.6, 121.9, 93.9, 93.3,
93.0, 90.2, 88.7, 45.7, 44.4, 34.4, 34.3, 34.2, 31.8, 31.8,
31.7, 31.6, 30.8, 30.7, 29.8, 29.4, 29.3, 29.2, 23.8, 22.7, 22.6,
22.4, 14.1, 13.7, 13.2, 12.7. Analysis: C93H130INO requires
C, 79.50; H, 9.33; N, 1.00. Found: C, 81.23; H, 8.79; N, 2.65.
4.2.41. Compound 42. Yield: 0.009 g, 15%; 1H NMR
(300 MHz): d 8.50 and 8.40 (2H), 7.55–7.28 (18H), 6.78
and 6.69 (2H), 3.23–3.10 (m, 4H), 2.86–2.82 (m, 28H),
1.74–1.66 (m, 28H), 1.43–1.24 (m, 108H), 0.89–0.87 (m,
42H); MALDI-TOF (in DTH): 2311.65 ((M+1)+).
4.2.42. Compound 43. A mixture of 33 (4.98 g, 10 mmol),
acetamide (750 mg, 15 mmol), K3PO4 (5 g), CuI (110 mg),
and N,N0-dimethylethylenediamine (110 mg) was heated to
80 ꢀC for 24 h and then cooled to room temperature. After

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8215
addition of 40 mL ethyl acetate, the resulting mixture was
filtered through a plug of silica gel and rinsed with several
portions of ethyl acetate. The solvent was removed and the
residue dried under vacuum. The residue was redissolved
in a 1:1 mixture of ethanol and dichloromethane (100 mL).
To this solution was added 25 g of silica gel with stirring.
The solvent was removed and the residue dried slowly under
vacuum. The silica with the adsorbed product mixture was
added to the top of a silica gel column (4ꢂ20 cm), which
had been prepared with a 99:1 mixture of hexane/ethyl ace-
tate. Remaining 33 (1.1 g, 2.2 mmol) was eluted with the
same solvent mixture. The product was eluted with a 10:1
mixture of hexane/ethyl acetate. Yield: 1.99 g, 59% based
on consumed starting material; IR (KBr, cmꢁ1): 3020,
2957, 2929, 2858, 1688, 1501, 1465; 1H NMR (300 MHz):
7.68 (s, 1H), 7.59 (s, 1H), 6.91 (br s, 1H), 2.64 (m, 2H),
2.45 (m, 2H), 2.18 (s, 3H), 1.59–1.52 (m, 4H), 1.40–1.26
(m, 12H), 0.91–0.87 (m, 6H); 13C NMR (100 MHz):
d 168.3, 143.8, 139.7, 135.3, 133.4, 124.4, 96.1, 40.5,
31.6, 31.6, 30.5, 30.2, 29.6, 29.1, 29.0, 24.3, 22.6, 22.5,
14.1, 14.0; FABMS: m/z 430.36 (M+). Analysis:
C20H32INO requires C, 55.94; H, 7.51; N, 3.26. Found: C,
55.53; H, 7.40; N, 3.18.
(300 MHz): d 8.47 (d, J¼1 Hz) and 8.07 (d, J¼12 Hz)
(1H), 7.40–7.34 (6H), 7.28 (d, J¼12 Hz) and 6.83 (s)
(1H), 3.79 (q, J¼7.2 Hz, 4H), 3.27–3.07 (m, 2H), 2.84–
2.76 (m, 8H), 1.73–1.57 (m, 8H), 1.45–1.23 (m, 42H),
0.96–0.87 (m, 12H); 13C NMR (100 MHz): d 165.0, 160.5,
148.5, 146.9, 146.4, 143.7, 142.9, 142.3, 141.7, 134.9,
134.7, 133.8, 133.8, 132.3, 132.2, 130.0, 129.7, 127.1,
126.9, 124.2, 124.0, 123.8, 123.5, 121.8, 121.6, 119.0,
118.9, 118.6, 116.4, 116.3, 94.3, 94.1, 93.7, 93.3, 91.2,
91.1, 89.1, 88.6, 34.7, 34.4, 34.2, 31.8, 31.8, 31.4, 31.3,
31.2, 31.0, 30.9, 30.8, 29.7, 29.4, 29.3, 28.8, 28.4, 23.5,
22.6, 14.1; FABMS: m/z 842.07 ((M+1)+); Analysis:
C57H84N4O requires C, 81.37; H, 10.06; N, 6.66. Found:
C, 80.35; H, 10.36; N, 5.79.
