Preparation of nitrogen-containing 25-membered pentaolefinic macrocycles: (E,E,E,E,E)-1,6,11,16,21-penta(arylsulfonyl)-1,6,11,16,21- pentaazacyclopentacosa-3,8,13,18,23-pentaenes

Article abstract of DOI:10.1055/s-2004-834938

A stepwise preparation of a series of nitrogen-containing 25-membered pentaolefinic macrocycles is presented. The corresponding arenesulfonamides and trans-1,4-dibromo-2-butene served as precursors for the synthesis. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2004-834938

374
PAPER
Preparation of Nitrogen-Containing 25-Membered Pentaolefinic Macrocycles:
(E,E,E,E,E)-1,6,11,16,21-Penta(arylsulfonyl)-1,6,11,16,21-pentaazacyclopen-
tacosa-3,8,13,18,23-pentaenes
P
reparation of
N
i
e
trogen-Con
l
taining
é
25-Membe
n
re
d
Pentaolefinic
M
B
acrocycles lanco,a Jesper Christensen,a Ignasi Maurel,a Roser Pleixats,*a Anna Serra,a Anna Pla-Quintana,b
Anna Roglans,*b Jordi Benet-Buchholzc
a
Department of Chemistry, Universitat Autònoma de Barcelona, Cerdanyola, 08193 Barcelona, Spain
Fax +34(9)35811265, +34(9)72418150; E-mail: roser.pleixats@uab.es and anna.roglans@udg.es
Department of Chemistry, Universitat de Girona, Campus de Montilivi, 17071 Girona, Spain
Bayer Industry Services, Analytics X-ray Laboratory, Geb. Q18, Raum 490, Bayer AG, 51368 Leverkusen, Germany
Received 26 July 2004; revised 18 October 2004
b
c
Dedicated to Prof. Marcial Moreno-Mañas on the occasion of his 63rd birthday.
of the nitrogen-containing triolefinic 15-membered mac-
Abstract: A stepwise preparation of a series of nitrogen-containing
25-membered pentaolefinic macrocycles is presented. The corre-
sponding arenesulfonamides and trans-1,4-dibromo-2-butene
served as precursors for the synthesis.
rocycles. As the intermediates required for the different fi-
nal cyclisation steps leading to 15-membered rings are
efficiently obtained in terms of yield and simplicity, we
considered the possibility of preparing related 25-mem-
bered rings of type 1 (Scheme 1) by using the building
blocks required for the lower-membered counterparts.
Arenesulfonamides were chosen as to confer, enhance or
modulate certain properties in the macrocycles.6 The aim
was to study the coordination properties of the penta-
olefinic macrocycles with transition metals and to com-
pare them with those found for the triolefinic
macrocycles. Few complexes of transition metals with
several types of triolefinic macrocycles are known.7 To
our knowledge, no metal complexes of tetra- and penta-
olefinic macrocyles have been described.
Key words: alkenes, heterocycles, macrocycles, sulfonamides
Nitrogen-containing 25-membered macrocycles are rela-
tively frequent.1,2 However, nitrogen-containing macro-
cycles of this size with endocyclic olefinic double bonds
are uncommon. 25-Membered macrocycles featuring five
-N-C-C-C-C- units in any pattern of substitution or degree
of unsaturation are even rarer. We have reported3,4 the for-
mation of complex mixtures of 10-, 15- and 20-membered
macrocycles by non-selective Pd(0)-catalyzed allylation
of arenesulfonamides with cis-2-butene-1,4-diol dicar-
bonate; minor amounts of 25-membered ring compounds
being also detected in those mixtures. A bibliographic
search showed that only the aforementioned 25-mem-
bered macrocycles have been reported3,4 with olefinic
bonds in these units, and that five of those endocyclic sat-
urated units (1,6,11,16,21-pentaazacyclopentacosane
moieties) are found in synthetic cyclopeptides and deriv-
atives.5
25-Membered macrocycles 1 were prepared by reaction
of dibrominated compounds 2 and intermediates 3
(Scheme 1 and Table 1) in the presence of K2CO3 in re-
fluxing MeCN. In some cases, the use of sodium hydride
in dimethylformamide gave better results. Variable yields
of 1 were obtained after chromatographic purification.
The yields can be considered moderate to good if com-
pared with the reported cyclisation methods for the prep-
aration of macrocycles of this size. Higher macrocycles
We have described6 the synthesis, coordination properties
and catalytic activity [in the case of the Pd(0) complexes]
SO2Ar2
N
NHSO2Ar2
Ar1SO2
Br
N
SO2Ar1
N
i or ii
Ar2SO2
N
Ar2SO2
N
+
N
NHSO2Ar2
Ar1SO2
Br
N
2
3
N
SO2Ar1
Ar2SO2
1
Scheme 1 Preparation of 1. Reagents and conditions: i) K2CO3, refluxing CH3CN; ii) NaH on 3 in DMF, then 2 in DMF, 90 °C.
SYNTHESIS 2005, No. 3, pp 0374–0380
x
x
.
x
x
.2
0
0
5
Advanced online publication: 01.12.2004
DOI: 10.1055/s-2004-834938; Art ID: T08704SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Preparation of Nitrogen-Containing 25-Membered Pentaolefinic Macrocycles
375
Table 1 Data of Pentaolefinic Macrocycles 1
Compound
1aaaaa
1bbbbb
1aabbb
1ccccc
Ar1
Ar2
Yield (%) Method (i or ii)
Mp (°C)
157–159
93–94
4-Me-C6H4-
ferrocenyl
4-Me-C6H4-
ferrocenyl
19 (i)
28 (i)
23 (i)
24 (ii)
48 (ii)
27 (i)
4-Me-C6H4-
4-F-C6H4-
ferrocenyl
82–84
4-F-C6H4-
168–171
> 360
1ddddd
1aaeee
2,4,6-triisopropylphenyl
4-Me-C6H4-
2,4,6-triisopropylphenyl
4-Br-C6H4-
176–178
and lineal oligomers were also detected in the crude mix- Dibromides 2 were obtained by the sequence outlined in
tures (MALDI–TOF MS).
