Synthesis of nitrogen-containing 15-membered triacetylenic macrocycles. Stable complex with palladium(0)

Article abstract of DOI:10.1021/om034384o

Selective and efficient preparation of a new type of nitrogen-containing 15-membered triacetylenic macrocycles named 1,6,11-tris(arylsulfonyl)-1,6,11- triazacyclopentadeca-3,8,-13-triynes (1) (Ar¹ = Ar² = Ar³ = 4-methylphenyl, 1aaa; Ar¹ = Ar² = 4-methylphenyl, Ar³ = ferrocenyl, 1aab) has been achieved. Macrocycle 1aaa forms a very stable complex with Pd⁰, being the first palladium(O) complex with a macrocyclic triyne. The three triple bonds in 1aaa are responsible for the complexation. The X-ray structures of both the ligand 1aaa and its Pd⁰ complex are presented. Furthermore, compound 1aaa undergoes cycloisomerization into the corresponding 2,5,8-tris[(4-methlphenyl) sulfonyl]-2,5,8-triazatrindane, 11aaa, when treated with Pd(PPh ₃)₄ in refluxing toluene.

Full text of DOI:10.1021/om034384o

2762
Organometallics 2004, 23, 2762-2767
Syn th esis of Nitr ogen -Con ta in in g 15-Mem ber ed
Tr ia cetylen ic Ma cr ocycles. Sta ble Com p lex w ith
P a lla d iu m (0)
Anna Pla-Quintana, Anna Roglans,* and Anna Torrent
Department of Chemistry, Universitat de Girona, Campus de Montilivi,
s/ n. E-17071-Girona, Spain
Marcial Moreno-Man˜as
Department of Chemistry, Universitat Auto`noma de Barcelona, Cerdanyola del Valle`s,
E-08193-Barcelona, Spain
J ordi Benet-Buchholz
Bayer Industry Services, Analytics X-ray Laboratory, Geb. Q18, Raum 490, Bayer AG,
D-51368-Leverkusen, Germany
Received December 18, 2003
Selective and efficient preparation of a new type of nitrogen-containing 15-membered
triacetylenic macrocycles named 1,6,11-tris(arylsulfonyl)-1,6,11-triazacyclopentadeca-3,8,-
13-triynes (1) (Ar1 ) Ar2 ) Ar3 ) 4-methylphenyl, 1a a a ; Ar1 ) Ar2 ) 4-methylphenyl, Ar3
) ferrocenyl, 1a a b) has been achieved. Macrocycle 1a a a forms a very stable complex with
Pd0, being the first palladium(0) complex with a macrocyclic triyne. The three triple bonds
in 1a a a are responsible for the complexation. The X-ray structures of both the ligand 1a a a
and its Pd0 complex are presented. Furthermore, compound 1a a a undergoes cycloisomer-
ization into the corresponding 2,5,8-tris[(4-methlphenyl)sulfonyl]-2,5,8-triazatrindane, 11a a a ,
when treated with Pd(PPh3)4 in refluxing toluene.
palladium(0) complexes of the 15-membered triolefinic
In tr od u ction
macrocycles have shown excellent catalytic activity in
certain C-C bond formation reactions.7
The synthesis and properties of macrocyclic com-
pounds are important topics in supramolecular chem-
istry.1 Synthetic approaches toward these compounds
usually suffer from low yields, polymer formation during
the macrocyclization step, and the need of high dilution
conditions and template effect. Nitrogen-containing
cycloalkynes, especially with the amine functionality in
the propargylic position, are uncommon.2 Thus, com-
pounds of type -(N-C-CtC-C-)n (n ) 3) have been
isolated as side products in the preparation of 10-
membered rings (n ) 2).3 In the past few years, we have
reported a very selective and efficient preparation of
nitrogen-containing 15-,4 20-,5 and 30-membered4c poly-
olefinic macrocycles as well as their coordinating prop-
erties with some transition metals.6 In particular,
On the other hand, the ability of transition metals to
bind to π-systems of alkynes is well-known.8 In particu-
lar, the chemistry of alkynes with palladium complexes
is extremely rich and useful. First, oxidative addition
to yield PdII alkynyl hydrides seems to be the preferred
pathway of Pd0 complexes with terminal alkynes. Also,
palladium alkyne complexes have received considerable
attention as intermediates in a variety of alkyne oligo-
merizations. However, few alkyne complexes have been
isolated. Among them, several stable Pd0-alkyne com-
plexes containing phosphanes have been reported.9
Po¨rschke et al. have even published the first isolated
(5) Blanco, B.; Cerezo, S.; Moreno-Man˜as, M.; Pleixats, R.; Spengler,
J . Tetrahedron Lett. 2001, 42, 9001.
(6) Cerezo, S.; Corte`s, J .; Lago, E.; Molins, E.; Moreno-Man˜as, M.;
Parella, T.; Pleixats, R.; Torrejo´n, J .; Vallribera, A. Eur. J . Inorg. Chem.
2001, 1999.
* To whom correspondence should be addressed. E-mail:
anna.roglans@udg.es.
