Recognition of the chain length of α,ω-diamines by a meso-ternaphthalene derivative with two crown ethers

Article abstract of DOI:10.1016/S0040-4039(00)01018-2

A new ditopic receptor 2 consisting of a meso-ternaphthalene backbone and two crown rings has been shown to selectively complex and transfer dipicrate of 1,9-diaminononane and 1,10-diaminodecane from aqueous solution into the organic phase. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4039(00)01018-2

Tetrahedron Letters 41 (2000) 6089±6093
Recognition of the chain length of a,o-diamines by a
meso-ternaphthalene derivative with two crown ethers
Kazunori Tsubaki,a Hiroyuki Tanaka,a Takumi Furuta,a Takayoshi Kinoshitab
and Kaoru Fujia,*
aInstitute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
bExploratory Research Laboratories, Fujisawa Pharmaceutical Co., Ltd., Kashima, Yodogawa, Osaka 532-8514, Japan
Received 15 May 2000; revised 15 June 2000; accepted 16 June 2000
Abstract
A new ditopic receptor 2 consisting of a meso-ternaphthalene backbone and two crown rings has been
shown to selectively complex and transfer dipicrate of 1,9-diaminononane and 1,10-diaminodecane from
aqueous solution into the organic phase. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: crown ethers; molecular recognition; diamines.
Over the past two decades, many synthetic receptors have been constructed based on the fact
that some of their properties, such as shape, size and functional groups, complement those of a
guest molecule. Several ditopic receptors have been reported to recognize the length of a,o-
diamines. They have carboxylic acids1 or crown ethers2 to bind to amines using speci®c hydrogen-
bonding interactions. Recently, we reported the preparation of chiral ter- and quaternaphthalene
derivatives.3 These compounds are expected to be backbones for host molecules for recognizing
the length of a,o-diamines due to their upright nature. In this paper, we report new ditopic
receptors 1 and 2 consisting of a meso-ternaphthalene backbone and two crown rings, the latter
of which showed sharp recognition of the length of a,o-diamines 3.
The synthetic route to the host molecules 1 and 2 is outlined in Scheme 1. Racemic
ternaphthalene 43 was methylated and then subjected to deacetylation followed by reductive
removal of the benzyl group to give meso-ternaphthalene 5, which was then converted to ditri¯ate
6 in 74% overall yield from 4. The coupling partner 7 was prepared from the corresponding
bromide4 in 50% yield. The reaction of tri¯ate 6 with boric acid 7 under modi®ed Suzuki
coupling conditions5 gave the desired host 1 in 80% yield. Simultaneous deprotection of an allylic
group took place under these reaction conditions. Methylation of 1 gave 2 in 65% yield.
* Corresponding author. Fax: +81-774-38-3197; e-mail: fuji@scl.kyoto-u.ac.jp
0040-4039/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(00)01018-2

6090
Scheme 1. Reactions and conditions: (i) MeI, K2CO3, acetone, re¯ux; (ii) NaOH, H2O±THF, rt; (iii) Pd/C, HCO2NH4,
THF±MeOH, 60ꢀC, 1 h; (iv) Tf2O, i-Pr2NEt, CH2Cl2, rt; (v) Pd(PPh3)4, Na2CO3, toluene±MeOH±H2O, 80ꢀC, 26 h;
(vi) MeI, NaH, DMF, 0ꢀC±rt
Interaction between host 1 and a,o-diamines 3 was examined by the UV±vis spectroscopic
method. Absorption at 375 nm increased upon addition of these diamines to the host 1 in
THF:H2O (4:1). Job plots suggested that the host:guest ratio in complexes was 1:1 at 25ꢀC. The
association constants (Ka) were determined by titration, and analyzed by the Rose±Drago
method.6 The results are summarized in Table 1. No relationship was observed between the
association constants and the length of a,o-diamines (entries 1±5). The behavior of 1 and non-
ylamine indicated 1:1 complexation, and its Ka of 139þ13 (entry 6) was almost the same as those