4.2.46. Alternative route to 35. A mixture of 46 (0.035 g,
0.04 mmol) and methyl iodide (0.29 g, 2.0 mmol) was
heated to 110 ꢀC in a sealed tube for 10 h. Then, the mixture
was cooled to room temperature, diluted with hexanes, and
purified over silica gel using hexanes/ethyl acetate (1:1).
Yield: 0.025 g, 72%.
4.2.47. Compound 47. Yield: 0.240, 37%; IR (KBr, cmꢁ1):
3380, 3234, 2961, 2927, 2856, 1779, 1732, 1679; 1H
NMR (300 MHz): d 8.56 (s, 2H), 8.51 (d, J¼1 Hz) and
8.04 (d, J¼12 Hz) (2H), 7.46 (s), 7.42 (s), 7.41 (s), 7.36
(s) (12H), 6.82 (d, J¼12 Hz) and 6.64 (s, J¼1 Hz) (2H),
3.22 (septet) and 3.12 (septet) (4H), 2.86–2.81 (m, 8H),
2.68 (septet, 4H), 1.74–1.68 (m, 8H), 1.45–1.33 (m, 24H),
1.25 (d, J¼7 Hz, 24H), 1.21 (d, J¼7 Hz, 24H), 0.92–0.87
(m, 12H); 13C NMR (75 MHz): d 165.8, 165.0, 147.4,
146.9, 146.5, 142.5, 142.4, 137.2, 132.4, 130.2, 127.4,
127.1, 126.9, 126.2, 125.9, 124.0, 122.7, 122.2, 119.8,
94.2, 93.6, 88.8, 88.3, 85.7, 34.3, 31.7, 30.7, 29.4, 28.8,
28.4, 23.8, 23.5, 22.7, 14.1. Analysis: C104H126N4O6
requires: C, 81.74; H, 8.31; N, 3.67. Found: C, 80.32; H,
8.22; N, 3.66.
4.2.43. Compound 44. A mixture of 43 (2 g), 10 mL concd
HCl, and 5 mL ethanol was heated to 85 ꢀC for 5 h. After
cooling to room temperature, 40 mL of water was added.
Then a 40% KOH solution was added until the solution
became basic. The product was extracted with ether to give
the product as a light brown oil, which partly crystallized
after solvent removal. (This raw product was sufficiently
pure for the next stage.) A sample was further purified by
chromatography on silica gel using a 10:1 mixture of hex-
ane/ethyl acetate as the eluent. The purified product partly
crystallized in the form of colorless crystals. 1H NMR
(400 MHz): d 7.42 (s, 1H), 6.56 (s, 1H), 3.57 (s, 2H), 2.57
(m, 2H), 2.39 (m, 2H), 1.60–1.54 (m, 4H), 1.40–1.33 (m,
12H), 0.91 (m, 6H); 13C NMR (100 MHz): d 144.2, 143.4,
139.3, 127.1, 116.3, 86.5, 40.3, 31.7, 30.5, 30.3, 29.4, 29.3,
29.1, 28.6, 22.6, 14.1.
