An expeditious preparation of 15-membered nitrogen-containing olefinic and benzo macrocycles

Article abstract of DOI:10.1002/ejoc.200300171

(E,E)-1,6,11-Tris(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclopentadeca-8, 13-dienes (2) and 1,6,11-tris(arenesulfonyl)-3,4; 8,9,13,14-tribenzo-1,6,11-triazacyclopentadecanes (3) were prepared from arenesulfonamides, trans-1,4-dibromobutene, and 1,2-bis(bromomethyl) benzene. They form unstable complexes with silver tetrafluoroborate. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejoc.200300171

FULL PAPER
An Expeditious Preparation of 15-Membered Nitrogen-Containing Olefinic and
Benzo Macrocycles
[a]
[a]
[a]
´
˜
Rosa M. Sebastian,* Marcial Moreno-Manas, and Adelina Vallribera
Keywords: Alkene ligands / Heterocycles / Macrocycles / Silver
(E,E)-1,6,11-Tris(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclo-
pentadeca-8,13-dienes (2) and 1,6,11-tris(arenesulfonyl)-3,4;
8,9;13,14-tribenzo-1,6,11-triazacyclopentadecanes (3) were
prepared from arenesulfonamides, trans-1,4-dibromobutene,
and 1,2-bis(bromomethyl)benzene. They form unstable com-
plexes with silver tetrafluoroborate.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
of macrocycles, and high-dilution techniques are frequently
adopted. This, though, is not the case with macrocycles
1a.[3f] It should be noted that the sulfonamide moiety has
non-coordinating nitrogen atoms and that the sulfonamides
are not incorporated as protecting groups for the secondary
amines. Instead, the sulfonamide permits tuning of such
properties of the macrocycle as solubility in organic sol-
vents (Ar ϭ 2,4,6-triisopropylphenyl), crystallinity for X-
ray diffraction (Ar ϭ 4-tolyl and others), and visibility for
chromatographic recovery (Ar ϭ ferrocenyl).
Macrocycles 1a are reminiscent of the 12-membered
carbocyclic cyclododeca-1,5,9-trienes (1b) formed by tri-
merization of butadiene and have an important organomet-
allic chemistry. Their Ni0 complexes have thus played fun-
damental roles in catalysis and in organonickel chemistry.[6]
Supporting Information for this article, consisting of spec-
tra of reported compounds, is available (see also footnote
on the first page of this article).
Nitrogen-containing 15-membered macrocycles featuring
internal double bonds are rare.[1] The few examples known
from other groups contain only one double bond, and the
key step in their preparation is metathesis.[2]
We are interested in the preparation and organometallic
chemistry of 15-membered triolefinic macrocycles, and have
described macrocycles 1a (Figure 1), containing three non-
coordinating nitrogen atoms. Compounds 1a coordinate
Pd0, Pt0, and AgI [3] through their olefinic double bonds.
Their palladium complexes function as catalysts or precata-
lysts in Suzuki couplings,[3a] hydroarylation of alkynes,[3]
butadiene telomerization,[4] and in Heck reactions.[5]
Figure 1. Previously described products
Macrocycles 1a are easily made by any of three different
routes that converge in trans-1,4-dibromobutene and arene-
sulfonamides as starting materials. The concentration of re-
agents is frequently a crucial problem in the preparation
[a]
`
Department of Chemistry, Universitat Autonoma de Barcelona
Cerdanyola, 08193-Barcelona, Spain
Fax: (internat.) ϩ34-935/811265
E-mail: rosamaria.sebastian@uab.es
Scheme 1. Preparation of macrocycles 2; i.- K2CO3, refluxing
CH3CN, see ref.[3b] ii.- TFAA, CH2Cl2, room temp, see ref.[3b] iii.-
6 (2 mol), K2CO3, refluxing CH3CN.
Supporting information for this article is available on the
WWW under http://www.eurjoc.org or from the author.
3382
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/ejoc.200300171
Eur. J. Org. Chem. 2003, 3382Ϫ3386

15-Membered Nitrogen-Containing Olefinic and Benzo Macrocycles
FULL PAPER
The rich organometallic chemistry of compounds 1a, the well, higher rings and polymers formation not being a prob-
facility of their preparation, the potential for tuning of their lem. Introduction of different arenes at different steps con-
properties through variation of sulfonamides, and the cata- fers versatility on the preparation.
lytic properties of the metallic complexes motivated us to
launch a project aimed at access to a broad selection of lies upon the availability of starting materials. Appropriate
structures related to 1a. selection of sulfonamides permits the properties of the
The extreme simplicity of this modular synthesis also re-
Here we present the preparation of (E,E)-1,6,11-tris- macrocycles, such as solubility, to be tuned. Moreover, the
(arenesulfonyl)-3,4-benzo-1,6,11-triazacyclopentadeca-8,13- nitrogen atoms in 2 and in 3 are non-coordinating, the co-
dienes (2, Scheme 1) and 1,6,11-tris(arenesulfonyl)- ordinating ability, if any, being concentrated in the olefinic
3,4,8,9,13,14-tribenzo-1,6,11-triazacyclopentadecanes
(3, and benzo moieties.
Macrocycles 2 and 3 exhibit very weak coordinating
Scheme 2). Compounds similar to 3, with sulfur and phos-
phorus in place of nitrogen, have been prepared by routes ability towards silver() tetrafluoroborate[8,9] and none
different[7] from that proposed here.
towards silver triflate or Pd0. Mixing of equimolar amounts
of 2 or 3 and AgBF4 in refluxing acetone, followed by evap-
oration, gave residues that were discrete compounds rather
than mixtures, as evidenced by very different mps and dif-
ferent NMR spectra. However, isolation for further studies
failed due to instability. Macrocycles 2aaa, 2bbb, 3aaa, and
3aab were treated with Cr(CO)6 in refluxing di-n-butyl ether
under inert atmosphere. In all cases extremely insoluble
complexes were formed. Each of them showed two strong
infrared peaks in the 1898Ϯ6 and 1972Ϯ4 cmϪ1 regions, as
required for trigonal-pyramidal complexes of the
L3Cr(CO)3 type. Peaks at m/z values corresponding to the
molecular weight were detected for the complexes 2bbb-
Cr(CO)3 and 3aab-Cr(CO)3 by HRMS, but the extreme in-
solubility of these complexes prevented any further studies.
