Metal complexes of 15-membered triolefinic macrocycles. (E,E,Z)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6, 11-triazacyclopentadeca-3,8,13-triene and its palladium(0), platinum(0), and silver(I) complexes

Article abstract of DOI:10.1016/S0040-4039(01)00758-4

The preparation of the 15-membered macrocycle (E,E,Z)-1,6,11-tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6, 11-triazacyclopentadeca-3,8,13-triene is reported. This cyclic triolefin forms stable complexes with palladium(0) and platinum(0), and a moderately stable complex with silver(I) tetrafluoroborate.

Full text of DOI:10.1016/S0040-4039(01)00758-4

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 42 (2001) 4337–4339
Metal complexes of 15-membered triolefinic macrocycles.
(E,E,Z)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-
1,6,11-triazacyclopentadeca-3,8,13-triene and its palladium(0),
platinum(0), and silver(I) complexes
Jordi Corte`s, Marcial Moreno-Man˜as* and Roser Pleixats
Department of Chemistry, Universitat Auto`noma de Barcelona, Cerdanyola, 08193 Barcelona, Spain
Received 23 March 2001; accepted 1 May 2001
Abstract—The preparation of the 15-membered macrocycle (E,E,Z)-1,6,11-tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triazacyclo-
pentadeca-3,8,13-triene is reported. This cyclic triolefin forms stable complexes with palladium(0) and platinum(0), and a
moderately stable complex with silver(I) tetrafluoroborate. © 2001 Elsevier Science Ltd. All rights reserved.
Nitrogen-containing 15-membered macrocycles are
commonplace.1,2 However, nitrogen-containing 15-
membered macrocycles featuring internal olefinic dou-
ble bonds are exceptional. The few known examples
contain only one double bond, and metathesis is the
key step for their preparation.3 We have reported the
formation of some novel triazatriolefinic macrocycles
with the structure of (E,E,E)-1,6,11-tris(arylsulfonyl)-
1,6,11-triazacyclopentadeca-3,8,13-triene by non-selec-
tive palladium(0)-catalyzed Tsuji–Trost allylation of
arenesulfonamides with (Z)-2-butene-1,4-diol biscar-
bonate.4 More recently, we have published synthetic
procedures for these macrocycles5,6 as well as on the
preparation and structures of their complexes with pal-
ladium(0), platinum(0), and silver(I).7 The air-stable
phosphine-free complex 1 (Fig. 1) shows great catalytic
activity and recovery in Suzuki cross-couplings.5
Anchoring to a polystyrene framework affords an insol-
uble version of the catalyst which can be recovered
after filtration and reused several times without loss of
catalytic activity.5
All this led us to undertake the synthesis of the
trans,trans,cis isomer: (E,E,Z)-1,6,11-tris[(2,4,6-triiso-
propylphenyl)sulfonyl]-1,6,11-triazacyclopentadeca-3,8,
13-triene (6) and to study its complexating ability
towards some transition metals.
Macrocycle 6 was prepared by the sequence outlined in
Scheme 1. Reaction of 26 with 0.5 equiv. of (Z)-1,4-
dibromo-2-butene9 afforded 310 in quantitative yield.
Deprotection gave bis-sulfonamide 4.10 On the other
hand, dibromide 510 was obtained by reaction of 2,4,6-
triisopropylbenzenesulfonamide with excess (E)-1,4-
dibromo-2-butene (9 equiv.). Then, macrocycle 610 was
SO2
N
The complexing behavior of 1 and congeners featuring
other aryl groups is reminiscent of the behavior of the
geometric isomers of 12-membered cyclododeca-1,5,9-
triene in nickel(0) chemistry.8
Pd
SO2
N
N SO2
Keywords: macrocycles; triene complexes; palladium; platinum; silver.
* Corresponding author. Fax: 34-935811265; e-mail: marcial.moreno
@uab.es
1
Figure 1.
0040-4039/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(01)00758-4