Scheme 2 (see also Table 2). Protected sulfonamides 4,
prepared from the corresponding arenesulfonamides ac-
cording to the general method described in the literature,9
were treated with 0.5 equivalents of (E)-1,4-dibromo-2-
butene in refluxing MeCN using K2CO3 as base. Com-
pounds 5 were deprotected with trifluoroacetic acid, and
the resulting intermediates 6 were dialkylated by treat-
ment with excess of (E)-1,4-dibromo-2-butene in the pres-
ence of K2CO3 as base. This reaction gave variable yields
depending on the aryl substitution.
The molecular structure of 1aaaaa, was confirmed by sin-
gle crystal X-ray structure analysis. Figure 1 shows the
Ortep-Plot diagram for the compound together with its la-
belling scheme. Compound 1aaaaa is crystallizing free of
solvents with a C1 symmetry. Bond distances and angles
are within expected values. The macrocyclic ring is highly
folded with two of the aromatic rest orientated upwards
and the other three orientated downwards. The planes of
the double bonds at the macrocyclic ring are orientated
randomly in different directions.8
Ar1SO2
Ar1SO2
Boc
i
ii
N
Ar1SO2NHBoc
N
Boc
4a,b,c,d
5aa, 5bb, 5cc, 5dd
SO2Ar1
Ar1O2S
N
Ar1SO2
N
iii
Ar1SO2
N
N
H
H
6aa, 6bb, 6cc, 6dd
Br
Br
2aa, 2bb, 2cc, 2dd
Scheme 2 Preparation of 2. Reagents and conditions: i) (E)-1,4-di-
bromo-2-butene (0.5 equiv), K2CO3, refluxing CH3CN; ii) trifluoro-
acetic acid-CH2Cl2 1:1, r.t.; iii) (E)-1,4-dibromo-2-butene (ca 7
equiv), K2CO3, refluxing MeCN.
Compounds 3 were prepared by the sequence outlined in
Scheme 3 (see also Table 3). Reaction of protected sul-
fonamides 4 with one equivalent of (E)-1,4-dibromo-2-
butene in refluxing MeCN, in the presence of K2CO3, af-
forded the monoalkylated compounds 7. These were treat-
ed with 0.5 equivalents of arenesulfonamides under
analogous conditions to afford compounds 8, which were
deprotected by the usual procedure to afford the desired
intermediates 3 in good yields.
Figure 1 Ortep-Plot (50%) of compound 1aaaaa. Hydrogen atoms,
except the ones of the double bonds, are omitted to fully appreciate
the geometry of the compound.
In summary, we report an efficient stepwise preparation
of 25-membered macrocycles featuring five all trans ole-
finic double bonds and five arylsulfonyl moieties. The
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York

376
B. Blanco et al.
Table 2 Data of Compounds 5, 6 and 2 (Scheme 2)
Compound Ar1
Yield Mp
PAPER
Table 3 Data of Compounds 7, 8 and 3 (Scheme 3)
Compound Ar2
Yield Mp
Lit. mp
(°C)
Lit. mp
(°C)
(%)
(°C)
(%)
(°C)
7c
4-F-C6H4-
78
oil
oil13
–
5bb
6bb
6dd
ferrocenyl
70
160–161
200–202
183
–
7d
2,4,6-triisopropy-
lphenyl
54
86–88
ferrocenyl
50
–
2,4,6-triisopro-
pylphenyl
84
18310
7e
4-Br-C6H4-
ferrocenyl
4-F-C6H4-
28
100
99
70–72
85–88
–
2aa
2bb
2cc
2dd
4-Me-C6H4-
ferrocenyl
4-F-C6H4-
31
51
77
67
112–113
158–160
97–99
11211
8bbb
8ccc
8ddd
–
oil
oil13
–
–
93–9512
123–12510
2,4,6-triisopropy-
lphenyl
85
127–129
2,4,6-triisopro-
pylphenyl
123–125
8eee
3bbb
3ccc
3ddd
4-Br-C6H4-
ferrocenyl
4-F-C6H4-
38
86
86
91
90–92
71–74
–
–
174–176
145–147
174–17613
–
Ar2SO2
Br
i
ii
Ar2SO2NHBoc
N
2,4,6-triisopropy-
lphenyl
Boc
4a,b,c,d,e
7a, 7b, 7c, 7d, 7e
3eee
4-Br-C6H4-
100
174–176
–
Ar2SO2
N
Ar2SO2
N
iii
(E,E,E,E,E)-1,6,11,16,21-Pentakis[(4-methylphenyl)sulfonyl]-
1,6,11,16,21-pentaazacyclopentacosa-3,8,13,18,23-pentaene
(1aaaaa); General Procedure
A mixture of 3aaa, (300 mg, 0.5 mmol), and anhyd K2CO3 (370 mg,
2.7 mmol) in MeCN (18 mL) was heated at 70 °C under stirring for
30 min. Then a solution of 2aa, (320 mg, 0.5 mmol) in MeCN (30
mL) was added and the mixture was refluxed for 22 h (TLC moni-
toring). After cooling to r.t., the salts were filtered off and the filtrate
was evaporated. The residue was purified by column chromatogra-
phy through silica gel (230–400 mesh) with mixtures of hexane–
Boc
Boc
N
SO2Ar2
HN
SO2Ar2
NH
SO2Ar2
N
SO2Ar2
8aaa, 8bbb, 8ccc,
8ddd, 8eee
3aaa, 3bbb, 3ccc,
3ddd, 3eee
Scheme 3 Preparation of 3. Reagents and conditions: i) (E)-1,4-di-
bromo-2-butene (1 equiv), K2CO3, refluxing CH3CN; ii) Ar2-SO2NH2
(0.5 equiv), K2CO3, refluxing CH3CN; iii) CF3CO2H–CH2Cl2 1:1, r.t.
