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Yashima et al.
changes of biopolymers such as DNA and proteins.9 In these
cases, the host molecules are chiral, but if a guest is achiral
and chromophoric, the host-guest complex will show an
induced CD (ICD) in the UV and/or visible region of the guest
molecule, and their binding constants and guest orientations can
1
0
be determined by using CD titrations or ICD curves.
Recently, a very interesting approach has been performed with
6
e,11
achiral, chromophoric hosts, calixarenes,
resocinol cyclic
12
13
tetramers, porphyrin derivatives, and diboronic acid deriva-
tives.14 They can form complexes with particular guests, such
as chiral ammoniums, polyols, amino acid esters, and saccha-
rides, respectively, and the complexes exhibited a characteristic,
one-handed helix upon complexation with chiral amines and
amino alcohols, and the complexes showed a characteristic,
exciton-type coupled ICDs in the UV-visible region.17 The
Cotton effect signs corresponding to the helical sense can be
used as a novel probe for the chirality assignments of amines.1
This may be the first example of the prevailing helix induction
on an optically inactive polymer due to an acid-base interac-
8,19
15
exciton-type coupled ICD in the absorption region of the hosts,
the sign of which reflects the absolute configuration of the
guests.16
2
0,21
tion.
Very recently, we also found a similar phenomenon for the
complexes of an optically inactive, chromophoric polymer with
chiral amines; a stereoregular poly((4-carboxyphenyl)acetylene)
From the previous results of poly-1, we expected that related
stereoregular poly(phenylacetylenes) bearing other functional
groups, for instance, a boronic acid residue or an amino group,
would also respond to chiral compounds capable of interacting
with these functional groups on the phenyl groups and show a
characteristic ICD depending on the stereochemistry of the chiral
(poly-1) can change its structure into the prevailing, dynamic
(
9) For reviews, see: (a) Hatano, M. Induced Circular Dichroism in
Biopolymer-Dye Systems; SVH: Berlin, 1986. (b) Woody, R. W. In Circular
DichroismsPrinciples and Applications; Nakanishi, K., Berova, N., Woody,
R. W., Eds.; VCH: New York, 1994; Chapter 17. (c) Johnson, W. C. In
Circular DichroismsPrinciples and Applications; Nakanishi, K., Berova,
N., Woody, R. W., Eds.; VCH: New York, 1994; Chapter 19.
(16) For recent examples of chirality recognition with chiral hosts, see:
(a) Kaneda, T.; Hirose, K.; Misumi, S. J. Am. Chem. Soc. 1989, 111, 742-
743. (b) Shinkai, S.; Nishi, T.; Matsuda, T. Chem. Lett. 1991, 437-440.
(c) Ueno, A.; Kuwabara, T.; Nakamura, A.; Toda, F. Nature 1992, 356,
136-137. (d) James, T. D.; Harada, T.; Shinkai, S. J. Chem. Soc., Chem.
Commun. 1993, 857-858. (e) James, T. D.; Sandanayake, K. R. A. S.;
Iguchi, R.; Shinkai, S. J. Am. Chem. Soc. 1995, 117, 8982-8987. (f) James,
T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Nature 1995, 374, 345-347.
(g) James, T. D.; Kawabata, H.; Ludwig, R.; Murata, K.; Shinkai, S.
Tetrahedron 1995, 51, 555-566.
(17) Yashima, E.; Matsushima, T.; Okamoto, Y. J. Am. Chem. Soc. 1995,
117, 11596-11597.
(18) For examples of chirality assignments of amines by CD, see refs
15e-g and 19. (a) Smith, H. E. Chem. ReV. 1983, 83, 359-377. (b) Hoye,
T. R.; Renner, M. K. J. Org. Chem. 1996, 61, 2056-2064. (c) Smith, H.
E.; Neergaard, J. R. J. Am. Chem. Soc. 1996, 118, 7694-7701.