(1) Comprehensive Supramolecular Chemistry; Lehn, J . M., Atwood,
J . L., Davies, J . E. D., McNicol, D. D., Vo¨gtle, F., Eds.; Pergamon:
Oxford, 1996; Vol. 1-2.
(2) Gleiter, R. Angew. Chem., Int. Ed. Engl. 1992, 31, 27. (b)
Epsztein, R.; Le Goff, N. Tetrahedron Lett. 1985, 26, 3203.
(3) Gleiter, R.; Ritter, J .; Irngartinger, H.; Lichtentha¨ler, J . Tetra-
hedron Lett. 1991, 32, 2887. (b) Ritter, J .; Gleiter, R. Liebigs Ann./
Recl. 1997, 2113.
(4) Cerezo, S.; Corte`s, J .; Galvan, D.; Lago, E.; Marchi, C.; Molins,
E.; Moreno-Man˜as, M.; Pleixats, R.; Torrejo´n, J .; Vallribera, A. Eur.
J . Org. Chem. 2001, 329. (b) Llobet, A.; Masllorens, E.; Moreno-Man˜as,
M.; Pla-Quintana, A.; Rodr´ıguez, M.; Roglans, A. Tetrahedron Lett.
2002, 43, 1425. (c) Moreno-Man˜as, M.; Spengler, J . Tetrahedron 2002,
58, 7769.
(7) For Suzuki cross-coupling reactions see: (a) Corte´s, J .; Moreno-
Man˜as, M.; Pleixats, R. Eur. J . Org. Chem. 2000, 239. (b) Ref 4b. For
Heck reactions see: (c) Masllorens, J .; Moreno-Man˜as, M.; Pla-
Quintana, A.; Roglans, A. Org. Lett. 2003, 5, 1559. (d) Ref 4b. For the
telomerization of butadiene see: (e) Estrine, B.; Blanco, B.; Bouquillon,
S.; He´nin, F.; Moreno-Man˜as, M.; Muzart, J .; Pena, C.; Pleixats, R.
Tetrahedron Lett. 2001, 42, 7055. (f) Moreno-Man˜as, M.; Pleixats, R.;
Spengler, J .; Chevrin, C.; Estrine, B.; Bouquillon, S.; He´nin, F.; Muzart,
J .; Pla-Quintana, A.; Roglans, A. Eur. J . Org. Chem. 2003, 274. For
the hydroarylation of alkynes see: (g) Cacchi, S.; Fabrizi, G.; Goggia-
mani, A.; Moreno-Man˜as, M.; Vallribera, A. Tetrahedron Lett. 2002,
43, 5537.
(8) Youngs, W. J .; Tessier, C. A.; Bradshaw, J . D. Chem. Rev. 1999,
99, 3153, and references therein.
10.1021/om034384o CCC: $27.50 © 2004 American Chemical Society
Publication on Web 04/22/2004

N-Containing 15-Membered Triacetylenic Macrocycles
Organometallics, Vol. 23, No. 11, 2004 2763
Sch em e 1. Syn th esis of Ma cr ocycles 1a a a a n d 1a a b
Pd0-1-alkyne complex with bidentate phosphanes.9d
Recently, Yamamoto et al. have reported the first
palladium(0) trisalkyne complex, being an efficient cata-
lyst precursor for the cyclization of the triyne ligand.10
We wish to describe in this paper an efficient and
simple synthesis of two new 15-membered triazatri-
acetylenic macrocycles of type 1 (Scheme 1) as well as
their coordinating capacity with palladium(0) (Scheme
2). To the best of our knowledge, we describe the first
palladium(0) complex of a cyclic triyne ligand.
analysis for their homologous 15-membered triolefinic
macrocycles4a and is shown in Scheme 1. Compound 4a
was prepared from sulfonamide 3a according to the
method described in the literature.11 Reaction of 4a with
4 equiv of 1,4-dibromo-2-butyne, 5, afforded 7a in 66%
yield. In this step, we also explored 1,4-bis(methane-
sulfonyloxy)-2-butyne, 6, as a 1,4-butadien-2-ylating
reagent, obtaining derivative 8a in 56% yield. Conden-
sation of 7a with 0.5 equiv of arylsulfonamides 3a and
3b led to tert-butyloxycarbonyl (Boc)-protected trisul-
fonamides 9a a a and 9a a b in 86% and 100% yield,
respectively. Compounds 9 were also obtained in good
yields from methanesulfonate 8a . Elimination of the Boc
groups in compounds 9 resulted in the isolation of
derivatives 10. Final ring closure was achieved by
treatment of 10 with 1.16 equiv of dibromide 5 or with
bismethanesulfonate 6 to afford macrocycles 1 in good
yields. From a synthetic point of view, the use of 1,4-
bis(methanesulfonyloxy)-2-butyne, 6, or 1,4-dibromo-2-
butyne, 5, did not make any difference. However, it is
noteworthy that dibromo 5 is a powerful vesicant and
lachrymator agent, and therefore, on a multigram scale
the bismethanesulfonate protocol may be more useful.