EtOAc–CH2Cl2 of increasing polarity as eluent (9:1:0
→
16:3.5:0.5) to afford 1aaaaa. Yield: 110 mg (19%); white solid; mp
157–159 °C.
IR (KBr): 2921, 1330, 1151 cm–1.
1H NMR (200 MHz, CDCl3): d = 2.43 (s, 15 H), 3.62 (br s, 20 H),
5.44 (br s, 10 H), 7.31 (d, J = 8.2 Hz, 10 H), 7.64 (d, J = 8.2 Hz, 10
H).
13C NMR (50 MHz, CDCl3): d = 21.5, 49.0, 127.2, 129.3, 129.8,
136.3, 143.6.
MS (ESI): m/z = 1116 [M + H]+.
type of dielectrophilic and dinucleophilic compounds
used in the cyclisation reaction are versatile intermediates
that can also be used for the synthesis of 15-membered tri-
olefinic macrocycles, arenesulfonamides and (E)-1,4-di-
bromo-2-butene being the ultimate precursors.
Complexation experiments of macrocycles 1 with metals
will be reported in due course.
Anal. Calcd for C55H65N5O10S5: C, 59.17; N, 6.27; H, 5.87; S, 14.36.
Found: C, 58.77; N, 6.21; H, 5.97; S, 14.17.
1H (250 MHz or 200 MHz) and 13C (62.5 MHz or 50 MHz) NMR
chemical shifts are expressed relative to CHCl3 (d = 7.26 and d =
77.0, respectively) and TMS (d = 0.00). MALDI–TOF spectra were
recorded on a system equipped with a pulsed nitrogen laser (337
nm), operating in positive-ion reflector mode, using 19 kV acceler-
ation voltage and a matrix of a-cyano-4-hydroxycinnamic acid. ESI
mass spectra were acquired using a Navigator quadrupole instru-
ment; the instrument was operated in the positive ion mode (ES+)
at a probe tip voltage of 3 kV. Ferrocenesulfonamide was prepared
from ferrocene as previously reported.14 N-(tert-Butyloxycarbon-
yl)arenesulfonamides 4a,9 4b,15,16 4c,12 4d,11 and 4e17 were prepared
according to a general method described in the literature.9 Com-
pounds 5aa,11 5cc,12 5dd,11 6aa,11 6cc,12 7a,11 7b,15,16 8aaa,11
3aaa,11 were prepared as previously reported by us.
(E,E,E,E,E)-1,6,11,16,21-Pentakis(ferrocenylsulfonyl)-
1,6,11,16,21-pentaazacyclopentacosa-3,8,13,18,23-pentaene
(1bbbbb)
It was prepared from 2bb and 3bbb following the procedure em-
ployed for 1aaaaa [silica gel chromatography, hexane–EtOAc–
CH2Cl2, (7:1:2 → 4:3:3)]. Yield: 40 mg (28%); orange solid; mp
93–94 °C.
IR (KBr): 2919, 1332, 1132 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.47 (br s, 20 H), 4.40 (br s, 35 H),
4.54 (br s, 10 H), 5.32 (br s, 10 H).
13C NMR (50 MHz, CDCl3): d = 48.8, 68.6, 70.6, 70.8, 86.7, 129.1.
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York

PAPER
Preparation of Nitrogen-Containing 25-Membered Pentaolefinic Macrocycles
377
MS (MALDI–TOF): m/z = 1585 [M]+.
(E,E,E,E,E)-1,6,11-Tris[4-bromophenyl)sulfonyl]-16,21-bis[(4-
methylphenyl)sulfonyl]-1,6,11,16,21-pentaazacyclopentacosa-
3,8,13,18,23-pentaene (1aaeee)
Anal. Calcd for C70H75Fe5N5O10S5: C, 53.01; N, 4.42; H, 4.77; S,
10.11. Found: C, 52.87; N, 4.11; H, 5.05; S, 9.81.
A solution of 2aa (325 mg, 0.49 mmol) and 3eee (400 mg, 0.49
mmol) in MeCN–THF (100 mL of each solvent) was slowly added
to a refluxing and mechanically stirred mixture of anhyd K2CO3
(953 mg, 6.9 mmol) in MeCN–THF (150 mL of each solvent). The
mixture was refluxed for 20 h; then it was filtered and evaporated.
The residue was purified by column chromatography through silica
gel under pressure with hexane–EtOAc (8:2) as eluent, to afford
1aaeee. Yield: 177 mg (27%); white solid; mp 176–178 °C.
IR (neat): 2961, 1572, 1333, 1259, 1154 cm–1.
1H NMR (250 MHz, CDCl3): d = 2.44 (s, 6 H), 3.64 (m, 20 H), 5.48
(m, 10 H), 7.32 (d, J = 8.0 Hz, 4 H), 7.63 (m, 16 H).
(E,E,E,E,E)-1,6,11-Tris(ferrocenylsulfonyl)-16,21-bis[(4-meth-
ylphenyl)sulfonyl]-1,6,11,16,21-pentaazacyclopentacosa-
3,8,13,18,23-pentaene (1aabbb)
It was prepared from 2aa and 3bbb following the procedure em-
ployed for 1aaaaa (silica gel chromatography, hexane–EtOAc, 9:1
→ 6:4). Yield: 120 mg (23%); orange solid; mp 82–84 °C.
IR (KBr): 2920, 1331, 1156, 1133 cm–1.
1H NMR (200 MHz, CDCl3): d = 2.44 (s, 6 H), 3.45–3.61 (m, 20 H),
4.40 (br s, 21 H), 4.55 (br s, 6 H), 5.34–5.40 (m, 10 H), 7.32 (d, J =
8.2 Hz, 4 H), 7.64 (d, J = 8.2 Hz, 4 H).
13C NMR (50 MHz, CDCl3): d = 21.5, 48.7, 48.8, 68.6, 70.6, 70.7,
86.5, 127.2, 128.7, 129.0, 129.2, 129.6, 129.8, 136.6, 143.5.
