Ali Adeeb Al-Sheikh, Benson Ronald E, Blumentritt Sascha, Cameron T Stanley, Linden Anthony, Wolstenholme David, Thompson Alison
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia, B3H 4J3, Canada.
J Org Chem. 2007 Jun 22;72(13):4947-52. doi: 10.1021/jo070569j. Epub 2007 May 27.
The diastereoselective syntheses of Zn(II) bis(dipyrrinato) helicates is reported, involving ligands templated by the incorporation of homochiral binol within the linker joining the two dipyrrinato units. The most diastereoselective formation of dinuclear bis(dipyrrinato) helicates to date is reported. The formation of either mononuclear or dinuclear helicates can be tuned by varying the length of the linker between the dipyrrinato units and by varying the complexation procedure. The neutral dipyrrinato helicates were readily analyzed by HPLC to ascertain diastereoselectivity, and circular dichroism studies revealed the helical nature of the complexes. The molar ellipticities of the helicates produced by diastereoselective complexation are very large in the visible region and typically correspond to binol moieties in the UV region. Extensive X-ray crystallographic investigations further confirmed the helicity of the mononuclear Zn(II) helicates and identified significant interlayer displacement and bending within crystals.
报道了锌（II）双（二吡咯啉基）螺旋配合物的非对映选择性合成，其中涉及通过在连接两个二吡咯啉基单元的连接体中引入手性联萘酚作为模板的配体。报道了迄今为止双核双（二吡咯啉基）螺旋配合物最具非对映选择性的形成。通过改变二吡咯啉基单元之间连接体的长度以及改变络合过程，可以调节单核或双核螺旋配合物的形成。中性二吡咯啉基螺旋配合物很容易通过高效液相色谱法进行分析以确定非对映选择性，圆二色性研究揭示了配合物的螺旋性质。通过非对映选择性络合产生的螺旋配合物的摩尔椭圆率在可见光区域非常大，并且在紫外区域通常对应于联萘酚部分。广泛的X射线晶体学研究进一步证实了单核锌（II）螺旋配合物的螺旋性，并确定了晶体内显著的层间位移和弯曲。