The structure of macrocycle 1a a a was confirmed by
X-ray analysis. A perspective view of the molecule is
shown in Figure 1. The molecule shows a folded struc-
Resu lts a n d Discu ssion
The preparation of macrocyclic triacetylenic deriva-
tives 1a a a and 1a a b is based on the retrosynthetic
(9) McGinnety, J . A. J . Chem. Soc., Dalton Trans. 1974, 1038. (b)
J acobson, S.; Carty, A. J .; Mathew, M.; Palenik, G. J . J . Am. Chem.
Soc. 1974, 96, 4330. (c) Farrar, D. H.; Payne, N. C. J . Organomet.
Chem. 1981, 220, 239. (d) Krause, J .; Bonrath, W.; Po¨rschke, K. R.
Organometallics 1992, 11, 1158. (e) Schager, F.; Bonrath, W.; Po¨rschke,
K. R.; Kessler, M.; Kru¨ger, C.; Seevogel, K. Organometallics 1997, 16,
4276, and references therein. (f) Carvalho, M. F. N. N.; Galvao, A. M.;
Pombeiro, A. J . L.; Cerma´k, J .; Sabata, S.; Vojt´ısek, P.; Podlaha, J . J .
Organomet. Chem. 2000, 598, 318. (g) Dervisi, A.; Edwards, P. G.;
Newman, P. D.; Tooze, R. P. J . Chem. Soc., Dalton Trans. 2000, 523.
(h) Klosin, J .; Abboud, K. A.; J ones W. M. Organometallics 1996, 15,
2465. (i) Retboll, M.; Edwards, A. J .; Rae, A. D.; Willis, A. C.; Bennett,
M. A.; Wenger, E. J . Am. Chem. Soc. 2002, 124, 8348.
(10) Yamamoto, Y.; Nagata, A.; Arikawa, Y.; Tatsumi, K.; Itoh, K.
Organometallics 2000, 19, 2403. (b) Yamamoto, Y.; Nagata, A.; Nagata,
H.; Ando, Y.; Arikawa, Y.; Tatsumi, K.; Itoh, K. Chem. Eur. J . 2003,
9, 2469.
(11) Neustadt, B. R. Tetrahedron Lett. 1994, 35, 379.

2764 Organometallics, Vol. 23, No. 11, 2004
Pla-Quintana et al.
Sch em e 2. Syn th esis of P d 0 Com p lex 2a a a a n d Tr ia za in d a n e 11a a a
Ta ble 1. Cr ysta llogr a p h ic Da ta for 1a a a a n d 2a a a
ture with the linear substituted triple bonds ordered in
different planes. Crystal data for the structure are given
in Table 1.
1a a a
2a a a
formula
fw
C
33H33N3O6S3
C
33H33N3O6Pd1S3
663.80
770.20
Macrocycle 1a a a was treated with 1 equiv of Pd-
(PPh3)4 in THF at room temperature to afford Pd0
complex 2a a a as an air- and moisture-stable crystalline
compound (Scheme 2). Complex 2a a a has been charac-
cryst size (mm3)
cryst color
temp (K)
cryst syst
space group
a (Å)
0.8 × 0.8 × 0.8
colorless
153(2)
0.006 × 0.06 × 0.06
colorless
153(2)
monoclinic
P21/n (No. 14)
23.4132(9)
6.1253(2)
24.7974(9)
115.5920(10)
3207.4(2)
4
1.375
0.281
31.55
46 790
monoclinic
P21/c (No. 14)
8.5644(7)
10.4573(9)
35.603(3)
94.302(4)
3179.6(5)
4
1.609
0.832
31.52
47 579
1
terized by MS and H and 13C NMR spectra. The ESI
mass spectra of 2a a a showed a cluster centered at m/z
792 assigned to ion [M + Na]+ by the characteristic
isotope distribution of the palladium atom. The cluster
corresponding to the molecular ion [M + H]+ centered
at m/z 770 was observed by MALDI-TOF mass spec-
b (Å)
c (Å)
â (deg)
V (Å3)
Z
F (g/cm3)
1
trometry. In the H NMR spectrum of 2a a a the absorp-
µ (mm-1
)
tion due to the 12 methylenic protons of the ring (δ 4.38
ppm) was shifted (0.42 ppm) to lower field in comparison
to that of the free macrocyclic ligand, 1a a a (δ 3.96 ppm).
In the 13C NMR spectrum, the signals of the six
acetylenic carbons (δ 74.1 ppm) and the six CH2 groups
(δ 36.4 ppm) in 2a a a were displaced by 4.9 and 1.2 ppm,
respectively, to upper field compared to 1a a a . These
θmax (deg)
no. of reflns measd
no. of unique reflns
10 276 [Rint
0.0762]
)
10 194 [Rint
0.1692]
)
absorp corr
SADABS
SADABS
(Bruker-AXS)
0.6921/1.0000
538
(Bruker-AXS)
0.7278/1.0000
418
transmn min./max.
no. of params
R1/wR2 [I>2σ(I)]
R1/wR2 [all data]
goodness-of-fit on F2
0.0447/0.1085
0.0665/0.1169
1.013
0.0554/0.0880
0.1649/0.1095
0.812
largest diff peak and 0.431 and -0.641 0.736 and -1.244
hole (e/Å3)
values are in accordance to those described for a related
Pd0 trialkyne complex,10 but differ significantly from
those of mixed alkyne/phosphane-Pd0 complexes, since
the presence of other ligands such as phosphanes can
change considerably the nature of the Pd-alkyne bond-
ing.9
The single-crystal X-ray structure analysis of 2a a a
confirmed the expected organometallic nature of the
complex. Crystal data for the structure are given in
Table 1. The obtained structure is shown in Figure 2.