Conclusion
Easy, versatile, and efficient preparations of 15-mem-
bered triazamacrocycles containing internal olefins or fused
benzene rings, starting from easily available materials, are
described. The macrocycles coordinate silver very weakly.
Cr0 complexes are too insoluble for further studies.
Experimental Section
Scheme 2. Preparation of macrocycles 3; i.- 6 (4 mol), K2CO3, re-
fluxing CH3CN; ii Ar2SO2NH2 (1/2 mol), K2CO3, refluxing
CH3CN; iii.- TFAA, CH2Cl2, room temp; iv.- 6 (1 mol) K2CO3,
refluxing CH3CN.
General Remarks: Melting points were determined with a Kofler
apparatus and are uncorrected. IR spectra were recorded with a
Nicolet FT-IR 510 ZDX. NMR spectra were recorded with a
1
Bruker-Analytik AC 250 instrument. H NMR (250 MHz) chemi-
cal shifts are reported relative to CHCl3 at δ ϭ 7.26 and tetrameth-
ylsilane at δ ϭ 0.00, and 13C NMR (62.5 MHz) are reported rela-
tive to chloroform at δ ϭ 77.00 and tetramethylsilane at δ ϭ 0.0.
Mass spectra (EIMS) were obtained with a HewlettϪPackard
5989A spectrometer and determined at an ionizing voltage of
70 eV; relevant data are listed as m/z (%). MALDI-TOF spectra
were recorded on a BIFLEX spectrometer (Bruker-Franzen Analy-
tik) equipped with a pulsed nitrogen laser (337 nm), operating in
positive-ion reflector mode, and using 19 kV acceleration voltage.
Matrices (α-cyanocinnamic acid) were prepared at 5 mg/mL in
THF. Analytes were dissolved at concentrations between 0.1 and
5 mg/mL in THF or chloroform. Elemental analyses were deter-
Results and Discussion
Our preparation of macrocycles 2 is versatile, permitting
the introduction of different aryl groups at different syn-
thetic steps. Products 4bbb and 5bbb are known,[3b] while
all other compounds 4 and 5 were prepared similarly
(Scheme 1). The cyclization step proceeds excellently, the
formation of higher cycles and/or polymers not being a
problem.
Tribenzomacrocycles 3 are also easily prepared by con-
trolled condensations of 1,2-bis(bromomethyl)benzene (6)
with Boc-protected arenesulfonamides in the first step to
afford compounds 7, and with bis-sulfonamides 9 in the last
`
´
`
mined at the ‘‘Servei dЈAnalisi Quımica de la Universitat Auton-
oma de Barcelona’’.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris[(2,4,6-triisopropyl-
step (Scheme 2). Once more, the cyclization step works very phenyl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (4aaa): This com-
Eur. J. Org. Chem. 2003, 3382Ϫ3386
www.eurjoc.org  2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 3383

´
R. M. Sebastian, M. Moreno-Man˜as, A. Vallribera
FULL PAPER
pound was prepared in 97% yield as for 4bbb. M.p. 66Ϫ68 °C. IR acetonitrile (75 mL). The mixture was heated at reflux overnight
1
(KBr): ν˜ ϭ 2961, 1728, 1369, 1338, 1153 cmϪ1. H NMR (CDCl3,
and filtered. The filtrate was evaporated and the residue was chro-
matographed through a column of silica gel with cyclohexane/ethyl
250 MHz): δ ϭ 1.21 (s, 18 H), 1.26 (complex absorption, 54 H),
2.93 (sept, J ϭ 6.9 Hz, 3 H), 3.85 (d, J ϭ 5.0 Hz, 4 H), 3.93 (sept, acetate (9:1) as eluent to afford 2aaa as a white solid (0.53 g, 97%).
1
J ϭ 6.7 Hz, 4 H), 4.18 (sept, J ϭ 6.7 Hz, 2 H), 4.42 (d, J ϭ 4.5 Hz, M.p. 90Ϫ92 °C. IR (KBr): ν˜ ϭ 2959, 1320, 1153 cmϪ1. H NMR
4 H), 5.65Ϫ5.95 (m, 4 H), 7.15 (s, 4 H), 7.19 (s, 2 H) ppm. 13C
NMR (CDCl3, 62.5 MHz): δ ϭ 23.3, 23.3, 24.2, 24.6, 27.5, 29.0,
33.9, 46.0, 46.1, 83.2, 123.1, 123.6, 127.8, 130.1, 130.9, 134.0, 149.9,
(CDCl3, 250 MHz): δ ϭ 1.16Ϫ1.28 (complex absorption, 54 H),
2.88 (sept, J ϭ 6.9 Hz, 1 H), 2.89 (sept, J ϭ 6.9, 2 H), 3.80 (m, 8
H), 4.09 (sept, J ϭ 6.7 Hz, 2 H), 4.11 (sept, J ϭ 6.7 Hz, 4 H), 4.39
150.6, 151.3, 152.6, 152.7 ppm. C63H99N3O10S3 (1154.7): calcd. C (apparent s, 4 H), 5.57 (dt, J ϭ 15.6, 5.4 Hz, 2 H), 5.68 (dt, J ϭ
65.53, H 8.64, N 3.64; found C 65.54, H 8.76, N 3.62, S 8.11.