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J. Corte`s et al. / Tetrahedron Letters 42 (2001) 4337–4339
Boc
Boc
i
ii
100 %
Ar-SO2NH(Boc)
Ar-SO2N
N SO2-Ar
Ar-SO2NH2
93 %
2
3
iv
88 %
iii
63 %
Br
Br
H
H
Ar-SO2N
N SO2-Ar
Ar-SO2N
5
4
v
69 %
Ar =
SO2-Ar
N
SO2-Ar
N
vi, vii, or viii
X
M
Ar-SO2N
N SO2-Ar
Ar-SO2N
N SO2-Ar
M
X
Yield
6
7a
7b
7c
Pd
Pt
Ag+ BF4
--
--
90 %
56 %
-
100 %
Scheme 1. (i) (tBuOCO)2O, Et3N, DMAP, CH2Cl2, rt, 24 h; (ii) (Z)-1,4-dibromo-2-butene9 (0.5 equiv.), K2CO3, refluxing CH3CN,
20 h; (iii) TFAA, CH2Cl2, rt, 3 h; (iv) (E)-1,4-dibromo-2-butene (9 equiv.), DMF, 100°C, 6 h, then column chromatography; (v)
K2CO3, refluxing CH3CN, 24 h; (vi) Pd(PPh3)4, refluxing THF, 5 h; (vii) Pt(PPh3)4, DMF, 130°C, 96 h; (viii) AgBF4, refluxing
acetone, 5 h.
shift displacement of the olefinic signals to lower field
being observed.
formed in 69% yield by reaction of equimolar amounts
of 4 and 5 in refluxing acetonitrile using potassium
carbonate as a base. Concentrations below 0.02 M are
optimal.
In summary, the novel triolefinic macrocycle 6 forms
stable complexes with Pd(0) and with Pt(0).
Macrocycle 6 shows a complexing ability towards tran-
sition metals which is comparable to those obtained
before for its trans,trans,trans isomer 1.7 Thus, reaction
Acknowledgements
of
6
with
1
equiv. of tetrakis(triphenylphos-
phine)palladium(0) led to complex 7a.10 The related
Pt(0) complex (7b)10 was formed by treating 6 with
tetrakis(triphenylphosphine)platinum(0) in DMF at
130°C. Both 7a and 7b are air-stable and have been
purified by column chromatography in silica gel giving
Financial support from DGESIC (Project PB98-0902)
and CIRIT-Generalitat de Catalunya (Projects SGR98-
0056 and SGR2000-0062, and a predoctoral scholarship
to J.C.) is gratefully acknowledged.
1
correct elementary analysis. Their H NMR spectra are
quite similar to each other showing the classical dis-
placement of the signals of the olefinic protons to
higher fields with respect to the free ligand 6.
References
Reaction of 6 with 1 equiv. of silver tetrafluoroborate
in refluxing acetone under a nitrogen atmosphere gives
the ionic complex 7c10 in quantitative yield. On the
contrary to 7a and to 7b, 7c showed low stability when
treated with most solvents. It was characterized by
NMR and MALDI-TOF MS. Its H NMR spectrum
was quite different to those of 7a and 7b, with chemical
1. For a general monograph on macrocyclic compounds,
see: Dietrich, B.; Viout, P.; Lehn, J.-M. Aspects de la
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2. For a review on nitrogen-bridged macrocycles, see: Take-
mura, H.; Shinmyozu, T.; Inazu, T. Coord. Chem. Rev.
1996, 156, 183–200.
1