The triple bonds are located on the same plane bonding
symmetrically to a central palladium atom. As a result
of the attractive interaction with the palladium, the
acetylenic atoms are shifted to the center of the mol-
ecule. They show a deviation of approximately 22° with
respect to the expected linearity for a substituted triple
bond. In comparison the triple bonds in the metal-free
F igu r e 1. ORTEP plot (50%) of the structure of 1a a a .
Selected bond distances (Å) and angles (deg): C(2)-C(3):
1.1873(19); C(6)-C(7): 1.1843(19); C(10)-C(11): 1.190(2);
C(1)-C(2)-C(3): 177.09(14); C(2)-C(3)-C(4): 174.39(14);
C(5)-C(6)-C(7): 175.41(15); C(6)-C(7)-C(8): 176.19(15);
C(9)-C(10)-C(11): 178.19(17); C(10)-C(11)-C(12): 176.84-
(16).

N-Containing 15-Membered Triacetylenic Macrocycles
Organometallics, Vol. 23, No. 11, 2004 2765
Exp er im en ta l Section
IR spectra were recorded with a FT-IR using a single-
1
reflection ATR system as a sampling accessory. H NMR (13C
NMR) were recorded at 200 MHz (50 MHz) using Me4Si as
internal standard. Chemical shifts are given in δ units. ESI
mass spectra were acquired using a Navigator quadrupole
instrument (Finnigan AQA ThermoQuest) equipped with an
electrospray ion source. MALDI-TOF mass spectra were
obtained on a BIFLEX spectrometer (Bruker-Franzen Analy-
tik) equipped with a pulsed nitrogen laser (337 nm). Elemental
analyses were determined at “Servei d'Ana`lisi Qu´ımica de la
Universitat de Girona”.
(4-Methylphenyl)sulfonamide, 3a , is commercially available
and was used without further purification. Ferrocenesulfona-
mide,13 3b, N-(tert-butyloxycarbonyl)(4-methylphenyl)sulfona-
mide,11 4a , 1,4-dibromo-2-butyne,14 5, and 1,4-bis(methane-
sulfonyloxy)-2-butyne,15 6, were prepared as previously reported.
N-(4-Br om o-2-b u t yn yl)-N-(ter t-b u t yloxyca r b on yl)(4-
m eth ylph en yl)su lfon am ide (7a). A stirred mixture of N-(tert-
butyloxycarbonyl)(4-methylphenyl)sulfonamide, 4a (1.21 g,
4.46 mmol), 1,4-dibromo-2-butyne, 5 (3.75 g, 17.70 mmol),
anhydrous potassium carbonate (3.12 g, 22.61 mmol), and
acetonitrile (50 mL) was refluxed for 1.5 h (TLC monitoring).
The salts were filtered off, and the filtrate was evaporated.
The oily residue was chromatographed through silica gel with
hexane/ethyl acetate (10:1) to afford 7a (1.18 g, 66%) as a
colorless solid; mp 116-117 °C; IR (neat) 2986, 1716, 1356,
F igu r e 2. ORTEP plot (50%) of the structure of 2a a a .
Selected bond distances (Å) and angles (deg): Pd(1)-C(2):
2.125(4), Pd(1)-C(3): 2.149(4); Pd(1)-C(6): 2.134(5); Pd-
(1)-C(7): 2.141(4); Pd(1)-C(10): 2.146(4); Pd(1)-C(11):
2.138(4); C(2)-C(3): 1.249(6); C(6)-C(7): 1.235(6); C(10)-
C(11): 1.231(6); C(1)-C(2)-C(3): 155.6(4); C(2)-C(3)-
C(4): 160.1(5); C(5)-C(6)-(7): 157.9(5); C(6)-C(7)-C(8):
158.9(5); C(9)-C(10)-C(11): 160.7(5); C(10)-C(11)-
C(12): 158.3(4).
compound 1a a a show an asymmetrical arrangement
with a bending of only approximately 4°. As a result of
complexation, the triple bonds in 2a a a are elongated
0.051 Å on average, as compared to 1a a a (from 1.1870-
(15) to 1.238(5) Å). The distances of the palladium atom
to the center of the acetylenic bonds are identical (2.047-
(3) Å) considering the standard deviations. The only
previously described compound with three triple bonds
complexing a palladium atom shows planar arrange-
ments and bond distances similar to those of 2a a a .10
Curiously in the crystal packing of 2a a a two of the
aromatic rings are positioned like a sandwich on the
top and on the bottom of the central part of the molecule.
For the aromatic ring C27-C32 there is an approximate
distance from C27 to Pd1 of 3.74 Å. The aromatic ring
C20-C25 is closer to the triple bond C2-C3 than to
Pd1, with an approximate distance center of C20-C25
to C2 of 3.72 Å.
