Synthesis of Precise Unnatural Oligomers Using Well-Defined Synthetic or DNA Templates

使用具有特定长度、结构和构象的非自然和自然（DNA）模板（亲本），描述了快速构建具有精确分子量、结构，在某些情况下甚至是立体化学的有机低聚物的新途径。利用精确定义的刚性棒状合成模板，将尝试快速构建与模板长度几乎相同的低聚物。非天然单体通过非共价键基团（NCBMs）与模板形成离子键或氢键，然后通过化学或光化学诱导寡聚化形成超分子的亲子双相结构。由于模板反应在单体-单体取向上是伪固态或伪拓扑化学的，因此聚合反应在动力学上应该是有利的。离子键或h键双亲双链的断裂将产生新的合成子寡聚物，该子寡聚物保留了母体模板的特定长度信息，以及可能的立体化学信息，如螺旋感。可以设想将父模板和子模板重新用作新模板的方法，从而使整个过程在模板中具有催化作用，最终在生产能力上类似于自然或类似于聚合酶链反应（pcr）。这些精密的大分子系统在电子学、光子学、分子电子学、催化学、分离科学、纳米工程和纳米生物工程中变得越来越重要。这个项目，如果成功，可以大大简化精确定义的大分子结构的制备，目前只能通过费力的分步程序或多次分析分离来制备。＊＊＊

9612172 Tour New routes are described for the facile construction of organic oligomers of precise molecular weight, constitution, and in some cases, even stereochemistry, using unnatural and natural (DNA) templates (parents) of specific length, constitution, and conformation. Taking advantage of precisely-defined synthetic templates that are rigid-rod- like, the rapid construction of oligomers of nearly the same length as the templates will be attempted. Unnatural monomers will be ionically- or hydrogen-bonded to the templates via non-covalent bonding moieties (NCBMs), then oligomerization will be induced chemically or photochemically to afford a supramolecular parent-daughter duplex. The polymerizations should be kinetically favored since the templated reaction is pseudo-solid state or pseudo- topochemical in its monomer-monomer orientations. Cleavage of the ionically- or H-bound parent-daughter duplex would afford a new synthetic daughter oligomer that retains the specific length information of the parent template, as well as, possibly, the stereochemical information such as the helical sense. Methods can be envisioned to re-use the parent template and the daughter(s) as new templates, thus making the entire process catalytic in template, and ultimately natural-like or polymerase chain reaction-like (PCR-like) in its productive capabilities. %%% These precise macromolecular systems are becoming important for electronics, photonics, molecular electronics, catalysis, separation science, nano-engineering, and nano- bioengineering. This project, if successful, could significantly simplify the preparation of precisely defined macromolecular architectures which are currently prepared only by laborious step-wise procedures or multiple analytical separations. ***