6091
of 1 and diamines. These results indicate that complexation is based on acid-base interaction
between only one of the phenol crown rings of 1 and one of the amino groups of a,o-diamines 3.7
Table 1
The association constant (Ka) of the complexes of the hosts 1 and 2 with diamines 3
The ability of the ditopic receptor 2 to recognize dipicrates of a,o-diamines 3 was investigated
by the method based on picrate liquid±liquid extraction from H2O to CHCl3 at 25ꢀC.2i,8 The Ka
values were calculated, assuming that a 1:1 complex was formed. The Ka values clearly depend on
the chain length of the guests (entries 7±13). It was shown that the host 2 speci®cally bind dia-
mines 3 (n=9 and 10). The Ka values clearly decreased for complexes of 2 with 1,11-diamino-
undecane or the longer and with 1,8-diaminooctane or the shorter, due to the rigid nature of the
framework of the host 2. In general, ditopic receptors sharply distinguish the amine with optimal
length from those of a shorter length, while the recognition of the length is rather loose for dia-
mines longer than that of optimal length. As can be seen from Table 1, the Ka value for 1,11-
diaminoundecane is approximately six times less than that of 1,10-diaminodecane (see entries 11
and 10). The only example showing sharp discrimination of the length of guest includes a bisan-
thracenyl macrotricyclic receptor reported by Lehn et al.2
The structures of 1 and 2 were determined by an X-ray crystallographic analysis.9 Host 1
cocrystallized with two disordered toluene molecules. The central naphthyl ring was also dis-
ordered in the opposite sense in a ratio of about 1:1 in the crystalline state (Fig. 1a,b). The crys-
tals of host 2 obtained from acetonitrile contain two molecules of the solvent. No disorder of the
central naphthyl ring was observed, although an oxygen atom in the crown ring was disordered
(Fig. 1c).10 A marked di€erence between the crystal structures of 1 and 2 was found in the

6092
conformation of the crown rings. Two rings of 2 were bent over to create a cavity, while those of
1 were spread out, which may explain the selective complexation of 2 with diamines.
Figure 1. X-Ray crystal structures of 1 (a) and (b), and 2 (c). Hydrogen atoms and solvent molecules have been
omitted for clarity
Acknowledgements
This work was partially supported by a Grant-in-Aid for Scienti®c Research from the Ministry
of Education, Science, Sports and Culture of Japan.
References
1. Li, C.; Medina, J. C.; Maguire, G. E. M.; Abel, E.; Atwood, J. L.; Gokel, G. W. J. Am. Chem. Soc. 1997, 119,
1609±1618.