13C NMR (62.5 MHz, CDCl3): d = 20.7, 48.2, 48.4, 48.5, 48.6,
126.4, 126.8, 127.9, 128.0, 128.5, 128.6, 128.7, 129.0, 129.3, 131.7,
135.2, 137.6, 142.8.
MS (ESI): m/z = 1397 [M]+.
MS (MALDI–TOF): m/z = 1330–1339 [M + Na]+, 1346–1355 [M +
K]+.
Anal. Calcd for C64H71Fe3N5O10S5: C, 54.98; N, 5.01; H, 5.12; S,
11.47. Found: C, 55.09; N, 4.68; H, 5.47; S, 10.91.
HRMS: m/z calcd for C52H56Br3N5O10S5 + Na: 1330.0073; found:
1330.0101.
(E,E,E,E,E)-1,6,11,16,21-Pentakis[(4-fluorophenyl)sulfonyl]-
1,6,11,16,21-pentaazacyclopentacosa-3,8,13,18,23-pentaene
(1ccccc)
(E)-N,N¢-Bis(tert-butyloxycarbonyl)-N,N¢-bis(ferrocenylsulfo-
nyl)-2-butene-1,4-diamine (5bb)
A mixture of 3ccc (50 mg, 0.08 mmol), NaH (60% dispersion in
mineral oil, 12 mg, 0.29 mmol) in dimethylformamide (4 mL) was
heated under stirring at 90 °C for 30 min. Then 2cc, (42 mg, 0.06
mmol) was added and the mixture was heated at 90 °C for 20 h. Af-
ter cooling to r.t. water (5 mL) was added and the solvent was evap-
orated under reduced pressure. The residue was dissolved in CH2Cl2
and washed three times with water. The organic phase was dried
with anhyd Na2SO4 and the solvent was evaporated. The residue
was purified by column chromatography under pressure through a
reversed phase silica gel column (Bakerbond octadecyl C18, 40 mm)
with a mixture of MeOH–MeCN (5:1) as eluent, to afford 1ccccc.
Yield: 17 mg (24%); white solid; mp 168–171 °C.
A mixture of 4b (1.82 g, 5.0 mmol) and anhyd K2CO3 (2.15 g, 14.5
mmol) in MeCN (65 mL) was heated under stirring at 70 °C for 20
min, then a solution of (E)-1,4-dibromo-2-butene (570 mg, 2.7
mmol) in MeCN (25 mL) was added and the suspension was re-
fluxed for 23 h (TLC monitoring). The mixture was filtered and
evaporated. The residue was purified by column chromatography
through silica gel under pressure with hexane–EtOAc (4:1) as elu-
ent, affording 5bb. Yield: 1.35 g (70%); orange solid; mp 160–161
°C.
IR (KBr): 2978, 1713, 1350, 1143 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.41 (s, 18 H), 4.26 (br abs, 4 H),
4.41 (s, 10 H), 4.39–4.43 (m, 4 H), 4.76 (app t, J = 2.0 Hz, 4 H), 5.61
(m, 2 H).
IR (neat): 2919, 1591, 1492, 1335, 1152 cm–1.
1H NMR (250 MHz, CDCl3): d = 3.65 (m, 20 H), 5.51 (m, 10 H),
7.19 (dd, J = 8.9, 8.3 Hz, 10 H), 7.79 (dd, J = 8.9, 5.0 Hz, 10 H).
13C NMR (50 MHz, CDCl3): d = 28.0, 47.8, 70.2, 70.6, 70.9, 83.6,
87.0, 128.4, 150.9.
MS (ESI): m/z = 782 [M]+, 800 [M + NH4]+, 805 [M + Na]+.
13C NMR (62.5 MHz, CDCl3): d = 49.7, 116.9 (d, J = 21.9 Hz),
129.9, 130.25 (d, J = 8.6 Hz), 135.7 (d, J = 3.8 Hz), 165.5 (d, J =
253.7).
Anal. Calcd for C34H42Fe2N2O8S2: C, 52.19; N, 3.58; H, 5.41; S,
8.19. Found: C, 52.41; N, 3.58; H, 5.45; S, 8.75.
MS (MALDI–TOF): m/z = 1159 [M + Na]+, 1175 [M + K]+.
Anal. Calcd for C50H50F5N5O10S5: C, 52.85; N, 6.16; H, 4.44; S,
14.11. Found: C, 52.27; N, 5.97; H, 4.61; S, 13.70.
(E)-N,N¢-Bis(ferrocenylsulfonyl)-2-butene-1,4-diamine (6bb)
A solution of 5bb (1.16 g, 1.5 mmol) in trifluoroacetic acid–CH2Cl2
(10 mL, 1:1) was stirred at r.t. for 2 h (TLC monitoring). Then, the
solution was evaporated and the residue was taken in CH2Cl2 (25
mL), washed with water (2 × 20 mL) and a sat. aq solution of NaCl
(25 mL). The organic layer was dried with anhyd Na2SO4 and the
solvent was evaporated. The residue was purified by column chro-
matography through silica gel under pressure with CH2Cl2 as eluent,
to afford 6bb. Yield: 430 mg (50%); orange solid; mp 200–202 °C.
(E,E,E,E,E)-1,6,11,16,21-Pentakis[(2,4,6-triisopropylphe-
nyl)sulfonyl]-1,6,11,16,21-pentaazacyclopentacosa-
3,8,13,18,23-pentaene (1ddddd)
It was prepared from 2dd and 3ddd following the procedure em-
ployed for 1ccccc [silica gel chromatography, hexane–EtOAc,
(8:2)]. Yield: 169 mg (48%); white solid; mp > 360 °C.
IR (neat): 2958, 1600, 1461, 1363, 1310, 1148 cm–1.
IR (KBr): 3267, 3096, 1322, 1135 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.20 (m, 90 H), 2.87 (septet, J =
7.1 Hz, 5 H), 3.74 (m, 20 H), 4.05 (septet, J = 7.1 Hz, 10 H), 5.67
(m, 10 H), 7.11 (s, 10 H).