(19) (a) Tokura, N.; Nagai, T.; Takenaka, S.; Oshima, T. J. Chem. Soc.,
Perkin Trans. 2 1974, 337-342. (b) Takenaka, S.; Kondo, K.; Tokura, N.
J. Chem. Soc., Perkin Trans. 2 1975, 1520-1524. (c) Takenaka, S.;
Miyauchi, Y.; Tokura, N. Tetrahedron Lett. 1976, 3811-3814. (d)
Takenaka, S.; Ako, M.; Kotani, T.; Matsubara, A.; Tokura, N. J. Chem.
Soc., Perkin Trans. 2 1978, 95-99. (e) Takenaka, S.; Koden, M. J. Chem.
Soc., Chem. Commun. 1978, 830. (f) Schipper, P. E.; O’Brien, J. M.; Ridley,
D. D. J. Phys. Chem. 1985, 89, 5805-5810.
(
10) Forman, J. E.; Barrans, R. E., Jr.; Dougherty, D. A. J. Am. Chem.
Soc. 1995, 117, 9213-9228 and references cited therein.
11) (a) Arimura, T.; Edamitsu, S.; Shinkai, S.; Manabe, O.; Muramatsu,
(
T.; Tashiro, M. Chem. Lett. 1987, 2269-2272. (b) Arimura, T.; Shinkai,
S. Bull. Chem. Soc. Jpn. 1991, 64, 1896-1900. (c) Morozumi, T.; Shinkai,
S. J. Chem. Soc., Chem. Commun. 1994, 1219-1220. (d) Morozumi, T.;
Shinkai, S. Chem. Lett. 1994, 1515-1518.
(
12) (a) Kikuchi, Y.; Kobayashi, K.; Aoyama, Y. J. Am. Chem. Soc.
1
992, 114, 1351-1358. (b) Kikuchi, Y.; Tanaka, Y.; Sutarto, S.; Kobayashi,
K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302-10306. (c)
Kobayashi, K.; Asakawa, Y.; Kikuchi, Y.; Toi, H.; Aoyama, Y. J. Am.
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(13) (a) Mizutani, T.; Ema, T.; Yoshida, T.; Kuroda, Y.; Ogoshi, H. Inorg.
Chem. 1993, 32, 2072-2077. (b) Mizutani, T.; Murakami, T.; Kurahashi,
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(
14) (a) Tsukagoshi, K.; Shinkai, S. J. Org. Chem. 1991, 56, 4089-
4
091. (b) Kondo, K.; Shiomi, Y.; Saisho, M.; Harada, T.; Shinkai, S.
Tetrahedron 1992, 48, 8239-8252. (c) Shiomi, Y.; Saisho, M.; Tsukagoshi,
K.; Shinkai, S. J. Chem. Soc., Perkin Trans. 1 1993, 2111-2117. (d) Deng,
G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567-4572.
(e) Imada, T.; Murakami, H.; Shinkai, S. J. Chem. Soc., Chem. Commun.
(20) For CD studies of a predominantly one-handed helix induction of
polymers, see: (a) Green, M. M.; Andreola, C.; Munoz, B.; Reidy, M. P.
J. Am. Chem. Soc. 1988, 110, 4063-4065. (b) Green, M. M.; Lifson, S.;
Teramoto, A. Chirality 1991, 3, 285-291. (c) Green, M. M.; Khatri, C.;
Peterson, N. C. J. Am. Chem. Soc. 1993, 115, 4941-4942. (d) Fujiki, M.
J. Am. Chem. Soc. 1994, 116, 11976-11981. (e) Khatri, C. A.; Vaidya, M.
M.; Levon, K.; Jha, S. K.; Green, M. M. Macromolecules 1995, 28, 4719-
4728. For examples of CD studies on a one-handed helix formation of
polypeptides, see: (f) Libman, J.; Tor, Y.; Shanzer, A. J. Am. Chem. Soc.
1987, 109, 5880-5881. (g) Ruan, F.; Chen, Y.; Hopkins, P. B. J. Am. Chem.
Soc. 1990, 112, 9403-9404. (h) Ghadiri, M. R.; Soares, C.; Choi, C. J.