4.2.48. Compound 48. Yield: 0.192 g, 56%; IR (KBr,
cmꢁ1): 3386, 3245, 2959, 2926, 2855, 1779, 1730, 1691;
1H NMR (300 MHz): d 8.57 (s, 2H), 8.49 (d, J¼1 Hz) and
8.05 (d, J¼12 Hz) (2H), 7.48 (s, 4H), 7.43–7.36 (12H),
7.14 (d, J¼12H) and 6.81 (s) (2H), 3.27–3.08 (m, 4H),
2.88–2.83 (m, 16H), 2.74–2.64 (m, 4H), 1.74–1.71 (m,
16H), 1.45–1.27 (m, 48H), 1.27–1.21 (m, 48H), 0.92–0.88
(m, 24H); 13C NMR (75 MHz): d 165.7, 164.9, 147.4,
146.9, 146.5, 142.5, 142.4, 142.0, 137.3, 132.6, 132.4,
132.3, 130.1, 129.7, 127.4, 127.1, 126.9, 126.3, 126.0,
124.0, 123.9, 123.0, 122.8, 122.5, 122.2, 119.8, 93.6, 93.0,
89.3, 88.9, 88.4, 85.8, 34.4, 34.2, 31.8, 31.7, 30.8, 30.7,
29.5, 29.3, 28.8, 28.4, 23.8, 23.5, 22.7, 14.1; MALDI-TOF
(in DTH): 2065.38 (M+); Analysis: C144H182N4O6 requires
C, 83.75; H, 8.88; N, 2.71. Found: C, 80.24; H, 8.59; N, 2.73.
4.2.44. Compound 45. To a stirred mixture of 44 (0.774 g,
2 mmol) and BF3$Et2O (0.37 mL, 3 mmol) in 10 mL
CH2Cl2 at 0 ꢀC was added t-BuNO (0.3 mL, 2.5 mmol)
and stirring was continued for 30 min at the same tempera-
ture. Then K2CO3 (1 g) and HNEt2 (1 mL) were added se-
quentially. After stirring for 1 h at room temperature, the
mixture was poured into water. The organic product was ex-
tracted with ethyl acetate. The combined extracts were dried
with MgSO4 and filtered, and then the solvent was removed
under vacuum. The product was purified by chromatography
on silica gel, using hexane/ethyl acetate (98:2) as the eluent.
Yellow-orange oil. Yield: 0.869 g, 92%; IR (toluene, cmꢁ1):
1
2957, 2930, 2857, 1467, 1379, 1394, 1237, 1100, 755; H
NMR (300 MHz): d 7.59 (s, 1H), 7.19 (s, 1H), 3.75 (q,
J¼7.2 Hz, 4H), 2.73–2.62 (m, 4H), 1.63–1.52 (m, 4H),
1.42–1.25 (m, 18H), 0.93–0.86 (m, 6H); 13C NMR
(100 MHz): d 148.7, 142.9, 140.0, 137.0, 117.1, 95.7,
40.6, 31.7, 31.7, 31.1, 31.0, 30.4, 29.3, 29.1, 22.6, 22.6,
14.1; FABMS: m/z 472.41 ((M+1)+).
4.2.49. Compound 49. Yield: 0.200 g, 95%; IR (KBr,
cmꢁ1): 3400, 3300, 2958, 2925, 2855, 1730, 1690; 1H
NMR (300 MHz): d 8.57 (s, 2H), 8.50 (s) and 8.05 (d,
J¼12 Hz) (2H), 7.47 (s, 4H), 7.43–7.36 (20H), 6.90 (d)
and 6.72 (s) (2H), 3.22 (septet) and 3.12 (septet) (4H),
2.90–2.80 (m, 24H), 2.69 (septet, 4H), 1.78–1.68 (m,
24H), 1.48–1.21 (m, 120H), 0.90–0.88 (m, 36H); 13C
NMR (75 MHz): d 165.9, 164.8, 147.4, 147.0, 146.5,
142.5, 142.4, 141.9, 137.3, 132.5, 132.5, 132.4, 130.0,
4.2.45. Compound 46. Yield: 0.302 g, 90%; IR (KBr,
cmꢁ1): 2959, 2929, 2857, 1691, 1466; 1H NMR

8216
A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
127.4, 127.1, 126.9, 126.3, 123.9, 122.8, 122.2, 119.8, 93.6,
93.1, 93.0, 89.3, 88.6, 34.4, 34.2, 31.8, 31.8, 30.8, 30.7, 29.5,
29.3, 23.8, 23.5, 22.7, 14.1; MALDI-TOF (in DTH):
2604.08 ((M+2)+); Analysis: C184H238N4O6 requires C,
84.94; H, 9.22; N, 2.15. Found: C, 83.11; H, 9.14; N, 2.08.