15.6, 6.1 Hz, 2 H), 7.12 (s, 2 H), 7.16 (s, 4 H), 7.27 (double m, 4
H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 23.2, 24.4, 24.7, 28.9,
29.4, 33.9, 53.7, 46.3, 49.4, 123.6, 123.8, 127.1, 127.3, 130.4, 130.8,
132.7, 133.2, 151.2, 153.0, 153.1 ppm. MALDI-TOF MS: m/z ϭ
1055.6 [M ϩ H], 1079.1 [M ϩ Na], 1095 [M ϩ K]. C61H89N3O6S3
(1056.6): calcd. C 69.34, H 8.49, N 3.98; found C 69.59, H 9.12,
N 3.71.
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris[(4-methylphenyl)-
sulfonyl]-1,6,11-triazaundeca-3,8-diene (4bbb): See ref.[3b]
(E,E)-1,11-Bis(tert-butyloxycarbonyl)-6-[(4-methylphenyl)sulfonyl]-
1,11-bis[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triazaundeca-3,8-
diene (4aab): This compound was prepared in 71% yield as for 4bbb.
M.p. 64Ϫ66 °C. IR (KBr): ν˜ ϭ 2962, 1728, 1369, 1338, 1158 cmϪ1
.
(E,E)-1,6,11-Tris[(4-methylphenyl)sulfonyl]-3,4-benzo-1,6,11-triaza-
cyclopentadeca-8,13-diene (2bbb): This compound was prepared in
68% yield as for 2aaa. M.p. 102Ϫ104 °C. IR (KBr): ν˜ ϭ 1340, 1161
1H NMR (CDCl3, 250 MHz): δ ϭ 1.20 (s, 18 H), 1.26 (d, J ϭ
6.8 Hz, 24 H), 1.27 (d, J ϭ 6.9 Hz, 12 H), 2.44 (s, 3 H), 2.93 (sept,
J ϭ 6.9 Hz, 2 H), 3.87 (d, J ϭ 6.3 Hz, 4 H), 3.91 (sept, J ϭ 6.8 Hz,
4 H), 4.38 (d, J ϭ 5.0 Hz, 4 H), 5.65 (dt, J ϭ 15.4, 6.2 Hz, 2 H),
5.80 (dt, J ϭ 15.4 and 5.0 Hz, 2 H), 7.15 (s, 4 H), 7.34 (d, J ϭ
8.2 Hz, 2 H), 7.75 (d, J ϭ 8.2 Hz, 2 H) ppm. 13C NMR (CDCl3,
62.5 MHz): δ ϭ 21.2, 23.3, 24.2, 27.5, 28.9, 33.9, 46.0, 47.6, 83.3,
123.1, 127.0, 127.6, 129.5, 129.7, 133.9, 137.1, 142.7, 149.9, 150.6,
152.8 ppm. C55H83N3O10S3 (1042.5): calcd. C 63.37, H 8.02, N
4.03; found C 63.30, H 8.08, N 4.05.
1
cmϪ1. H NMR (CDCl3, 250 MHz): δ ϭ 2.43 (s, 3 H), 2.47 (s, 6
H), 3.43 (d, J ϭ 5.4 Hz, 4 H), 3.66 (d, J ϭ 6.5 Hz, 4 H), 4.35
(apparent s, 4 H), 5.20 (dt, J ϭ 15.4, 5.4 Hz, 2 H), 5.36 (dt, J ϭ
15.4, 6.5 Hz, 2 H), 7.23Ϫ7.35 (m, 6 H), 7.37 (d, J ϭ 8.2 Hz, 4 H),
7.60 (d, J ϭ 8.4 Hz, 2 H), 7.74 (d, J ϭ 8.2 Hz, 4 H) ppm. 13C
NMR (CDCl3, 62.5 MHz): δ ϭ 21.3, 49.2, 49.8, 50.8, 126.8, 127.1,
127.2, 127.5, 128.1, 129.5, 129.6, 131.1, 134.1, 135.5, 143.4 ppm.
MALDI-TOF MS: m/z ϭ 742.4 [M ϩ Na], 758.4 [M ϩ K]. FAB-
HRMS: m/z ϭ 720.22 [M ϩ H], 737.23 [M ϩ NH4]. C37H41N3O6S3
(719.9): calcd. C 61.73, H 5.74, N, 5.84; found C 61.44, H 6.34;
N 5.36.
(E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triaza-
undeca-3,8-diene (5aaa): This compound was prepared in 99% yield
as for 5bbb. M.p.144Ϫ146 °C. IR (KBr): ν˜ ϭ 3273, 2960, 1152
1
cmϪ1. H NMR (CDCl3, 250 MHz): δ ϭ 1.23Ϫ1.30 (complex ab-
(E,E)-11-[(4-Methylphenyl)sulfonyl]-1,6-bis[(2,4,6-triisopropyl-
phenyl)sulfonyl]-3,4-benzo-1,6,11-triazacyclopentadeca-8,13-diene
(2aab): This compound was prepared in 85% yield as for 2aaa. M.p.
sorption, 54 H), 2.92 (sept, J ϭ 6.9 Hz, 1 H), 2.93 (sept, J ϭ 6.9,
2 H), 3.56 (t, J ϭ 5.7 Hz, 4 H), 3.72 (d, J ϭ 5.7 Hz, 4 H), 4.08
(sept, J ϭ 6.9 Hz, 2 H), 4.18 (sept, J ϭ 6.7 Hz, 4 H), 4.62 (t, J ϭ
6.2 Hz, 2 H), 5.58 (dt, J ϭ 15.3 and 6.2 Hz, 2 H), 5.69 (dt, J ϭ
15.3 and 5.7 Hz, 2 H), 7.17 (s, 2 H), 7.19 (s, 4 H) ppm. 13C NMR
(CDCl3, 62.5 MHz): δ ϭ 23.2, 23.3, 24.5, 24.6, 29.0, 29.3, 33.9,
43.9, 46.3, 123.5, 123.6, 127.6, 130.6, 130.7, 131.9, 150.0, 151.2,
152.6, 153.0 ppm. C53H83N3O6S3 (954.5): calcd. C 66.70, H 8.76,
N 4.40, S 10.08; found C 66.66, H 8.86, N 4.41, S 9.99.