Am. Chem. Soc. 1992, 114, 825-831. (i) Wittung, P.; Nielsen, P. E.;
Buchardt, O.; Egholm, M.; Nord e´ n, B. Nature 1994, 368, 561-563. For
CD studies of a chiral helix induction of small molecules, see ref 13. (j)
Lightner, D. A.; Gawronski, J. K.; Gawronska, K. J. Am. Chem. Soc. 1985,
107, 2456-2461. (k) Lightner, D. A.; Gawronski, J. K.; Wijekoon, W. M.
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(o) Charbonni e´ re, L. J.; Gilet, M.-F.; Bernauer, K.; Williams, A. F. J. Chem.
Soc., Chem. Commun. 1996, 39-40. (p) S a´ nchez-Quesada, J.; Seel, C.;
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C. R.; Benaglia, M.; Cozzi, F.; Siegel, J. S. Angew. Chem., Int. Ed. Engl.
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Okamoto, Y.; Nakano, T. Chem. ReV. 1994, 94, 349-372. (s) Nolte, R. J.
M. Chem. Soc. ReV. 1994, 11-19. (t) Qin, M.; Bartus, J.; Vogl, O.
Macromol. Symp. 1995, 98, 387-402. (u) Patten, T. E.; Novak, B. M. J.
Am. Chem. Soc. 1996, 118, 1906-1916.
1
4
1
994, 1557-1558. (f) Nakashima, K.; Shinkai, S. Chem. Lett. 1995, 443-
44. (g) Mikami, M.; Shinkai, S. J. Chem. Soc., Chem. Commun. 1995,
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(
1
j) Suenaga, H.; Arimori, S.; Shinkai, S. J. Chem. Soc., Perkin Trans. 2
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1
Angew. Chem., Int. Ed. Engl. 1996, 35, 1911-1922.
(15) The CD exciton chirality method developed by Nakanishi and
Harada has been extensively applied for determining the absolute configura-
tions of chiral molecules. For reviews, see: (a) Harada, N.; Nakanishi, K.
Circular Dichroic SpectroscopysExciton Coupling in Organic Stereochem-
istry; University Science Book: Mill Valley, CA, 1983. (b) Nakanishi, K.;
Berova, N. In Circular DichroismsPrinciples and Applications; Nakanishi,
K., Berova, N., Woody, R. W., Eds.; VCH: New York, 1994; Chapter 13.
For recent examples, see: (c) Wiesler, W. T.; Nakanishi, K. J. Am. Chem.
Soc. 1990, 112, 5574-5583. (d) Harada, N.; Saito, A.; Ono, H.; Gawronski,
J.; Gawronska, K.; Sugioka, T.; Uda, H.; Kuriki, T. J. Am. Chem. Soc.
1991, 113, 3842-3850. (e) Berova, N.; Gargiulo, D.; Nakanishi, K.; Harada,
N. J. Am. Chem. Soc. 1993, 115, 4769-4775. (f) Gargiulo, D.; Cai, G.;
Ikemoto, N.; Bozhkova, N.; Odingo, J.; Berova, N.; Nakanishi, K. Angew.
Chem., Int. Ed. Engl. 1993, 32, 888-891. (g) Gargiulo, D.; Ikemoto, N.;
Odingo, J.; Bozhkova, N.; Iwashita, T.; Berova, N.; Nakanishi, K. J. Am.
Chem. Soc. 1994, 116, 3760-3767. (h) Matile, S.; Berova, N.; Nakanishi,
K.; Novkova, S.; Philipova, I.; Blagoev, B. J. Am. Chem. Soc. 1995, 117,
7
021-7022. (i) Matile, S.; Berova, N.; Nakanishi, K.; Fleischhauer, J.;
Woody, R. W. J. Am. Chem. Soc. 1996, 118, 5198-5206. (j) Rele, D.;
Zhao, N.; Nakanishi, K.; Berova, N. Tetrahedron 1996, 52, 2759-2776.