13C NMR (62.5 MHz, CDCl3): d = 23.3, 24.55, 28.9, 33.9, 46.8,
123.6, 129.4, 130.8, 151.1, 152.9.
1H NMR (200 MHz, CDCl3): d = 3.45–3.48 (m, 4 H), 4.10 (t, J =
6.0 Hz, 2 H), 4.39 (s, 10 H), 4.37–4.40 (m, 4 H), 4.60 (app t, J = 1.8
Hz, 4 H), 5.40–5.44 (m, 2 H).
13C NMR (50 MHz, CDCl3): d = 44.4, 68.6, 70.5, 70.8, 87.4, 128.4.
MS (ESI): m/z = 582 [M]+, 583 [M + H]+.
MS (MALDI–TOF): m/z = 1699 [M + Na]+, 1715 [M + K]+.
Anal. Calcd for C24H26Fe2N2O4S2: C, 49.50; N, 4.81; H, 4.50; S,
11.01. Found: C, 49.52; N, 4.80; H, 4.50; S, 10.83.
HRMS: m/z calcd for C95H145N5O10S5 + Na: 1698.9487; found:
1698.9526.
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York

378
B. Blanco et al.
PAPER
N-[(E)-4-Bromo-2-butenyl]-N-(tert-butyloxycarbonyl)-(2,4,6-
triisopropylphenyl)sulfonamide (7d)
(E)-N,N¢-Bis[(2,4,6-triisopropylphenyl)sulfonyl]-2-butene-1,4-
diamine (6dd)
It was prepared by the general method described for 6bb (84%
yield, no chromatography was needed; mp 183 °C). This compound
had been previously synthesized by us by another method.10
It was prepared from 4d following the procedure employed for 7c.
The crude mixture was purified by column chromatography through
silica gel with hexane–EtOAc (10:1) as eluent to afford 7d. Yield:
5.68 g (54%); white solid; mp 86–88 °C.
(E,E,E)-1,14-Dibromo-N,N¢-bis[(4-methylphenyl)sulfonyl]-
5,10-diazatetradeca-2,7,12-triene (2aa)
IR (KBr): 2959, 2934, 1719, 1598, 1367, 1337,1165, 1143 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.21 (m, 27 H), 2.89 (septet, J =
6.9 Hz, 1 H), 3.87 (septet, J = 6.9 Hz, 2 H), 3.95 (d, J = 7.2 Hz, 2
H), 4.40 (d, J = 5.2 Hz, 2 H), 5.85–6.06 (m, 2 H), 7.12 (s, 2 H).
13C NMR (62.5 MHz, CDCl3): d = 24.0, 24.9, 28.1, 29.7, 32.05,
34.6, 46.35, 84.25, 123.85, 130.2, 134.1, 150.6, 151.2, 153.6.
A stirred mixture of 6aa (1.00 g, 2.5 mmol), (E)-1,4-dibromo-2-
butene (5.53 g, 21.2 mmol) and anhyd K2CO3 (1.55 g, 11.2 mmol)
in MeCN (10 mL) was heated under reflux for 24 h. Then, the mix-
ture was filtered and evaporated. The residue was purified by col-
umn chromatography through silica gel under pressure with
hexane–EtOAc (5:3) as eluent, to afford 2aa. Yield: 520 mg (31%);
white solid; mp 112–113 ºC; lit.11 mp 112 °C.
Anal. Calcd for C24H38BrNO4S: C, 55.81; N, 2.71; H, 7.41; S, 6.21.
Found: C, 56.06; N, 2.82; H, 7.56; S, 6.00.
(E,E,E)-1,14-Dibromo-N,N'-bis(ferrocenylsulfonyl)-5,10-diaza-
tetradeca-2,7,12-triene (2bb)
It was prepared in 51% yield by the general method described for
2aa [mixtures of hexane–EtOAc (7:3 → 1:1) as eluent]; mp 158–
160 °C.
N-[(E)-4-Bromo-2-butenyl]-N-(tert-butyloxycarbonyl)-(4-bro-
mophenyl)sulfonamide (7e)
It was prepared from 4e following the procedure employed for 7c.
The crude mixture was purified by column chromatography through
silica gel with hexane–EtOAc (8:2) as eluent. Compound 7e eluted
from the column was washed with Et2O and petroleum ether to af-
ford 7e. Yield: 1.45 g (28%); white solid; mp 70–72 °C.
IR (KBr) 2905, 1335, 1132 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.56–3.65 (m, 8 H), 3.86 (d, J =
7.2 Hz, 4 H), 4.38–4.41 (m, 4 H), 4.40 (s, 10 H), 4.57 (app t, J = 1.8
Hz, 4 H), 5.37–5.81 (m, 6 H).
13C NMR (50 MHz, CDCl3): d = 31.5, 48.0, 48.4, 68.5, 70.6, 70.8,
87.2, 129.0, 129.9, 130.0.
IR (neat): 2983, 1719, 1572, 1360, 1145 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.38 (s, 9 H), 3.97 (d, J = 7.2 Hz,
2 H), 4.44 (d, J = 5.9 Hz, 2 H), 5.83 (dt, J = 15.2, 5.9 Hz, 1 H), 5.99
(dt, J = 15.2, 7.3 Hz, 1 H), 7.66 (d, J = 8.9 Hz, 2 H), 7.80 (d, J = 8.9
Hz, 2 H).
13C NMR (62.5 MHz, CDCl3): d = 28.3, 31.8, 47.6, 85.4, 128.8,
130.1, 130.2, 130.8, 132.4, 139.2, 150.7.
MS (ESI): m/z = 848 [M]+, 849 [M + H]+.
Anal. Calcd for C32H36Br2Fe2N2O4S2: C, 45.31; N, 3.30; H, 4.28;
found: C, 45.62; N, 3.25; H, 4.20.
Anal. Calcd for C15H19Br2NO4S: C, 38.40; N, 2.99; H, 4.08; S, 6.83.