84Ϫ86 °C. IR (KBr): ν˜ ϭ 2960, 2927, 1153 cmϪ1 1H NMR
.
(CDCl3, 250 MHz): δ ϭ 1.27 (d, J ϭ 6.9 Hz, 24 H), 1.28 (d, J ϭ
6.7 Hz, 12 H), 2.46 (s, 3 H), 2.69 (sept, J ϭ 6.7, 2 H), 3.73 (d, J ϭ
5.7 Hz, 4 H), 3.84 (d, J ϭ 6.5 Hz, 4 H), 4.12 (sept, J ϭ 6.9 Hz, 4
H), 4.38 (apparent s, 4 H), 5.52 (dt, J ϭ 15.6, 5.7 Hz, 2 H), 5.74
(dt, J ϭ 15.6, 6.5 Hz, 2 H), 7.19 (s, 4 H), 7.20Ϫ7.31 (m, 4 H), 7.33
(d, J ϭ 8.1 Hz, 2 H), 7.66 (d, J ϭ 8.1 Hz, 2 H) ppm. 13C NMR
(CDCl3, 62.5 MHz): δ ϭ 21.2, 23.3, 24.7, 26.7, 29.4, 33.9, 43.8,
46.5, 51.1, 123.9, 126.8, 127.1, 127.3, 127.6, 129.6, 130.8, 132.8,
132.9, 135.6, 143.3, 151.2, 153.2. ESI-MS: m/z ϭ 943 (M), 961 [M
ϩ NH4]. C53H73N3O6S3 (944.4): calcd. (ϩ 1/2 cyclohexane) C
68.18, H 8.07, N 4.26, S 9.75; found C 68.07, H 8.26, N 4.22,
S 9.59.
(E,E)-1,6,11-Tris[(4-methylphenyl)sulfonyl]-1,6,11-triazaundeca-3,8-
diene (5bbb): See ref.[3b]
(E,E)-6-[(4-Methylphenyl)sulfonyl]-1,11-bis[(2,4,6-triisopropyl-
phenyl)sulfonyl]-1,6,11-triazaundeca-3,8-diene (5aab): This com-
pound was prepared in 74% yield as for 5bbb. M.p. 150Ϫ152 °C.
IR (KBr): ν˜ ϭ 3344, 2960, 1323, 1161 cmϪ1 1H NMR (CDCl3,
.
N-(2-Bromomethylbenzyl)-N-(tert-butyloxycarbonyl)-(2,4,6-triiso-
propyl)benzenesulfonamide (7a). General Method: A mixture of N-
Boc-(2,4,6-triisopropyl)benzenesulfonamide (5.00 g, 13 mmol), 1,2-
bis(bromomethylbenzene), 6, (14.34 g, 52 mmol), anhydrous pot-
assium carbonate (2.70 g, 19 mmol), and acetonitrile (200 mL) was
heated at reflux for 14 h. After the mixture had cooled, the solids
were filtered off and the filtrate was evaporated. The residue was
chromatographed through a silica gel column with ethyl acetate/
hexanes mixtures of increasing polarity. Excess 6 was eluted first,
followed by 7a (5.63 g, 76%). M.p. 140Ϫ142 °C. IR (KBr): ν˜ ϭ
250 MHz): δ ϭ 1.27 (d, J ϭ 6.9 Hz, 24 H), 1.28 (d, J ϭ 6.9 Hz, 12
H), 2.45 (s, 3 H), 2.93 (sept, J ϭ 6.9 Hz, 2 H), 3.52 (t, J ϭ 5.7 Hz,
4 H), 3.72 (d, J ϭ 5.9 Hz, 4 H), 4.14 (sept, J ϭ 6.9 Hz, 4 H), 4.55
(d, J ϭ 6.4 Hz, 2 H), 5.47 (dt, J ϭ 15.5, 5.9 Hz, 2 H), 5.62 (dt, J ϭ
15.5, 5.7 Hz, 2 H), 7.18 (s, 4 H), 7.32 (d, J ϭ 8.2 Hz, 2 H), 7.67 (d,
J ϭ 8.2 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 21.2,
23.3, 24.6, 29.3, 33.8, 43.8, 48.0, 123.5, 126.9, 127.6, 129.5, 129.8,
131.9, 136.8, 143.3, 150.0, 152.6 ppm. C45H67N3O6S3 (842.2):
calcd.C 64.17, H 8.02, N 4.99, S 11.42; found C 64.06, H 8.24, N
4.96, S 11.16.
1
2965, 1718, 1368, 1337, 1153 cmϪ1. H NMR (CDCl3, 250 MHz):
(E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-3,4-benzo-
1,6,11-triazacyclopentadeca-8,13-diene (2aaa). General Method: A
solution of 5aaa (0.50 g, 0.24 mmol) and dibromo compound 6
δ ϭ 1.16 (s, 9 H), 1.30 (d, J ϭ 6.8 Hz, 6 H), 1.33 (d, J ϭ 6.8 Hz,
12 H), 2.97 (sept, J ϭ 6.8 Hz, 1 H), 4.06 (sept, J ϭ 6.8 Hz, 2 H),
4.70 (s, 2 H), 5.22 (s, 2 H), 7.20Ϫ7.40 (m, 3 H), 7.23 (s, 2 H), 7.70
(0.14 g, 0.52 mmol) in acetonitrile (75 mL) was added dropwise to a (d, J ϭ 7.5 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 24.1,
suspension of potassium carbonate (0.36 g, 2.6 mmol) in refluxing
3384
25.0, 28.1, 29.9, 31.9, 34.7, 45.9, 84.4, 124.0, 127.9, 128.2, 129.9,
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2003, 3382Ϫ3386

15-Membered Nitrogen-Containing Olefinic and Benzo Macrocycles
130.6, 134.1, 135.0, 136.8, 150.9, 151.4, 153.8 ppm. C28H40BrNO4S 1,6,11-Tris-[(2,4,6-triisopropylphenyl)sulfonyl]-3,4;8,9-dibenzo-
FULL PAPER
(566.6): calcd. C 59.36, H 7.12, N 2.47, S 5.66; found C 59.62, H
7.16, N 2.55, S 5.37,
1,6,11-triazaundecane (9aaa): This compound was prepared in 75%
yield as for 9bbb (vide infra). M.p. 87Ϫ89 °C. IR (KBr): ν˜ ϭ 2960,
2927, 1601, 1317, 1152 cmϪ1 1H NMR (CDCl3, 250 MHz): δ ϭ
.