99.1, 93.2, 90.1, 34.2, 34.1, 31.7, 31.6, 30.7, 30.5, 29.7,
29.3, 29.2, 22.6, 22.4, 14.1, 14.0, ꢁ0.1. MS: m/z 551.41 (M+).
4.2.55. Compound 55. Yield: 0.240 g, 98%; IR (KBr,
cmꢁ1): 2961, 2928, 2856, 2151, 2112, 1597, 1496, 1464;
1H NMR (300 MHz): d 7.39 (s, 1H), 7.37 (s, 1H), 7.33–
7.31 (4H), 3.02 (septet, 2H), 2.78–2.64 (m, 8H), 1.69–1.55
(m, 8H), 1.37–1.23 (m, 36H), 0.86–0.79 (m, 12H), 0.20 (s,
9H); 13C NMR (100 MHz): d 170.1, 145.2, 142.8, 142.4,
142.0, 141.8, 132.5, 132.4, 132.3, 126.5, 124.6, 123.9,
123.3, 122.9, 122.5, 121.9, 104.0, 99.0, 93.3, 93.2, 92.8,
90.2, 34.3, 34.2, 34.1, 34.1, 31.8, 31.7, 31.7, 30.8, 30.7,
30.6, 30.6, 29.8, 29.4, 29.3, 29.2, 22.6, 22.4, 14.1, 14.0,
0.0; MS: m/z 819.61 (M+).
4.2.50. Compound 50. Yield: 0.128 g, 91%; IR (cmꢁ1):
2958, 2927, 2856, 1717, 1684; 1H NMR (400 MHz):
d 8.93 (s, 4H), 8.57 (s) and 8.05 (d, J¼11 Hz) (2H), 7.52–
7.47 (12H), 7.37 (d, J¼11 Hz) and 6.78 (s) (2H), 3.12 (m,
4H), 2.83 (m, 8H), 2.71 (m, 4H), 1.82–1.35 (m, 32H),
1.18–1.26 (m, 48H), 0.92–0.88 (m, 12H); 13C NMR
(100 MHz): d 164.7, 162.9, 162.8, 146.9, 146.5, 146.0,
142.4, 132.5, 132.4, 131.7, 127.6, 127.1, 126.9, 125.2,
124.1, 94.0, 91.3, 85.9, 39.4, 34.4, 31.8, 31.7, 30.8, 29.5,
29.4, 28.4, 23.8, 23.5, 22.7, 14.1. Analysis: C108H128N4O6
requires: C, 82.19; H, 8.17; N, 3.55. Found: C, 80.16; H,
8.17; N, 3.40.
4.2.56. Compound 56. Yield: 0.212 g, 94%; IR (KBr,
cmꢁ1): 2959, 2926, 2855, 2150, 2111, 1599, 1500, 1466,
1461; H NMR (300 MHz): d 7.40 (s, 1H), 7.39 (s, 1H),
1
7.38 (s, 2H), 7.34–7.32 (4H), 3.40 (septet, 2H), 2.87–2.72
(m, 12H), 1.71–1.61 (m, 12H), 1.45–1.28 (m, 84H), 0.90
(m, 18H), 0.28 (s, 9H); 13C NMR (75 MHz): d 170.1,
145.3, 142.8, 142.5, 142.0, 141.9, 141.8, 132.5, 132.4,
132.4, 126.5, 124.6, 123.9, 123.3, 122.9, 122.9, 122.7,
122.4, 121.9, 104.0, 99.0, 93.3, 93.3, 93.0, 93.0, 92.9,
90.2, 34.3, 34.2, 34.1, 31.8, 31.7, 31.7, 30.8, 30.7, 30.6,
29.8, 29.4, 29.3, 22.6, 22.5, 14.1, 14.1, 0.0; MS: m/z
1087.77 (M+).