Found: C, 38.75; N, 2.84; H, 4.32; S, 6.70.
(E,E,E)-1,14-Dibromo-N,N'-bis[(4-fluorophenyl)sulfonyl]-5,10-
diazatetradeca-2,7,12-triene (2cc)
It was prepared in 77% yield by the general method described for
2aa [hexane–EtOAc, (4:1) as eluent]; mp 97–99 °C; lit.12 mp 93–95
°C.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris(ferrocenylsul-
fonyl)-1,6,11-triazaundeca-3,8-diene (8bbb)
A stirred mixture of ferrocenylsulfonamide (260 mg, 1.0 mmol), 7b
(1.00 g, 2.0 mmol), anhyd K2CO3 (830 mg, 6.0 mmol), and MeCN
(15 mL) was refluxed for 18 h (TLC monitoring). After cooling to
r.t., the mixture was filtered off and the filtrate was evaporated. The
residue was redissolved in EtOAc (15 mL), washed with water (3 ×
10 mL) and a sat. solution of NaCl. The organic phase was dried
with anhyd Na2SO4 and the solvent was evaporated to afford 8bbb
as an oil (1.10 g, 100%), which crystallized upon addition of hex-
ane; mp 85–88 °C (hexane).
(E,E,E)-1,14-Dibromo-N,N'-bis[(2,4,6-triisopropylphenyl)sul-
fonyl]-5,10-diazatetradeca-2,7,12-triene (2dd)
It was prepared in 67% yield by the general method described for
2aa. The crude mixture was not chromatographed, the remaining
(E)-1,4-dibromo-2-butene being eliminated by sublimation (50 °C,
0.3–0.5 mbar) and subsequent washing of the residue with pentane;
mp 123–125 °C; lit.10 mp 123–125 °C.
IR (KBr): 2973, 2922, 1720, 1359, 1130 cm–1.
N-[(E)-4-Bromo-2-butenyl]-N-(tert-butyloxycarbonyl)-(4-fluo-
rophenyl)sulfonamide (7c)
1H NMR (200 MHz, CDCl3): d = 1.42 (s, 18 H), 3.62 (app d, J = 5.0
Hz, 4 H), 4.19 (app d, J = 4.6 Hz, 4 H), 4.41 (s, 15 H), 4.35–4.42
(m, 6 H), 4.56 (app t, J = 1.9 Hz, 2 H), 4.74 (app t, J = 2.0 Hz, 4 H),
5.38–5.57 (m, 4 H).
13C NMR (50 MHz, CDCl3): d = 28.1, 47.7, 47.8, 68.6, 70.1, 70.5,
70.6, 70.7, 71.0, 83.7, 87.3, 87.8, 127.5, 129.7, 151.0.
A stirred mixture of 4c (6.73 g, 24.5 mmol), (E)-1,4-dibromo-2-
butene (25.57 g, 119.5 mmol), anhyd K2CO3 (7.01 g, 50.1 mmol),
and MeCN (90 mL) was refluxed for 20 h. After cooling at r.t., the
mixture was filtered off and the filtrate was evaporated. The residue
was sublimed at 50 °C (0.3–0.5 mbar) to eliminate most of the ex-
cess of (E)-1,4-dibromo-2-butene. The residue of sublimation was
purified by column chromatography through silica gel with a mix-
ture of hexane–EtOAc (9:1) as eluent to afford 7c. Yield: 7.74 g
(78%); oil.
Anal. Calcd for C48H57Fe3N3O10S3: C, 52.43; N, 3.82; H, 5.22; S,
8.75. Found: C, 52.10; N, 3.48; H, 5.40; S, 8.35.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris[(4-fluorophe-
nyl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (8ccc)
IR (neat): 2979, 1729, 1591, 1494, 1361, 1152 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.39 (s, 9 H), 3.99 (d, J = 7.2 Hz,
2 H), 4.46 (d, J = 5.6 Hz, 2 H), 5.87 (dt, J = 15.2, 5.7 Hz, 1 H), 6.02
(dt, J = 15.2, 7.2 Hz, 1 H), 7.20 (dd, J = 9.1, 8.2 Hz, 2 H), 7.97 (dd,
J = 9.1, 5.0 Hz, 2 H).13
It was prepared following the procedure employed for 8bbb, from
7c and 4-fluorophenylsulfonamide. Yield: 7.79 g (99%); oil.
IR (neat): 2981, 1726, 1591, 1494, 1353, 1151 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.36 (s, 18 H), 3.67 (d, J = 6.1 Hz,
4 H), 4.40 (d, J = 5.5 Hz, 4 H), 5.60 (dt, J = 15.5, 5.7 Hz, 2 H), 5.78
(dt, J = 15.4, 6.0 Hz, 2 H), 7.20 (dd, J = 9.1, 8.3 Hz, 6 H), 7.87 (dd,
J = 8.8, 5.0 Hz, 2 H), 7.92 (dd, J = 8.8, 5.0 Hz, 4 H).13
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York

PAPER
Preparation of Nitrogen-Containing 25-Membered Pentaolefinic Macrocycles
379
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris[(2,4,6-triiso-
propylphenyl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (8ddd)
It was prepared following the procedure employed for 8bbb, from
7d and (2,4,6-triisopropylphenyl)sulfonamide. Yield: 3.16 g (85%)
(after recrystallization of the crude mixture in MeOH); white solid;
mp 127–129 °C.
IR (neat): 3276, 1591, 1430, 1327, 1154 cm–1.
1H NMR (250 MHz, CD3SOCD3): d = 3.38 (m, 4 H), 3.61 (d, J =
5.9 Hz, 4 H), 5.33 (dt, J = 15.5, 5.7 Hz, 2 H), 5.45 (dt, J = 15.5, 5.2
Hz, 2 H), 7.46 (dd, J = 12.5, 8.7 Hz, 6 H), 7.86 (dd, J = 8.7, 5.2 Hz,
6 H).13
IR (KBr): 2958, 2870, 1732, 1601, 1368, 1339, 1259, 1149 cm–1.