N-(2-Bromomethylbenzyl)-N-(tert-butyloxycarbonyl)-4-methyl-
benzenesulfonamide (7b): This compound was prepared in 77%
yield as for 7a. M.p. 109Ϫ110 °C. IR (KBr): ν˜ ϭ 1719, 1353, 1173,
1.24 (d, J ϭ 6.7 Hz, 24 H), 1.29 (d, J ϭ 6.9 Hz, 12 H), 1.30 (d, J ϭ
6.7 Hz, 12 H), 1.33 (d, J ϭ 6.9 hz, 6 H), 1.46 (s, cyclohexane), 2.46
(sept, J ϭ 6.9 Hz, 3 H), 3.74 (d, J ϭ 6.2 Hz, 4 H), 4.06 (sept, J ϭ
6.7 Hz, 4 H), 4.20 (sept, J ϭ 6.7 Hz, 2 H), 4.56 (s, 4 H), 4.80 (t,
J ϭ 6.2 Hz, 2 H), 7.06Ϫ7.28 (m, 14 H) ppm. 13C NMR (CDCl3,
62.5 MHz): δ ϭ 23.3, 23.3, 24.6, 24.7, 26.7, 29.3, 29.7, 33.9, 43.6,
45.9, 123.5, 124.0, 127.6, 128.0, 128.9, 129.1, 131.6, 132.3, 133.7,
134.3, 150.2, 150.9, 152.5, 153.1 ppm. C61H87N3O6S3 (1054.6):
calcd. (ϩ C6H12) C 70.67, H 8.76, N, 3.69; found C 71.29, H 9.40,
N 3.52.
1
1152 cmϪ1. H NMR (CDCl3, 250 MHz): δ ϭ 1.35 (s, 9 H), 2.46
(s, 3 H), 4.67 (s, 2 H), 5.24 (s, 2 H), 7.24Ϫ7.42 (m, 4 H), 7.30 (d, J ϭ
8.4 Hz, 2 H), 7.72 (d, J ϭ 8.4 Hz, 2 H) ppm. 13C NMR (CDCl3,
62.5 MHz): δ ϭ 21.4, 27.6, 31.0, 46.3, 84.4, 127.3, 127.4, 127.9,
128.9, 130.1, 134.6, 136.2, 136.6, 144.1, 150.8 ppm. C20H24BrNO4S
(454.4): calcd. C 52.87, H 5.32, N 3.08, S 7.06; found C 53.03, H
5.44, N 3.10, S 6.82.
1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris-[(2,4,6-triisopropyl-
phenyl)sulfonyl]-3,4;8,9-dibenzo-1,6,11-triazaundecane (8aaa): This
compound was prepared in 69% yield as for 8bbb (vide infra). M.p.
1,6,11-Tris-[(4-methylphenyl)sulfonyl]-3,4;8,9-dibenzo-1,6,11-triaza-
undecane (9bbb), General Method: Trifluoroacetic acid (10 mL) was
added to a solution of 8bbb (0.87 g, 0.95 mmol) in dichloromethane
(10 mL). The mixture was stirred at room temp for 7 h and the
solvents were evaporated to dryness. The residue was partitioned
between dichloromethane and water. The organic layer was dried
with anhydrous Na2SO4 and the solvents were evaporated to afford
practically pure 9bbb (0.68 g, 100% yield). A sample for elemental
analysis was chromatographed through a column of silica gel with
cyclohexane/ethyl acetate (3:8). M.p. 76Ϫ78 °C. IR (KBr): ν˜ ϭ
1
73Ϫ75 °C. IR (KBr): ν˜ ϭ 2961, 2929, 1729, 1369, 1338, 1154. H
NMR (CDCl3, 250 MHz): δ ϭ 1.11 (s, 18 H), 1.28 (d, J ϭ 6.9 Hz,
36 H), 1.33 (d, J ϭ 6.5 Hz, 18 H), 2.95 (sept, J ϭ 6.5 Hz, 3 H),
3.93 (sept, J ϭ 6.9 Hz, 4 H), 4.30 (sept, J ca. 6.8 Hz, 2 H), 4.63 (s,
2 H), 4.79 (s, 2 H), 6.97 (d, J ϭ 6.9 Hz, 2 H), 7.12Ϫ7.32 (m, 10
H), 7.60 (d, J ϭ 7.9 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.5 MHz):
δ ϭ 23.3, 24.2, 24.8, 26.6 (cyclohexane), 27.4, 29.1, 29.8, 33.9, 33.9,
45.7, 46.0, 52.1, 83.3, 123.2, 123.6, 123.9, 127.0, 127.4, 129.5, 127.8,
128.9, 132.1, 133.4, 133.9, 135.8, 136.0, 150.3, 150.6, 152.8 ppm.
C71H103N3O10S3 (1254.8): calcd. (ϩ 3/2 C6H12) C 69.58, H 8.83, N
3.04, S 6.97; found C 69.83, H 9.03, N 3.20, S 6.75.
