Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
Beilstein J Org Chem. 2012;8:897-904. doi: 10.3762/bjoc.8.102. Epub 2012 Jun 19.
Quite extensive synthetic achievements vanish in the online supporting information of publications on functional systems. Underappreciated, their value is recognized by experts only. As an example, we here focus in on the recent synthesis of multicomponent photosystems with antiparallel charge-transfer cascades in co-axial hole- and electron-transporting channels. The synthetic steps are described one-by-one, starting with commercial starting materials and moving on to key intermediates, such as asparagusic acid, an intriguing natural product, as well as diphosphonate "feet", and panchromatic naphthalenediimides (NDIs), to finally reach the target molecules. These products are initiators and propagators for self-organizing surface-initiated polymerization (SOSIP), a new method introduced to secure facile access to complex architectures. Chemoorthogonal to the ring-opening disulfide exchange used for SOSIP, hydrazone exchange is then introduced to achieve stack exchange, which is a "switching" technology invented to drill giant holes into SOSIP architectures and fill them with functional π-stacks of free choice.
相当多的合成成果在功能系统相关出版物的在线支持信息中消失了。它们的价值未被充分认识，只有专家才认可。例如，我们在这里关注的是最近在同轴空穴和电子传输通道中具有反平行电荷转移级联的多组分光系统的合成。合成步骤是从商业起始原料开始，逐一描述，然后逐步得到关键中间体，如具有有趣的天然产物 asparagusic acid 以及双膦酸盐“feet”和全光萘二酰亚胺（NDIs），最终得到目标分子。这些产物是自组织表面引发聚合（SOSIP）的引发剂和传播剂，这是一种新方法，用于确保容易获得复杂结构。然后，引入与 SOSIP 中用于开环二硫键交换的化学正交的腙交换，以实现堆叠交换，这是一种“开关”技术，用于在 SOSIP 结构中钻大洞，并填充自由选择的功能π-堆叠。