(E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-tri-
azaundeca-3,8-diene (3ddd)
1H NMR (250 MHz, CDCl3): d = 1.21 (m, 72 H), 2.88 (septet, J =
6.9 Hz, 3 H), 3.80 (d, J = 5.3 Hz, 4 H), 3.86 (septet, J = 6.9 Hz, 4
H), 4.14 (septet, J = 6.9 Hz, 2 H), 4.37 (d, J = 4.7 Hz, 4 H), 5.77 (m,
4 H), 7.10 (s, 4 H), 7.14 (s, 2 H).
13C NMR (62.5 MHz, CDCl3): d = 23.91, 23.94, 24.8, 25.2, 28.1,
29.6, 34.51, 34.55, 46.68, 46.75, 83.9, 123.7, 124.2, 128.4, 130.7,
131.6, 134.6, 159.5, 151.2, 151.9, 153.27, 153.35.
It was prepared following the procedure employed for 3bbb, from
8ddd; (more CH2Cl2 was added to the reaction mixture and it was
washed with a sat. aq solution of Na2CO3, the organic phase being
dried and evaporated). Yield: 780 mg (91%); mp 145–147 °C
(Et2O).
IR (neat): 3294, 1600, 1461, 1424, 1363, 1149 cm–1.
1H NMR (250 MHz, CDCl3): d = 1.22 (m, 54 H), 2.87 (septet, J =
6.8 Hz, 3 H), 3.51 (app t, J = 5.3 Hz, 4 H), 3.80 (d, J = 7.0 Hz, 4 H),
4.10 (m, 6 H), 4.55 (t, J = 6.2 Hz, 2 H), 5.58 (m, 4 H), 7.12 (s, 2 H),
7.14 (s, 4 H).
Anal. Calcd for C63H99N3O10S3: C, 65.53; N, 3.64; H, 8.64; S, 8.33:
Found: C, 65.37; N, 3.62; H, 8.81; S, 8.01.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris[(4-bromophe-
nyl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (8eee)
13C NMR (62.5 MHz, CDCl3): d = 23.9, 25.2, 29.6, 29.9, 34.5, 44.5,
It was prepared following the procedure employed for 8bbb, from
7e and (4-bromophenyl)sulfonamide [chromatography on silica gel
with hexane–EtOAc (7:3), then washing with petroleum ether].
Yield: 910 mg (38%); white solid; mp 90–92 °C.
46.9, 124.2, 128.2, 131.15, 131.8, 132.5, 150.7, 151.8, 153.2, 153.6.
Anal. Calcd for C53H83N3O6S3: C, 66.70; N, 4.40; H, 8.76; S, 10.08.
Found: C, 66.13; N, 4.41; H, 8.73; S, 9.56.
IR (neat): 2982, 1725, 1574, 1349, 1323, 1148 cm–1.
(E,E)-1,6,11-Tris[(4-bromophenyl)sulfonyl]-1,6,11-triazaunde-
ca-3,8-diene (3eee)
It was prepared following the procedure employed for 3bbb, from
8eee (the oily crude mixture crystallized upon addition of Et2O).
Yield: 1.13 g (ca. 100%); white solid; mp 174–176 °C.
1H NMR (250 MHz, CDCl3): d = 1.34 (s, 18 H), 3.84 (d, J = 6.2 Hz,
4 H), 4.37 (d, J = 5.5 Hz, 4 H), 5.59 (dt, J = 15.4, 6.1 Hz, 2 H), 5.77
(dt, J = 15.4, 5.6 Hz, 2 H), 7.66 (d, J = 8.8 Hz, 6 H), 7.76 (d, J = 8.8
Hz, 6 H).
13C NMR (62.5 MHz, CDCl3): d = 28.2, 48.0, 48.4, 85.3, 127.9,
128.4, 128.7, 129.0, 130.3, 132.4, 132.9, 139.4, 139.7, 150.7.
IR (neat): 3301, 3271, 1575, 1328, 1158 cm–1.
1H NMR (250 MHz, CD3SOCD3): d = 3.37 (masked d, 4 H), 3.58
(d, J = 5.9 Hz, 4 H), 5.40 (m, 4 H), 7.72 (d, J = 8.4 Hz, 6 H), 7.83
(d, J = 8.4 Hz, 6 H), 7.92 (m, 2 H).
13C NMR (62.5 MHz, CD3SOCD3): d = 44.5, 48.4, 127.0, 127.1,
127.6, 129.4, 129.8, 131.2, 133.2, 133.3, 139.9, 140.8.
Anal. Calcd for C36H42Br3N3O10S3: C, 42.70; N, 4.15; H, 4.18; S,
9.50. Found: C, 42.89; N, 4.05; H, 4.28; S, 9.18.
Partial deprotection of nitrogen was observed, as a second fraction
eluted from the column was unpurified with (E,E)-1-(tert-butyl-
oxycarbonyl)-1,6,11-tris[4-bromophenyl)sulfonyl]-1,6,11-triaza-
undeca-3,8-diene.
Anal. Calcd for C26H26Br3N3O6S3: C, 38.44; N, 5.17; H, 3.23; S,
11.84. Found: C, 38.14; N, 4.89; H, 3.14; S, 11.49.
(E,E)-1,6,11-Tris(ferrocenylsulfonyl)-1,6,11-triazaundeca-3,8-
diene (3bbb); General Procedure
X-ray Crystallographic Study
Suitable crystals of 1aaaaa were grown by slow evaporation of a n-
hexane–EtOAc–CH2Cl2 solution at r.t. The measured crystal (700 ×
40 × 20 mm3) was prepared routinely under inert conditions im-
mersed in perfluoropolyether as protecting oil for manipulation,
even if macrocycles 1 are very stable compounds. The measurement
was made on a Siemens P4 diffractometer equipped with a
SMART-CCD-1000 area detector, a MACScience Co rotating an-
ode with MoKa radiation, a graphite monochromator and a Siemens
low temperature device LT2 (T = –120 °C). The measurements
were made in the range 1.40°–31.49°. Fullsphere data collection
was done with w and j scans. Following programs were used: Data
collection Smart 5.625 (Bruker-AXS 2001), data reduction Saint
Plus Version 1.6 (Bruker-Nonius 2002), absorption correction
SADABS V. 2.03 (2002) and structure solution and refinement
SHELXTL Version 6.12 (Sheldrick, 2000).
