Centre for Systems Chemistry, Stratingh Institute, University of Groningen , Nijenborgh 4, 9747 AG Groningen, The Netherlands.
Faculty of Chemistry, University of Warsaw , Pasteura 1, 02-093 Warsaw, Poland.
J Am Chem Soc. 2017 May 17;139(19):6744-6751. doi: 10.1021/jacs.7b02575. Epub 2017 May 9.
The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we introduce the concept of antiparallel chemistries, in which the same functional group can be channeled into one of two reversible chemistries depending on a controllable parameter. Such systems allow both for achieving complexity, by combinatorial chemistry, and addressing it, by switching from one chemistry to another by controlling an external parameter. In our design the two antiparallel chemistries are thiol-disulfide exchange and thio-Michael addition, sharing the thiol as the common building block. By means of oxidation and reduction the system can be reversibly switched from predominantly thio-Michael chemistry to predominantly disulfide chemistry, as well as to any intermediate state. Both chemistries operate in water, at room temperature, and at mildly basic pH, which makes them a suitable platform for further development of systems chemistry.
设计具有高但可寻址复杂性的反应网络是制造高级功能化学系统的必要前提。动态组合化学已被证明是实现复杂性的有用工具，但在控制方面存在一些限制。本文介绍了反平行化学的概念，其中相同的官能团可以根据可控参数引导到两种可逆化学反应中的一种。这样的系统既可以通过组合化学来实现复杂性，也可以通过控制外部参数从一种化学转变为另一种化学来解决问题。在我们的设计中，两种反平行化学是硫醇-二硫化物交换和硫醇-Michael 加成，它们共享巯基作为共同的构建块。通过氧化还原反应，该系统可以可逆地从主要的硫醇-Michael 化学转变为主要的二硫化物化学，以及任何中间状态。两种化学都在水、室温下和弱碱性 pH 条件下运行，这使它们成为进一步发展系统化学的合适平台。
