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
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