1284, 1144, 1067 cm-1 1H NMR (200 MHz, CDCl3) 1.36 (s,
;
9H), 2.45 (s, 3H), 3.93 (t, J ) 2.0 Hz, 2H), 4.68 (t, J ) 2.0 Hz,
2H), 7.33 (AA′ part of the AA′BB′ system, J ) 8.4 Hz, 2H),
7.93 (BB′ part of the AA′BB′ system, J ) 8.4 Hz, 2H); 13C NMR
(50 MHz, CDCl3) 14.8, 22.3, 28.5, 36.6, 79.4, 82.7, 85.7, 128.9,
129.9, 137.3, 145.1, 150.8; ESI-MS (m/z) 424-426 [M + Na]+,
440-442 [M + K]+; C16H20BrNO4S (402.3) calcd C, 47.77; H,
5.01; N, 3.48; found C, 47.88 and 47.94; H, 5.09 and 4.98; N,
3.38 and 3.39.
N-(ter t-Bu tyloxyca r bon yl)-N-(4-m eth a n esu lfon yloxy-
2-bu tyn yl)-4-m eth ylp h en yl)su lfon a m id e (8a ). The experi-
mental procedure to obtain 8a starting from 4a and 1,4-
bis(methanesulfonyloxy)-2-butyne, 6, is the same as described
above; 24 h at room temperature; 8a , colorless solid, 56% yield;
mp 100-102 °C; IR (neat) 3023, 1716, 1353, 1149, 1072 cm-1
;
1H NMR (200 MHz, CDCl3) 1.35 (s, 9H), 2.46 (s, 3H), 3.10 (s,
3H), 4.69 (t, J ) 1.7 Hz, 2H), 4.89 (t, J ) 1.7 Hz, 2H), 7.35
(AA′ part of the AA′BB′ system, J ) 8.0 Hz, 2H), 7.87 (BB′
part of the AA′BB′ system, J ) 8.0 Hz, 2H); 13C NMR (50 MHz,
CDCl3) 22.3, 28.5, 36.3, 39.9, 58.4, 76.7, 86.0, 86.1, 128.8, 130.1,
137.2, 145.5, 150.8; ESI-MS (m/z) 418 [M + H]+, 435 [M +
NH4]+, 440 [M + Na]+; C17H23NO7S2 (417.5) calcd C, 48.91; H,
5.55; N, 3.35; found C, 49.38 and 49.16; H, 5.76 and 5.76; N,
3.35 and 3.24.
We also tested palladium-catalyzed cycloisomerization
of cyclotriyne 1a a a in order to obtain hexasubstituted
benzene derivatives. The reaction never proceeded
under catalytic conditions, but when macrocycle 1a a a
was treated with 1.1 equiv of Pd(PPh3)4 in refluxing
toluene, triazatrindane 11a a a was obtained in 54%
1,11-Bis(ter t-b u t yloxyca r b on yl)-1,6,11-t r is[(4-m e t h -
ylp h en yl)su lfon yl]-1,6,11-tr ia za u n d eca -3,8-d iyn e (9a a a ).
Gen er a l P r oced u r e. A stirred mixture of N-(4-bromo-2-
butynyl)-N-(tert-butyloxycarbonyl)(4-methylphenyl)sulfona-
mide, 7a (0.59 g, 1.47 mmol), (4-methylphenyl)sulfonamide,
3a (0.13 g, 0.76 mmol), anhydrous potassium carbonate (0.63
g, 4.56 mmol), and acetonitrile (24 mL) was refluxed for 3.5 h
(TLC monitoring). The salts were filtered off, and the filtrate
was evaporated. The oily residue was chromatographed through
silica gel with hexane/ethyl acetate (7:3) to afford 9a a a (0.52
g, 86%; 80% yield starting from 8a ) as a colorless solid; mp
1
yield (Scheme 2).12 The H NMR spectrum of cycloiso-
mer 11a a a was not very informative and served only
to confirm that a new compound was formed: the
absorption due to the 12 methylenic protons of 1a a a (δ
3.96 ppm) shifted to δ 4.52 ppm in the new product.
However, the 13C NMR spectrum changed considerably,
showing a new signal at δ 130 ppm corresponding to
the six equivalent benzene carbons and the absence of
the absorption at δ 79.0 ppm corresponding to the six
acetylenic carbons of 1a a a . Further studies on the
stability of palladium(0) complexes of type 2 and their
cycloisomerization process are now underway.
73-75 °C; IR (neat) 2982, 1728, 1351, 1255, 1149, 1089 cm-1
;
1H NMR (200 MHz, CDCl3) 1.32 (s, 18H), 2.43 (s, 3H), 2.45 (s,
(13) Slocum, D. W.; Achermann, W. Synth. React. Inorg. Met. Org.
Chem. 1982, 12, 397. (b) Knox, G.-R.; Pauson, P.-L. J . Chem. Soc. 1958,
692.
(14) J ohnson, A. W. J . Chem. Soc. 1946, 1009.
(15) Alcaide, B.; Almendros, P.; Rodr´ıguez-Acebes, R. J . Org. Chem.
2002, 67, 1925.
(12) The cycloisomerization process did not proceed when palladium-
(0) complex 2a a a was refluxed in anhydrous toluene in the presence
of 1.1 equiv of PPh3 under argon atmosphere for 1 day. Complex 2a a a
was almost recovered (83%), and only traces of cycloisomerized
compound 11a a a were isolated.