3268, 1334, 1321, 1161 cmϪ1 1H NMR (CDCl3, 250 MHz): δ ϭ
.
2.43 (s, 6 H), 2.49 (s, 3 H), 3.86 (d, J ϭ 6.2 Hz, 4 H), 4.30 (s, 4 H),
4.97 (d, J ϭ 6.2 Hz, 2 H), 7.30 (m, 8 H), 7.28 (d, J ϭ 8.3 Hz, 4 H),
7.38 (d, J ϭ 8.2 Hz, 2 H), 7.66 (d, J ϭ 8.3 Hz, 4 H), 7.74 (d, J ϭ
8.2 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 21.3, 21.3,
44.2, 49.2, 126.9, 127.2, 127.7, 127.8, 129.3, 129.4, 129.8, 133.8,
134.1, 135.2, 136.3, 143.2, 143.6 ppm. C37H39N3O6S3 (717.9): calcd.
C 61.90, H 5.48, N 5.85; found C 62.37, H 5.82, N 5.52.
1,11-Bis(tert-butyloxycarbonyl)-1,6,11-tris-[(4-methylphenyl)-
sulfonyl]-3,4;8,9-dibenzo-1,6,11-triazaundecane (8bbb). General
Method:
A mixture of 4-methylbenzenesulfonamide (0.19 g,
1.10 mmol), bromo compound 7b (1.00 g, 2.20 mmol), anhydrous
potassium carbonate (0.91 g, 6.6 mmol), and acetonitrile (30 mL)
was heated at reflux for 14 h. After the mixture had cooled, the
solids were filtered off and the filtrate was evaporated. The residue
was chromatographed through a silica gel column with ethyl acet-
ate/cyclohexane (3:7) to afford 8bbb in 93% yield (1.00 g), taking
into account that 8bbb crystallized with one mol of cyclohexane.
6-[(4-Methylphenyl)sulfonyl]-1,11-bis[(2,4,6-triisopropylphenyl)-
sulfonyl]-3,4;8,9-dibenzo-1,6,11-triazaundecane (9aab): This com-
pound was prepared in 95% yield as for 9bbb. M.p. 66Ϫ68 °C. IR
1
(KBr): ν˜ ϭ 2960, 2927, 1600, 1329, 1161 cmϪ1. H NMR (CDCl3,
250 MHz): δ ϭ 1.29 (t, J ϭ 6.9 Hz, 26 H), 1.46 (cyclohexane), 2.51
(s, 3 H), 2.95 (sept, J ϭ 6.9 Hz, 2 H), 3.96 (d, J ϭ 6.2 Hz, 4 H),
4.12 (sept, J ϭ 6.9 Hz, 4 H), 4.44 (br. s, 4 H), 4.78 (t, J ϭ 6.2 Hz,
2 H), 6.95Ϫ7.21 (m, 12 H), 7.40 (d, J ϭ 8.4 Hz, 2 H), 7.81 (d, J ϭ
8.4 Hz, 2 H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 21.3, 23.3,
24.6, 26.6 (cyclohexane), 29.4, 33.9, 44.0, 49.6, 123.5, 127.3, 127.6,
127.8, 129.2, 129.5, 129.8, 131.9, 134.2, 134.4, 135.1, 143.6, 150.0,
152.5 ppm. C53H71N3O6S3 (942.4): calcd. C 67.55, H 7.59, N 4.46;
found C 68.04, H 8.00, N 4.30.
1
M.p. 63Ϫ65 °C. IR (KBr): ν˜ ϭ 2927, 1729, 1359, 1157 cmϪ1. H
NMR (CDCl3, 250 MHz): δ ϭ 1.32 (s, 18 H), 1.44 (s, 12 H, cyclo-
hexane), 2.43 (s, 6 H), 2.47 (s, 3 H), 4.45 (s, 4 H), 4.95 (s, 4 H),
7.12 (m, 8 H), 7.25 (d, J ϭ 8.3 Hz, 4 H), 7.37 (d, J ϭ 8.2 Hz, 2 H),
7.60 (d, J ϭ 8.3 Hz, 4 H), 7.79 (d, J ϭ 8.2 Hz, 2 H) ppm. 13C
NMR (CDCl3, 62.5 MHz): δ ϭ 21.3, 26.7 (cyclohexane), 27.6, 46.5,
50.0, 84.1, 127.0, 127.3, 127.7, 128.8, 129.0, 129.6, 132.7, 135.4,
135.6, 136.7, 143.4, 143.9, 150.8 ppm. C47H55N3O10S3 (918.2):
calcd. (ϩ C6H12) C 63.51, H 6.73, N 4.19, S 9.59; found C 63.04,
H 6.88, N 4.12, S 9.48.
1,6,11-Tris-[(2,4,6-triisopropylphenyl)sulfonyl]-3,4;8,9;13,14-tri-
benzo-1,6,11-triazacyclopentadecane (3aaa): This compound was
prepared in 81% yield as for 3bbb (vide infra). M.p. 200Ϫ201 °C.
1,11-Bis(tert-butyloxycarbonyl)-6-[(4-methylphenyl)sulfonyl]-1,11-
bis)[(2,4,6-triisopropylphenylsulfonyl]-3,4;8,9-dibenzo-1,6,11-tri-
azaundecane (8aab): This compound was prepared in 82% yield as
for 8bbb. M.p. 85Ϫ87 °C. IR (KBr): ν˜ ϭ 2961, 2927, 1728, 1369,
1338, 1158 cmϪ1. 1H NMR (CDCl3, 250 MHz): δ ϭ 1.14 (s, 18 H),
1.30 (t, J ϭ 6.7 Hz, 36 H), 2.48 (s, 3 H), 2.96 (sept, J ϭ 6.7 Hz, 2
H), 4.00 (sept, J ϭ 6.7 Hz, 4 H), 4.55 (s, 4 H), 4.99 (s, 4 H), 6.92
(dd, J ϭ 7.6, 1.0 Hz, 2 H), 7.05 (dt, J ϭ 7.3, 1.1 Hz, 2 H), 7.18 (s,
4 H), 7.20 (dt, J ϭ 7.3 and 1.1 Hz, 2 H), 7.36 (d, J ϭ 8.1 Hz, 2
H), 7.47 (dd, J ϭ 7.6, 1.0 Hz, 2 H), 7.84 (d, J ϭ 8.1 Hz, 2 H) ppm.