4.2.51. Compound 51. Yield: 0.210 g, 58%; IR (cmꢁ1):
2957, 2926, 2856, 1718, 1683, 1598, 1580, 1499, 1466,
1459, 1338, 1248; H NMR (300 MHz): d 8.92 (s, 4H),
1
8.50 (s) and 8.05 (d, J¼12 Hz) (2H), 7.53 (s, 4H), 7.44–
7.37 (12H), 7.06 (d, J¼12 Hz) and 6.78 (s) (2H), 3.27–
3.08 (m, 4H), 2.86–2.68 (m, 20H), 1.78–1.70 (m, 16H),
1.44–1.20 (m, 96H), 0.94–0.84 (m, 24H); 13C NMR
(75 MHz): d 165.0, 162.8, 146.9, 146.4, 146.0, 142.4,
141.9, 132.5, 132.4, 131.7, 130.3, 127.6, 127.0, 126.8,
125.2, 122.8, 122.4, 94.1, 93.0, 88.6, 88.0, 85.8, 34.4,
34.2, 31.8, 31.8, 30.8, 30.7, 29.5, 29.3, 29.1, 28.4, 23.8,
23.5, 22.7, 14.1; Analysis: C148H184N4O6 requires C,
84.04; H, 8.77; N, 2.65. Found: C, 81.84; H, 8.73; N, 2.15.
4.2.57. Compound 57. Yield: 0.764 g, 62%; IR (KBr,
cmꢁ1): 2965, 2928, 2856, 2207, 2114, 1598, 1494, 1465;
1H NMR (300 MHz): d 7.40 (s, 2H), 7.31 (s, 4H), 3.88 (sep-
tet, 4H), 2.81 (m, 4H), 1.71 (m, 4H), 1.43 (m, 4H), 1.40–1.30
(m, 8H), 1.31 (d, 24H), 0.88 (m, 6H); 13C NMR (100 MHz):
d 170.1, 145.3, 142.5, 132.4, 126.5, 124.5, 122.4, 93.5, 90.0,
34.3, 31.7, 30.8, 29.8, 29.4, 22.6, 22.5, 14.0, 34.3, 31.7, 30.7,
29.8, 29.3, 22.6, 22.5, 14.0; MS: m/z 664.58 (M+).
4.2.52. Compound 52. IR (cmꢁ1): 2959, 2927, 2857, 1718,
1683; 1H NMR (400 MHz): d 8.92 (s, 4H), 8.48 (s) and 8.05
(d) (2H), 7.53 (s, 4H), 7.41–7.36 (16H), 7.49 (d) and 6.85 (s)
(2H), 3.25–3.12 (m, 4H), 2.85 (m, 24H), 2.77–2.70 (m, 4H),
1.74 (m, 24H), 1.45–1.26 (m, 72H), 1.25 (m, 24H), 1.21 (d,
J¼6.9 Hz, 24H), 0.94–0.89 (m, 36H); 13C NMR (75 MHz):
d 164.8, 162.8, 146.9, 146.5, 146.0, 142.4, 141.9, 132.4,
131.7, 130.2, 127.6, 127.1, 126.9, 125.2, 124.1, 122.8,
122.4, 94.0, 93.0, 88.8, 85.8, 34.4, 34.2, 31.8, 31.8, 31.7,
30.8, 30.7, 29.5, 29.4, 29.3, 23.8, 23.5, 22.7, 22.7, 14.1;