2766 Organometallics, Vol. 23, No. 11, 2004
Pla-Quintana et al.
6H), 4.15 (s, 4H), 4.47 (s, 4H), 7.31-7.37 (m, 6H), 7.74 (BB′
part of the AA′BB′ system, J ) 8.0 Hz, 2H), 7.85 (BB′ part of
the AA′BB′ system, J ) 8.2 Hz, 4H); 13C NMR (50 MHz, CDCl3)
22.2, 22.3, 28.5, 36.3, 37.2, 77.2, 81.9, 85.7, 128.4, 128.7, 130.1,
130.5, 136.0, 137.3, 144.8, 145.3, 150.8; ESI-MS (m/z) 831 [M
+ NH4]+, 836 [M + Na]+, 852 [M + K]+; C39H47N3O10S3 (814.0)
calcd C, 57.55; H, 5.82; N, 5.16; found C, 57.27 and 57.44; H,
6.07 and 5.76; N, 4.87 and 4.81.
1,11-Bis(ter t-bu tyloxyca r bon yl)-1,11-bis[(4-m eth ylp h e-
n yl)su lfon yl]-6-fer r ocen ylsu lfon yl-1,6,11-t r ia za u n d eca -
3,8-d iyn e (9a a b): orange solid (100% yield starting from 7a ;
79% yield starting from 8a ); mp 75-77 °C; IR (neat) 1728,
1351, 1139, 1089 cm-1; 1H NMR (200 MHz, CDCl3) 1.32 (br s,
18H), 2.45 (s, 6H), 4.03 (s, 4H), 4.40 (s, 5H), 4.42 (t, J ) 1.8
Hz, 2H), 4.48 (s, 4H), 4.66 (t, J ) 1.8 Hz, 2H), 7.35 (AA′ part
of the AA′BB′ system, J ) 9.0 Hz, 4H), 7.84 (BB′ part of the
AA′BB′ system, J ) 9.0 Hz, 4H); 13C NMR (50 MHz, CDCl3)
22.3, 28.5, 36.4, 37.2, 70.1, 71.4, 71.6, 77.4, 81.9, 85.6, 128.7,
130.1, 137.3, 145.3, 150.8; ESI-MS (m/z) 907 [M + H]+, 925
[M + NH4]+, 930 [M + Na]+, 946 [M + K]+; C42H49FeN3O10S3
(907.9) calcd C, 55.56; H, 5.44; N, 4.63; found C, 55.39 and
55.58; H, 5.71 and 5.78; N, 4.39 and 4.42.
Na]+, 702 [M + K]+; C33H33N3O6S3 (663.8) calcd C, 59.71; H,
5.01; N, 6.33; found C, 59.51 and 59.37; H, 4.89 and 4.98; N,
5.94 and 6.04.
6,11-Bis[(4-m eth ylp h en yl)su lfon yl]-1-fer r ocen ylsu lfo-
n yl-1,6,11-tr ia za ciclop en ta d eca -3,8,13-tr iyn e (1a a b): or-
ange solid (75% yield starting from 1,4-dibromo-2-butyne, 5;
53% yield starting from 1,4-bis(methanesulfonyloxy)-2-butyne,
6); mp 179-182 °C; IR (neat) 2923, 1332, 1157 cm-1; 1H NMR
(200 MHz, CDCl3) 2.44 (s, 6H), 3.73 (br abs, 4H), 3.88 (br abs,
8H), 4.37-4.39 (br abs, 2H), 4.40 (s, 5H), 4.56 (t, J ) 1.8 Hz,
2H), 7.29 (AA′ part of the AA′BB′ system, J ) 8.2 Hz, 4H),
7.63 (BB′ part of the AA′BB′ system, J ) 8.2 Hz, 4H); 13C NMR
(50 MHz, CDCl3) 22.2, 30.4, 38.2, 38.4, 69.9, 71.3, 71.5, 79.4,
79.5, 79.7, 85.3, 128.5, 130.2, 135.9, 144.7; ESI-MS (m/z) 758
[M + H]+, 775 [M + NH4]+, 780 [M + Na]+, 796 [M + K]+;
C
36H35FeN3O6S3 (757.7) calcd C, 57.07; H, 4.66; N, 5.55; found
C, 57.31 and 57.47; H, 4.78 and 4.90; N, 5.50 and 5.48.
1,6,11-Tr is[(4-m et h ylp h en yl)su lfon yl]-1,6,11-t r ia za ci-
clop en ta d eca -3,8,13-tr iyn ep a lla d iu m (0) (2a a a ). A mixture
of 1a a a (0.10 g, 0.15 mmol), tetrakis(triphenylphosphane)-
palladium(0) (0.19 g, 0.17 mmol), and tetrahydrofuran (10 mL)
was stirred at room temperature for 1 h (TLC monitoring).