1
IR (KBr): ν˜ ϭ 2942, 1596, 1458, 1360, 1156, 1049, 762 cmϪ1. H
NMR (CDCl3, 250 MHz): δ ϭ 1.22 (d, J ϭ 6.7 Hz, 36 H), 1.28 (d,
J ϭ 6.9 Hz, 18 H), 2.93 (sept, J ϭ 6.9 Hz, 3 H), 4.03 (sept, J ϭ
6.7 Hz, 6 H), 4.21 (s, 12 H), 7.12 (m, 6 H), 7.17 (s, 6 H), 7.30 (s, 6
H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 23.3, 24.6, 29.6, 33.8,
46.3, 123.9, 127.6, 128.5, 131.9, 133.3, 150.8, 153.1. ESI-MS:
m/z ϭ 1155.1 (M). C69H93N3O6S3 (1156.7): calcd. C 71.65, H 8.10,
N 3.63; found C 71.55, H 8.16, N 3.48.
13C NMR (CDCl3, 62.5 MHz): δ ϭ 21.3, 23.3, 24.3, 26.7, 27.4, 1,6,11-Tris-[(4-methylphenyl)sulfonyl]-3,4;8,9;13,14-tribenzo-1,6,11-
29.1, 34.0, 46.0, 49.4, 83.3, 123.2, 126.8, 127.2, 127.3, 127.8, 129.0,
129.5, 132.2, 133.8, 135.6, 136.1, 143.1, 150.3, 150.7, 152.9 ppm.
triazacyclopentadecane (3bbb). General Method: A mixture of 9bbb
(1.77 g, 2.47 mmol), dibromo compound 6 (0.68 g, 2.47 mmol), and
C63H87N3O10S3 (1142.6): calcd. C 66.23, H 7.67, N 3.68, S 8.42; acetonitrile (75 mL) was added dropwise (2 h) to anhydrous potass-
found C 66.12, H 8.01, N 3.67, S 8.15.
ium carbonate (1.71 g) in refluxing acetonitrile (75 mL). The mix-
3385
Eur. J. Org. Chem. 2003, 3382Ϫ3386
www.eurjoc.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

´
R. M. Sebastian, M. Moreno-Man˜as, A. Vallribera
FULL PAPER
Chem. Lett. 1998, 8, 357Ϫ360. [2b] W. P. D. Goldring, L. Weiler,
Org. Lett. 1999, 1, 1471Ϫ1473.
ture was stirred for 24 h (1H NMR monitoring). After the mixture
had cooled, the solids were filtered off and the filtrate was evapo-
rated to afford 3bbb (0.30 g). Solid 3bbb precipitated before evapor-
ation, however, so the filtered solids were extracted several times
with hot chloroform, and the chloroform was evaporated to afford
more 3bbb (total yield 79%). M.p. 271Ϫ272 °C. IR (KBr): ν˜ ϭ
[3] [3a]
´
J. Cortes, M. Moreno-Man˜as, R. Pleixats, Eur. J. Org.
[3b]
`
S. Cerezo, J. Cortes, D. Galvan, E.
Chem. 2000, 239Ϫ243.
Lago, C. Marchi, E. Molins, M. Moreno-Man˜as, R. Pleixats,
´
J. Torrejon, A. Vallribera, Eur. J. Org. Chem. 2001, 329Ϫ337.
[3c]
`
J. Cortes, M. Moreno-Man˜as, R. Pleixats, Tetrahedron Lett.
1
1339, 1164 cmϪ1. H NMR (CDCl3, 250 MHz): δ ϭ 2.50 (s, 9 H),
2001, 42, 4337Ϫ4339. [3d] S. Cerezo, J. Cortes, E. Lago, E. Mol-
`
4.11 (s, 12 H), 7.03Ϫ7.12 (m, 12 H), 7.36 (d, J ϭ 8.2 Hz, 6 H), 7.69
(d, J ϭ 8.2 Hz, 6 H) ppm. 13C NMR (CDCl3, 62.5 MHz): δ ϭ 21.3,
48.5, 127.0, 127.3, 127.6, 128.9, 129.5, 129.7, 130.4, 133.4, 134.4,
135.5, 143.4. ESI-MS: m/z ϭ 819.9 (M), 839.0 [M ϩ NH4], 857.0
(M ϩ2NH4). FAB HRMS: m/z ϭ C45H45N3O6S3 ϩ H: calcd.
820.255748; found 820.256.
´
ins, M. Moreno-Man˜as, T. Parella, R. Pleixats, J. Torrejon, A.
[3e]
Vallribera, Eur. J. Inorg. Chem. 2001, 1999Ϫ2006.
bet, E. Masllorens, M. Moreno-Man˜as, A. Pla-Quintana, M.
A. Llo-
´
Rodrıguez, A. Roglans, Tetrahedron Lett. 2002, 43, 1425Ϫ1428.
[3f]
M. Moreno-Man˜as, J. Spengler, Tetrahedron 2002, 58,
7769Ϫ7774.
[4]
S. Cacchi, G. Fabrizi, A. Goggiamani, M. Moreno-Man˜as, A.
Vallribera, Tetrahedron Lett. 2002, 43, 5537Ϫ5540.