6093
2. (a) Kotzyba-Hibert, F.; Lehn, J.-M.; Vierling, P. Tetrahedron Lett. 1980, 21, 941±944. (b) Kotzyba-Hibert, F.;
Lehn, J.-M.; Saigo, K. J. Am. Chem. Soc. 1981, 103, 4266±4268. (c) Kintzinger, J.-P.; Kotzyba-Hibert, F.; Lehn,
J.-M.; Pagelot, A.; Saigo, K. J. Chem. Soc., Chem. Commun. 1981, 833±836. (d) Pascard, C.; Riche, C.; Cesario,
M.; Kotzyba-Hilbert, F.; Lehn, J.-M. J. Chem. Soc., Chem. Commun. 1982, 557±560. (e) Shinkai, S.; Honda, Y.;
Kusano, Y.; Manabe, O. J. Chem. Soc., Chem. Commun. 1982, 848±850. (f) Shinkai, S.; Honda, Y.; Minami, T.;
Ueda, K.; Manabe, O.; Tashiro, M. Bull. Chem. Soc. Jpn. 1983, 56, 1700±1704. (g) Hamilton, A. D.; Lehn, J.-M.;
Sessler, J. L. J. Chem. Soc., Chem. Commun. 1984, 311±313. (h) Smeets, J. W. H.; Sijbesma, R. P.; van Dalen, L.;
Spek, A. L.; Smeets, W. J. J.; Nolte, R. J. M. J. Org. Chem. 1989, 54, 3710±3713. (i) Smeets, J. W. H.; Visser, H. C.;
Kaats-Richters, V. E. M.; Nolte, R. J. M. Rec. Trav. Chim. Pays-Bas, 1990, 109, 147±153. (j) Misumi, S. Pure
Appl. Chem. 1990, 62, 493±498. (k) Sutherland, I. O. Pure Appl. Chem. 1990, 62, 499±504. (l) de Silva, A. P.;
Sandanayake, K. R. A. S. Angew. Chem., Int. Ed. Engl. 1990, 29, 1173±1175. (m) Voyer, N.; Deschense, D.;
Bernier, J.; Roby, J. J. Chem. Soc., Chem. Commun. 1992, 134±136. (n) Fages, F.; Desvergne, J.-P.; Bouas-
Laurent, H.; Lehn, J.-M.; Konopelski, J. P.; Marsau, P.; Barrans, Y. J. Chem. Soc., Chem. Commun. 1990, 655±
658. (o) Fages, F.; Desvergne, J.-P.; Kampke, K.; Bouas-Laurent, H.; Lehn, J.-M.; Meyer, M.; Albrecht-Gary, A.-
M. J. Am. Chem. Soc. 1993, 115, 3658±3664. (p) Jeong, K.-S.; Park, J. W.; Cho, Y. L. Tetrahedron Lett. 1996, 37,
2795±2798. (q) Hayashi, T.; Nonoguchi, M.; Aya, T.; Ogoshi, H. Tetrahedron Lett. 1997, 38, 1603±1606. (r) Fuji,
K.; Tsubaki, K.; Tanaka, K.; Hayashi, N.; Otsubo, T.; Kinoshita, T. J. Am. Chem. Soc. 1999, 121, 3807±3808. (s)
Kubo, Y.; Murai, Y.; Yamanaka, J.; Tokita, S.; Ishimaru, Y. Tetrahedron Lett. 1999, 40, 6019±6023.
3. Tanaka, K.; Furuta, T.; Fuji, K.; Miwa, Y.; Taga, T. Tetrahedron: Asymmetry 1996, 7, 2199±2202.
4. von Gent, J.; Sudholter, E. J. R.; Lambeck, P. V.; Popma, T. J. A.; Gerritsma, G. J.; Reinhoudt, D. N. J. Chem.
Soc., Chem. Commun. 1988, 893±895.
5. Thompson, W. J.; Gaudino, J. J. Org. Chem. 1984, 49, 5237±5243.
6. Rose, N. J.; Drago, R. S. J. Am. Chem. Soc. 1959, 81, 6138±6145.
7. Browne, C. M.; Ferguson, G.; McKervey, M. A.; Mulholland, D. L.; O'Connor, T.; Parvez, M. J. Am. Chem. Soc.
1985, 107, 2703±2712.
8. Koenig, K. E.; Lein, G. M.; Stuckler, P.; Kaneda, T.; Cram, D. J. J. Am. Chem. Soc. 1979, 101, 3553±3566.
.
9. Crystal data for 1 (toluene)2: C80H88O16, M=1305.55, triclinic, a=10.334(3) A, b=33.582(5) A, c=10.303(2) A, ꢀ
=94.77(2)ꢀ, ꢁ=95.61(2)ꢀ, g=94.31(2)ꢀ, V=3533(1) A3, space group P-1(#2), z=2, D=1.227 g cm^1, ꢂ(Cu-
Ka)=6.87 cm^1, Rigaku AFC7R di€ractormeter with graphite-monochlomated Cu-Ka (l=1.54178 A, T=293
K). No. of measured re¯ections: 12422. Structure solution by direct method (SHELX-86), re®nement by full-
matrix least-squares using all re¯ections, R=0.083 (jF0j>4 s(F0)), Rw=0.101 (all re¯ections), GOF=2.79,
.
.
Occ.=0.5 for 1a and 0.5 for 1b. Crystal data for 2 (CH3CN)2 (H2O)2: C72H86N2O18, M=1267.47, triclinic,
a=15.172(1) A, b=17.771(2) A, c=14.481(2) A, ꢀ=106.29(1)ꢀ, ꢁ=109.718(9)ꢀ, g=67.694(7)ꢀ, V=3348.0(7) A3,
space group P-1(#2), z=2, D=1.257 g cm^1, ꢂ(Cu-Ka)=7.39 cm^1, Rigaku AFC7R di€ractormeter with
graphite-monochlomated Cu-Ka (l=1.54178 A, T=293 K). No. of measured re¯ections: 11844. Structure
solution by direct method (SHELX-97), re®nement by full-matrix least-squares using all re¯ections, R=0.089
(jF0j>5 s(F0)), Rw=0.129 (all re¯ections), GOF=3.45.
10. Disorder of the central naphthyl ring similar to that of 1 was found in the crystals obtained from acetone.