The liquid was distilled off under vacuum, and the residue
was chromatographed through silica gel with mixtures of
hexane/ethyl acetate/dichloromethane (polarity from 8:2:0 to
0:1:1) to afford 2a a a as a colorless solid (0.065 g, 56%); mp
1,6,11-Tr is[(4-m eth ylp h en yl)su lfon yl]-1,6,11-tr ia za u n -
d eca -3,8-d iyn e (10a a a ). Gen er a l P r oced u r e. A mixture of
9a a a (0.65 g, 0.80 mmol), trifluoroacetic acid (4 mL), and
dichloromethane (4 mL) was stirred at room temperature for
4.5 h (TLC monitoring). The liquid was distilled off under
vacuum, and the residue was dissolved in ethyl acetate (25
mL). The organic layer was sequentially washed with aqueous
sodium bicarbonate (3 × 10 mL), with H2O (3 × 10 mL), and
with brine (15 mL), dried (Na2SO4), and filtered. The solvent
was removed under reduced pressure to afford 10a a a as a
colorless solid (0.49 g, 100%). A pure sample of 10a a a was
obtained by column chromatography through silica gel, eluting
with hexane/ethyl acetate (6:4); mp 142-144 °C; IR (neat)
3275, 1597, 1324, 1154, 1092 cm-1; 1H NMR (200 MHz, CDCl3)
2.43 (s, 9H), 3.62 (d, J ) 5.8 Hz, 4H), 3.80 (s, 4H), 4.95 (t, J )
5.8 Hz, 2H), 7.30 (m, 6H), 7.60 (BB′ part of the AA′BB′ system,
J ) 8.2 Hz, 2H), 7.72 (BB′ part of the AA′BB′ system, J ) 8.2
Hz, 4H); 13C NMR (50 MHz, CDCl3) 22.2, 33.5, 37.2, 77.8, 80.9,
127.9, 128.6, 130.2, 130.4, 135.8, 137.1, 144.6, 144.9; ESI-MS
(m/z) 614 [M + H]+, 631 [M + NH4]+, 636 [M + Na]+, 652 [M
+ K]+; C29H31N3O6S3 (613.7) calcd C, 56.75; H, 5.09; N, 6.85;
found C, 56.87 and 56.68; H, 5.32 and 5.41; N, 6.52 and 6.59.
1,11-Bis[(4-m eth ylp h en yl)su lfon yl]-6-fer r ocen ylsu lfo-
n yl-1,6,11-tr ia za u n d eca -3,8-d iyn e (10a a b): orange solid
1
228 °C (dec); IR (KBr) 2981, 2013, 1349, 1162 cm-1; H NMR
(200 MHz, [D6]DMSO) 2.31 (s, 9H), 4.38 (s, 12H), 7.26 (AA′
part of the AA′BB′ system, J ) 8.1 Hz, 6H), 7.54 (BB′ part of
the AA′BB′ system, J ) 8.1 Hz, 6H); 13C NMR (50 MHz, [D6]-
DMSO) 20.8, 36.4, 74.1, 127.4, 129.1, 134.8, 143.4; ESI-MS
(m/z) 792 [M + Na]+; MALFI-TOF (m/z) 770 [M + H]+;
C
33H33N3O6S3Pd (770.2) calcd C, 51.46; H, 4.32; N, 5.46; found
C, 51.08; H, 4.44; N, 5.37.
2,5,8-Tr is[(4-m et h ylp h en yl)su lfon yl]-2,5,8-t r ia za t r in -
d a n e (11a a a ). A degassed mixture of macrocycle 1a a a (0.05
g, 0.07 mmol) and tetrakis(triphenylphosphane)palladium(0)
(0.097 g, 0.08 mmol) in anhydrous toluene was refluxed for
22 h under N2 (TLC monitoring). The solvent was then
evaporated, and the residue was chromatographed through
silica gel with dichloromethane/ethyl acetate (10:1) to afford
11a a a as a colorless solid (0.027 g, 54%); mp 258-260 °C (dec);
IR (KBr) 2858, 1345, 1162, 1096 cm-1 1H NMR (200 MHz,
;
[D6]DMSO) 2.41 (s, 9H), 4.52 (br abs, 12H), 7.42 (AA′ part of
the AA′BB′ system, J ) 7.8 Hz, 6H), 7.79 (BB′ part of the
AA′BB′ system, J ) 7.8 Hz, 6H); 13C NMR (50 MHz, [D6]-
DMSO) 20.9, 51.9, 127.5, 129.8, 130.3, 132.9, 143.6; ESI-MS
(m/z) 664 [M + H]+, 681 [M + NH4]+, 686 [M + Na]+;
(99%); mp 72-75 °C; IR (neat) 3275, 1324, 1156, 1138 cm-1
;
1H NMR (200 MHz, [D6]DMSO) 2.47 (s, 6H), 3.64 (br abs, 8H),
4.43 (s, 5H), 4.52 (br abs, 2H), 4.66 (br abs, 2H), 7.47 (AA′
part of the AA′BB′ system, J ) 7.8 Hz, 4H), 7.74 (BB′ part of
the AA′BB′ system, J ) 7.8 Hz, 4H), 8.06 (br abs, 2H); 13C
NMR (50 MHz, [D6]DMSO) 20.9, 31.9, 35.8, 69.2, 70.2, 70.6,
76.3, 81.1, 84.2, 126.6, 129.4, 137.5, 142.8; ESI-MS (m/z) 708
[M + H]+, 730 [M + Na]+, 746 [M + K]+; HRMS calcd for
(C32H33FeN3O6S3 + Na) 730.0773; found 730.0791.