[5] [5a]
11-[(4-Methylphenyl)sulfonyl]-1,6-bis[(2,4,6-triisopropylphenyl)-
sulfonyl]-3,4;8,9;13,14-tribenzo-1,6,11-triazacyclopentadecane
(3aab): This compound was prepared in 97% yield as for 3bbb. M.p.
222 °C. IR (KBr): ν˜ ϭ 2959, 2919, 1600, 1456, 1362, 1323, 1163,
´
B. Estrine, B. Blanco, S. Bouquillon, F. Henin, M. Moreno-
Man˜as, J. Muzart, C. Pena, R. Pleixats, Tetrahedron Lett. 2001,
42, 7055Ϫ7057. [5b] M. Moreno-Man˜as, R. Pleixats, J. Spengler,
´
C. Chevrin, B. Estrine, S. Bouquillon, F. Henin, J. Muzart, A.
1154, 766 cmϪ1 1H NMR (CDCl3, 250 MHz): δ ϭ 1.22 (d, J ϭ
.
Pla-Quintana, A. Roglans, Eur. J. Org. Chem. 2003, 274Ϫ283.
J. Masllorens, M. Moreno-Man˜as, A. Pla-Quintana, A. Rog-
lans, Org. Lett. 2003, 5, 1559Ϫ1561.
[6]
[7]
[8]
6.7 Hz, 24 H), 1.28 (d, J ϭ 6.9 Hz, 12 H), 2.52 (s, 3 H), 2.93 (sept,
J ϭ 6.9 Hz, 2 H), 3.93 (s, 4 H), 4.04 (sept, J ϭ 6.7 Hz, 4 H), 4.23
(s, 4 H), 4.29 (s, 4 H), 7.00Ϫ7.30 (m, 12 H), 7.19 (s, 4 H), 7.36 (d,
J ϭ 8.2 Hz, 2 H), 7.61 (d, J ϭ 8.2 Hz, 2 H) ppm. 13C NMR
(CDCl3, 62.5 MHz): δ ϭ 21.3, 23.3, 24.6, 29.6, 33.9, 45.6, 45.8,
49.6, 123.9, 127.2, 127.3, 127.4, 127.6, 127.9, 128.6, 129.3, 129.6,
132.3, 133.1, 133.4, 133.5, 134.8, 143.5, 150.7, 153.0. ESI MS: m/
z ϭ 1043.7 (M), 1060.5 [M ϩ NH4]. FAB HRMS: m/z ϭ 1044.504
[M ϩ H]. C61H77N3O6S3 (1044.5): calcd. C 70.15, H 7.43, N 4.02;
found C 70.55, H 7.76, N 3.93.
For a review see: G. Wilke, Angew. Chem. 1988, 100, 189Ϫ211;
Angew. Chem. Int. Ed. Engl. 1988, 27, 185Ϫ206.
[8a] P. B. Savage, S. K. Holmgren, S. H. Gellman, J. Am. Chem.
[8b]
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Am. Chem. Soc. 1993, 115, 10448Ϫ10449.
P. B. Savage, S. H. Gellman, J.
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S. K. Holmgren,
P. B. Savage, J. M. Desper, K. D. Schladetzky, D. R. Powell, S.
H. Gellman, Tetrahedron 1997, 53, 12249Ϫ12262.
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Koten, J. G. Noltes, in Comprehensive Organometallic Chemis-
[9]
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Pergamon Press, New York, 1982, pp. 709Ϫ763.
[9b]
G. van
Koten, S. L. James, J. T. B. H. Jastrzebski, in Comprehensive
Organometallic Chemistry II, Vol. 3 (E. W. Abel, F. G. A. Stone,
G. Wilkinson, Eds.), Pergamon Press, New York, 1995, pp.
57Ϫ133.
Acknowledgments
We acknowledge financial support from the Spanish ‘‘Ministerio
[10]
For related carbocyclic structures that coordinate silver() see:
[10a] C. Cohen-Addad, P. Baret, P. Chautemps, J.-L. Pierre, Acta
Crystallogr., Sect. C 1983, 39, 1346Ϫ1349. [10b] H. C. Kang, A.
´
Tecnologıa’’ (Projects PB98Ϫ0902 and
de Ciencia
y
BQU2002Ϫ04002) and the Generalitat de Catalunya (Project
2001SGR00181). One of us (R. M. S.) has been affiliated into the
research group through a ‘‘Ramon y Cajal’’ contract (MCYT-
FEDER/FSE).
W. Hanson, B. Eaton, V. Boekelheide, J. Am. Chem. Soc. 1985,
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107, 1979Ϫ1985.
F. R. Heirtzler, H. Hopf, P. G. Jones, P.
[10d]
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R. Heirtzler, H. Hopf, P. G. Jones, P. Bubenitschek, Chem. Ber.
F.
[10e]
1995, 128, 1079Ϫ1082.
P. G. Jones, P. Bubenitschek, F. R.
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T. A. Kaden, in Comprehensive Heterocyclic Chemistry, II
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(A. R. Katritzky, C. W. Rees, E. F. V Scriven, Eds.), Elsevier
1380Ϫ1384.
P. G. Jones, F. Heirtzler, H. Hopf, Acta Crys-
Science Ltd., Oxford, 1996, vol. 9, chapter 9.28, pp. 789Ϫ807.
tallogr., Sect. C 1996, 52, 1384Ϫ1388. [10g] M. Iyoda, Y. Kuwat-
ani, T. Yamauchi, M. Oda, J. Chem. Soc., Chem. Commun.
1988, 65Ϫ66. [10h] T. Yoshida, Y. Kuwatani, K. Hara, M. Yosh-
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[1b]
G. W. Gokel, M. F. Fedders, in Comprehensive Heterocyclic
Chemistry, II (A. R. Katritzky, C. W. Rees, E. F. V Scriven,
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A. S. Ripka, R. S. Bohacek, D. H. Rich, Bioorg. Med.
Received March 21, 2003
3386
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Org. Chem. 2003, 3382Ϫ3386