A solution of 8bbb, (910 mg, 1.0 mmol) in trifluoroacetic acid–
CH2Cl2 (20 mL, 1:1) was stirred at r.t. for 2 h (TLC monitoring).
Then, the solution was evaporated, the residue taken in EtOAc (15
mL), and washed with water (3 × 10 mL). The organic layer was
dried with anhyd Na2SO4 and the solvent evaporated to afford 3bbb
as an orange foam (650 mg, 86%). An orange solid was obtained
upon digestion with hexane; mp 71–74 °C.
IR (KBr): 3268, 3099, 2919, 2850, 1320, 1185, 1132 cm–1.
1H NMR (200 MHz, CDCl3): d = 3.46–3.57 (m, 8 H), 4.42 (br abs,
2 H), 4.43 (s, 15 H), 4.38–4.47 (m, 6 H), 4.57 (app t, J = 1.9 Hz, 2
H), 4.66 (app t, J = 1.9 Hz, 4 H), 5.42–5.48 (m, 4 H).
13C NMR (50 MHz, CDCl3): d = 44.4, 48.5, 68.6, 70.5, 70.6, 70.7,
87.2, 87.5, 127.9, 129.4.
MS (ESI): m/z = 900 [M + H]+, 917 [M + NH4]+.
Compound 1aaaaa
C55H65N5O10S5, Mr = 1116.42; monoclinic; space group P21/c, a =
16.4897 (7) Å, b = 11.4315 (6) Å, c = 29.2425 (14) Å, b = 94.841
(2)°, V = 5492.6 (5) Å3, Z = 4, rcal = 1.350 Mg/m3, m = 0.274
mm–1, 82074 reflections were collected of which 17675 are unique
(Rint = 0.0819), 12673 Fo > 4 s (Fo), 681 refined parameters, R1 [I >
2 s (I)] = 0.0484, wR2 [I > 2 s (I)] = 0.1214. Goodness of fit on
F2 = 1.032, maximum residual electron density 0.369 (–0.550) e Å3.
HRMS: m/z calcd for C38H41Fe3N3O6S3 899.0209; found: 899.0205.
(E,E)-1,6,11-Tris[(4-fluorophenyl)sulfonyl]-1,6,11-triazaunde-
ca-3,8-diene (3ccc)
It was prepared following the procedure employed for 3bbb, from
8ccc; (5.09 g, 86%, white solid precipitating upon addition of more
CH2Cl2 to the reaction mixture); mp 174–176 °C.
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York

380
B. Blanco et al.
PAPER
references: Lewandos, G. S.; Gregston, D. K.; Nelson, F. R.
J. Organomet. Chem. 1976, 118, 363. (h) Faure, R.;
Acknowledgment
Financial support from MCyT of Spain (Projects PB98-0902 and
BQU2002-04002-C02) and CIRIT-Generalitat de Catalunya (Pro-
jects SGR2000-00062, SGR2001-00181, and SGR2001-00291) is
gratefully acknowledged. We benefit from the Socrates Programme
for stages of students (J. C.). We thank Prof. M. Moreno-Mañas for
helpful comments.
Loiseleur, H.; Haufe, G.; Trauer, H. Acta Crystallogr. Sect.
C 1985, 41, 1593. (i) Jackson, R. B.; Streib, W. E. J. Am.
Chem. Soc. 1967, 89, 2539. (j) Iyoda, M.; Kuwatani, Y.;
Yamauchi, T.; Oda, M. J. Chem. Soc., Chem. Commun.
1988, 65. (k) Yoshida, T.; Kuwatani, Y.; Hara, K.; Yoshida,
M.; Matsuyama, H.; Iyoda, M.; Nagase, S. Tetrahedron Lett.
2001, 42, 53. (l) Kuwatani, Y.; Yoshida, T.; Kusaka, A.;
Oda, M.; Hara, K.; Yoshida, M.; Matsuyama, H.; Iyoda, M.
Tetrahedron 2001, 57, 3567. (m) For Cu(I) complexes, see
the following references: Chow, Y. L.; Cheng, X. E.; Buono-
Core, G. E. Organometallics 1987, 6, 1126. (n) Salomon,
R. G.; Kochi, J. K. J. Organomet. Chem. 1974, 64, 135.
(o) Salomon, R. G.; Kochi, J. K. J. Am. Chem. Soc. 1973, 95,
References
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(2) For a review on nitrogen-bridged macrocycles, see:
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(3) Cerezo, S.; Cortés, J.; López-Romero, J.-M.; Moreno-
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1889; and also ref.7j–l
.
(8) Crystallographic data (excluding structure factors) for the
structure in this paper has been deposited with the
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publication number CCDC 230218. Copies of the data can
be obtained, free of charge, on application to CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK [fax: +44
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(13) (a) This compound has also been described by: Badetti, E.
Master in Chemical Experimentation; Universitat
Autònoma de Barcelona: Barcelona Spain, 2003. (b) It gave
correct elemental analysis.
(14) Slocum, D. W.; Achermann, W. Synth. React. Inorg. Met.
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(6) For reviews about the synthesis, coordination and catalytic
properties of our triolefinic azamacrocycles, see:
(a) Moreno-Mañas, M.; Pleixats, R.; Roglans, A.; Sebastián,
R. M.; Vallribera, A. Arkivoc 2004, Part IV, 109; (http://
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Youngs, C. A.; Youngs, W. J. Organometallics 1989, 8,
2089. (g) For Ag(I) complexes, see the following
Synthesis 2005, No. 3, 374–380 © Thieme Stuttgart · New York