Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.
Nat Chem. 2011 Sep 18;3(11):856-61. doi: 10.1038/nchem.1146.
Long-range communication of stereochemical information is common in biological systems, particularly in enzyme-catalysed reactions. Here, we report the remote control of the dynamic chirality of metal centres, coordinated by 2,2'-bipyridine ligands bearing dynamic helical oligopeptides. The helical chirality of the oligopeptides is controlled by a stereocentre remote from the metal. We show that when a mixture of chiral and achiral peptide ligands is used, both the chirality of the metal centre and that of the achiral oligopeptide helices are significantly amplified. The amplification mechanism relies on several steps of chirality induction, first from a single chiral peptide to the helicity of an oligopeptide through the induction of propeller chirality at the metal centre, then on to induction of helical chirality in an achiral oligopeptide.
远程传递立体化学信息在生物系统中很常见,尤其是在酶催化反应中。在这里,我们报告了通过 2,2'-联吡啶配体与动态螺旋寡肽配位来远程控制金属中心的动态手性。寡肽的螺旋手性受远离金属的手性中心控制。我们表明,当使用手性和非手性肽配体的混合物时,金属中心的手性和非手性寡肽螺旋的手性都会显著放大。放大机制依赖于几个步骤的手性诱导,首先是从单个手性肽通过在金属中心诱导推进式手性到手性寡肽的螺旋性,然后再诱导非手性寡肽的螺旋手性。