J. Corte`s et al. / Tetrahedron Letters 42 (2001) 4337–4339
4339
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and 1H–13C HSQC experiments the following informa-
tion was acquired:11 1H NMR (CDCl3, 400 MHz): l
1.17–1.25 (m, 54H), 2.07 (dd, J=10.0 and 4.0, 2H), 2.08
(dd, J=10.0 and 4.0, 2H), 2.26 (dd, J=14.6 and 9.2 Hz,
2H), 2.88 (sept., J=7.0, 1H), 2.90 (sept., J=7.0, 2H),
3.98 (t, J=10.0 Hz, 2H), 4.09 (t, J=10.0, 2H), 4.17 (d,
J=14.6, 2H), 4.18 (sept., J=7.0 Hz, 6H), 4.20 (d, J=9.2
Hz, 2H), 4.44 (m, 2H), 4.49 (m, 2H), 7.15 (s, 2H), 7.16 (s,
4H); 13C NMR (CDCl3, 100 MHz): l 23.6, 24.9, 29.3,
34.2, 42.5, 46.5, 47.4, 75.9, 76.7, 77.2, 124.0, 131.0, 151.3,
151.4, 153.3; MALDI-TOF MS: m/z from 1108.48 to
1116.47, all peaks appear differing by 1 a.m.u. and corre-
sponding to the molecular isotopic distribution for
C57H87N3O6PdS3. An additional system of peaks corre-
sponding to [M+K] also appeared.
5. Corte`s, J.; Moreno-Man˜as, M.; Pleixats, R. Eur. J. Org.
Chem. 2000, 239–243.
6. Cerezo, S.; Corte`s, J.; Galva´n, D.; Lago, E.; Marchi, C.;
Molins, E.; Moreno-Man˜as, M.; Pleixats, R.; Torrejo´n,
J.; Vallribera, A. Eur. J. Org. Chem. 2001, 329–337.
7. Cerezo, S.; Corte`s, J.; Lago, E.; Molins, E.; Moreno-
Man˜as, M.; Parella, T.; Pleixats, R.; Torrejo´n, J.; Vallrib-
era, A. Eur. J. Inorg. Chem., in press.
8. (a) Wilke, G. Angew. Chem., Int. Ed. Engl. 1988, 27,
185–206; (b) Brauer, D. J.; Kru¨ger, C. J. Organomet.
Chem. 1972, 44, 397–402; (c) Po¨rschke, R.; Kleimann,
W.; Tsay, Y.-H.; Kru¨ger, C.; Wilke, G. Chem. Ber. 1990,
123, 1267–1273; (d) Taube, R.; Wache, S.; Sieler, J.;
Kempe, R. J. Organomet. Chem. 1993, 456, 131–136; (e)
Taube, R.; Wache, S.; Sieler, J. J. Organomet. Chem.
1993, 459, 335–347; (f) Brauer, D. J.; Kru¨ger, C.; Seku-
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198–202.
Compound 7b: mp 271–274°C (dec.); IR (KBr): 2958,
1
1319, 1151 cm−1; H NMR (CDCl3, 250 MHz): l 1.20–
1.26 (m, 54H), 1.85 (dd, J=10.4 and 4.8 Hz, 2H), 1.88
(dd, J=10.2 and 5.3 Hz, 2H), 2.04 (dd, J=14.1 and 9.0
Hz, 2H), 2.89 (sept., J=6.9 Hz, 3H), 3.42 (t, J=10.4 Hz,
2H), 3.55 (t, J=10.2 Hz, 2H), 3.82 (d, J=9.0 Hz, 2H),
4.10–4.30 (m, 8H), 4.40 (m, 2H), 4.46 (m, 2H), 7.15 (s,
2H), 7.16 (s, 4H); MALDI-TOF MS: m/z from 1198.72
to 1202.69, all peaks appear differing by 1 a.m.u. and
corresponding to the molecular isotopic distribution for
C57H87N3O6PtS3. An additional system of peaks corre-
sponding to [M+Na] also appeared.
10. Selected data for all new compounds:
Compound 3: mp 106–107°C.
Compound 4: mp 129–131°C.
Compound 7c: mp 177–180°C (dec.); IR (KBr): 2962,
Compound 5: mp 83–86°C.5
1322, 1154, 1104, 1060 cm−1 1H NMR (CDCl3, 250
;
Compound 6: mp 198–199°C; IR (KBr): 2961, 1317, 1153
MHz): l 1.19–1.25 (m, 54H), 2.86 (sept., J=6.9 Hz, 3H),
3.25 (m, 2H), 3.45 (m, 2H), 3.60 (m, 2H), 3.94 (sept.,
J=7.1 Hz, 6H), 4.10–4.50 (m, 6H), 6.07 (br s, 2H), 6.15
(br s, 4H), 7.14 (s, 4H), 7.16 (s, 2H); 13C NMR (CDCl3,
62.5 MHz): l 23.5, 24.6, 24.7, 29.4, 34.2, 42.8, 46.4, 47.2,
118.5 (br m), 120.5 (br), 124.2, 124.3, 129.9, 130.3, 151.4,
151.6, 153.7, 153.9; MALDI-TOF MS: m/z from 1113.40
to 1117.27, all peaks appear differing by 1 a.m.u. and
corresponding to the molecular isotopic distribution for
the C57H87AgN3O6S3 cation.
cm−1 1H NMR (CDCl3, 400 MHz): l 1.17–1.25 (m,
;
54H), 2.87 (sept., J=7.3 Hz, 3H), 3.73 (d, J=3.2 Hz,
4H), 3.76 (d, J=6.4 Hz, 4H), 3.78 (d, J=6.2 Hz, 4H),
4.04 (sept., J=6.6 Hz, 4+2H), 5.50 (t, J=3.2 Hz, 2H),
5.55 (dt J=15.6 and 6.4 Hz, 2H), 5.75 (dt, J=15.6 and
6.2 Hz, 2H), 7.12 (s, 2+4H); 13C NMR (CDCl3, 62.5
MHz): l 23.5, 24.8, 29.3, 34.2, 41.4, 46.4, 49.9, 124.0,
127.5, 128.9, 130.6, 132.8, 151.5, 153.3, 153.4; LSI MS
(3-nitrobenzyl alcohol matrix): m/z 472 (100, M−
2SO2Ar), 741 (48, M−SO2Ar), 1007 (54, M).
Good elemental analyses were secured for products 4, 6,
and 7a.
Compound 7a: mp 263–267°C (dec.); IR (KBr): 2956,
1319, 1151 cm−1; from TOCSY 1D, COSY, NOESY 2D,
11. To be published elsewhere.
.