Analysis: C188H240N4O6 requires C, 85.15; H, 9.12; N,
2.11. Found: C, 81.50; H, 8.84; N, 2.04.
4.2.58. Compound 58. Yield: 0.090 g, 72%; IR (KBr,
cmꢁ1): 2961, 2926, 2856, 2205, 2111, 1598, 1500, 1465;
1H NMR (300 MHz): d 7.41 (s, 2H), 7.39 (s, 2H), 7.32 (s,
4H), 3.39 (septet, 4H), 2.87–2.79 (m, 8H), 1.78–1.65 (m,
8H), 1.44–1.26 (m, 72H), 0.88 (m, 12H); 13C NMR
(75 MHz): d 170.1, 145.3, 142.5, 142.0, 132.5, 132.4,
126.5, 124.6, 123.9, 123.2, 122.1, 93.3, 93.1, 90.1, 34.3,
34.2, 31.8, 31.7, 30.8, 30.7, 29.8, 29.4, 29.3, 22.6, 22.5,
14.1, 14.0. MS: m/z 932.78 (M+).
4.2.53. Compound 53. Yield: 0.256 g, 93%; IR (cmꢁ1):
3380, 2960, 2926, 2856, 1717, 1682, 1599, 1581, 1499,
1467, 1459, 1336, 1250; H NMR (400 MHz): d 8.93 (s,
4.2.59. Compound 59. Yield: 0.142 g, 98%; IR (KBr,
cmꢁ1): 2960, 2926, 2855, 2204, 2111, 1597, 1501, 1464;
1H NMR (300 MHz): d 7.40 (s, 2H), 7.39–7.37 (4H),
7.32–7.30 (4H), 3.39 (septet, 4H), 2.87–2.75 (m, 12H),
1.77–1.68 (m, 12H), 1.45–1.26 (m, 84H), 0.89 (m, 18H);
13C NMR (75 MHz): d 170.1, 145.3, 145.2, 142.4, 142.0,
141.9, 132.5, 132.4, 132.3, 126.5, 126.4, 124.6, 123.2,
122.8, 121.9, 93.3, 93.2, 92.9, 90.2, 45.8, 34.3, 34.2, 31.8,
31.7, 30.8, 30.7, 30.6, 29.8, 29.4, 29.3, 22.6, 22.4, 14.1,
14.0; MS: m/z 1200.66 (M+).
1
4H), 8.50 (s) and 8.01 (d) (2H), 7.55 (s, 4H), 7.46–7.35
(20H), 7.50 (d) and 6.90 (s) (2H), 3.18 (m, 4H), 2.81 (m,
32H), 2.79–2.71 (m, 4H), 1.75–1.22 (m, 176H), 0.91 (m,
48H); 13C NMR (100 MHz): d 165.1, 162.8, 146.9, 146.4,
146.0, 142.4, 141.9, 132.4, 131.7, 127.7, 127.6, 127.0,
126.8,122.8,93.1, 34.2, 31.8, 30.7, 29.3, 23.8, 23.5, 22.6, 14.1.
4.2.54. Compound 54. Yield: 0.412 g, 83%; IR (KBr,
cmꢁ1): 2959, 2922, 2854, 2152, 2118, 1597, 1567, 1491,
1464; H NMR (300 MHz): d 7.34 (s, 1H), 7.31 (s, 1H),
1
Acknowledgements
7.30 (s, 2H), 3.39 (septet, 2H), 2.80–2.71 (m, 4H), 1.71–
1.59 (m, 4H), 1.43–1.27 (m, 24H), 0.90 (m, 6H), 0.27 (s,
9H); 13C NMR (75 MHz): d 170.2, 145.2, 142.8, 142.2,
132.6, 132.2, 126.4, 124.5, 123.9, 122.8, 122.1, 103.8,
We thank Prof. Konstantin K. Likharev for helpful discus-
sions. This work was supported by NSF and AFOSR.

A. Mayr et al. / Tetrahedron 63 (2007) 8206–8217
8217
Claridge, J. B.; zur Loye, H.-C.; Lieser, G. Chem. Mater.
1999, 11, 1416–1424.
7. Millich, F. Chem. Rev. 1972, 72, 101–113.
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