A Molecular Leverage for Helicity Control and Helix Inversion

被引:107
作者
Akine, Shigehisa [1 ]
Hotate, Sayaka [1 ]
Nabeshima, Tatsuya [1 ]
机构
[1] Univ Tsukuba, Grad Sch Pure & Appl Sci, Tsukuba, Ibaraki 3058571, Japan
关键词
DIAZA-COPE REARRANGEMENT; B DNA CONFORMATIONS; MACROMOLECULAR HELICITY; COBALT(II) COMPLEX; SENSE INVERSION; LANTHANIDE(III) COMPLEXES; ABIOTIC METALLOFOLDAMERS; ABSOLUTE HELICITY; COPPER-COMPLEXES; CHIRALITY;
D O I
10.1021/ja205570z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The helical tetranuclear complex [LZn(3)La-(OAc)(3)] having two benzocrown moieties was designed and synthesized as a novel molecular leverage for helicity control and helix inversion. Short alkanediammonium guests H(3)N(+)-(CH(2))(n)NH(3)(+) (n = 4, 6, 8) preferentially stabilized the P-helical isomer of [LZn(3)La(OAc)(3)], while the longer guest H(3)N(+)(CH(2))(12)NH(3)(+) caused a helix inversion to give the M-helical isomer as the major isomer. The differences in the molecular lengths were efficiently translated into helical handedness via the novel molecular leverage mechanism using the gauche/anti conversion of the trans-1,2-disubstituted ethylenediamine unit.
引用
收藏
页码:13868 / 13871
页数:4
相关论文
共 61 条
[51]   Two-dimensional surface chirality control by solvent-induced helicity inversion of a helical polyacetylene on graphite [J].
Sakurai, SI ;
Okoshi, K ;
Kumaki, J ;
Yashima, E .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (17) :5650-5651
[52]   HELIX-SENSE INVERSION IN POLYASPARTATES [J].
SASAKI, S ;
OGAWA, H ;
KIMURA, S .
POLYMER JOURNAL, 1991, 23 (11) :1325-1331
[53]   THEORY OF THE HELIX-SENSE INVERSION IN POLYPEPTIDES [J].
TORIUMI, H .
MACROMOLECULES, 1984, 17 (08) :1599-1605
[54]   Non-B DNA conformations, mutagenesis and disease [J].
Wells, Robert D. .
TRENDS IN BIOCHEMICAL SCIENCES, 2007, 32 (06) :271-278
[55]   Chiral inversion around a seven-coordinated cobalt center induced by an interaction between sugars and sulfate anions [J].
Yano, S ;
Nakagoshi, M ;
Teratani, A ;
Kato, M ;
Onaka, T ;
Iida, M ;
Tanase, T ;
Yamamoto, Y ;
Uekusa, H ;
Ohashi, Y .
INORGANIC CHEMISTRY, 1997, 36 (19) :4187-4194
[56]   Helix-helix transition of optically active poly((1R,2S)-N-(4-ethynylbenzyl)norephedrine) induced by diastereomeric acid-base complexation using chiral stimuli [J].
Yashima, E ;
Maeda, Y ;
Okamoto, Y .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (34) :8895-8896
[57]   Electron-induced inversion of helical chirality in copper complexes of N,N-dialkylmethionines [J].
Zahn, S ;
Canary, JW .
SCIENCE, 2000, 288 (5470) :1404-1407
[58]   Redox-induced ligand reorganization and helicity inversion in copper complexes of N,N-dialkylmethionine derivatives [J].
Zahn, Steffen ;
Das, Debasis ;
Canary, James W. .
INORGANIC CHEMISTRY, 2006, 45 (15) :6056-6063
[59]   Abiotic metallofoldamers as electrochemically responsive molecules [J].
Zhang, F ;
Bai, S ;
Yap, GPA ;
Tarwade, V ;
Fox, JM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (30) :10590-10599
[60]   Control of helical sense and tightness of amino acid-based poly(N-propargylamide) by temperature and solvents [J].
Zhao, HC ;
Sanda, F ;
Masuda, T .
MACROMOLECULAR CHEMISTRY AND PHYSICS, 2005, 206 (16) :1653-1658