C
33H33N3O6S3‚CH2Cl2 (748.76) calcd C, 54.54; H, 4.71; N, 5.61;
S, 12.85; found C, 54.73 and 54.78; H, 4.92 and 4.89; N, 5.80
and 5.80; S, 12.77 and 12.86.
Cr ysta l Str u ctu r e Deter m in a tion s. Colorless crystals of
1,6,11-tris[(4-methylphenyl)sulfonyl]-1,6,11-triazaciclopenta-
deca-3,8,13-triyne (1a a a ) were obtained by slow diffusion of
n-hexane into a dichloromethane/ethyl acetate solution of the
macrocycle. Colorless crystals of 1,6,11-tris[(4-methylphenyl)-
sulfonyl]-1,6,11-triazaciclopentadeca-3,8,13-triynepalladium-
(0) (2a a a ) were obtained by slow diffusion of n-pentane into
dichloromethane, yielding in most cases twinned planar
needles. After taking different data sets a carefully cut, under
polarized light, nontwinned small crystal with the dimensions
6 × 60 × 60 µm3 could be measured. Crystal structure
determinations for 1a a a and 2a a a were carried out using a
Siemens P4 diffractometer equipped with a SMART-CCD-1000
area detector, a MACScience Co rotating anode with Mo KR
radiation, a graphite monochromator, and a Siemens low-
temperature device LT2 (T ) -120 °C). The measurements
were made in the range 1.65-31.55°/31.52° for 1a a a /2a a a in
theta. Full sphere data collection was done with ω and æ scans.
The program used for data collection was Smart V. 5.060
(BrukerAXS 1999); for data reduction Saint + Version 6.02
1,6,11-Tr is[(4-m et h ylp h en yl)su lfon yl]-1,6,11-t r ia za ci-
clop en ta d eca -3,8,13-tr iyn e (1a a a ). Gen er a l P r oced u r e. A
stirred mixture of 10a a a (0.15 g, 0.24 mmol), 1,4-dibromo-2-
butyne, 5 (0.06 g, 0.28 mmol), anhydrous potassium carbonate
(0.17 g, 1.23 mmol), and acetonitrile (30 mL) was refluxed for
5.5 h (TLC monitoring). The salts were filtered off, and the
filtrate was evaporated. The oily residue was chromatographed
through silica gel with hexane/ethyl acetate (polarity from 9:1
to 6:4) to afford 1a a a (0.12 g, 74%; 70% yield starting from
1,4-bis(methanesulfonyloxy)-2-butyne, 6) as a colorless solid;
mp 219 °C (dec); IR (KBr) 2995, 1919, 1597, 1433, 1348, 1166,
1
1092 cm-1; H NMR (200 MHz, [D6]DMSO) 2.52 (s, 9H), 3.96
(s, 12H), 7.54 (AA′ part of the AA′BB′ system, J ) 8.1 Hz, 6H),
7.74 (BB′ part of the AA′BB′ system, J ) 8.1 Hz, 6H); 13C NMR
(50 MHz, [D6]DMSO) 21.2, 37.6, 79.0, 127.7, 129.9, 134.9,
144.0; ESI-MS (m/z) 664 [M + H]+, 681 [M + NH4]+, 686 [M +

N-Containing 15-Membered Triacetylenic Macrocycles
Organometallics, Vol. 23, No. 11, 2004 2767
(Bruker AXS 1999); and for absorption correction SADABS
(Bruker AXS 1999). Crystal structure solutions for 1a a a and
2a a a were achieved using direct methods as implemented in
SHELXTL Version 5.10 (Sheldrick, Universtita¨t Go¨ttingen
(Germany), 1998) and visualized using the XP program.
Missing atoms were subsequently located from difference
Fourier synthesis and added to the atom list. Least-squares
refinement on F2 using all measured intensities was carried
out using the program SHELXTL Version 5.10 (Sheldrick,
Universtita¨t Go¨ttingen (Germany), 1998). All non hydrogen
atoms were refined including anisotropic displacement pa-
rameters. Hydrogen atoms were freely refined for 1a a a and
invariably placed in geometrically optimized positions and
forced to ride on the atom to which they are attached in
2a a a .
the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, U.K.; fax +44 1223 336033 or e-mail
deposit@ccdc.cam.ac.uk).
Ack n ow led gm en t. Financial support from MCYT
of Spain (Project No. BQU2002-04002) and “Generalitat
de Catalunya” (Projects No. SGR2001-00291 and SGR-
00181) and a predoctoral grant (to A.T.) are gratefully
acknowledged.
Su p p or tin g In for m a tion Ava ila ble: Details of the two
structure determinations, including atomic coordinates, bond
lengths and angles, thermal parameters, least-squares planes,
and interatomic contacts of complexes 1a a a and 2a a a . This
material is available free of charge via the Internet at
http://pubs.acs.org.
The supplementary crystallographic data for this paper
(CCDC 230219 and CCDC 230220) can be obtained free of
charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from
OM034384O