Jian Huahua, Tour James M
Department of Chemistry, Center for Nanoscale Science and Technology, MS-222, Rice University, 6100 South Main Street, Houston, Texas 77005, USA.
J Org Chem. 2005 Apr 29;70(9):3396-424. doi: 10.1021/jo048051s.
[structure: see text] A series of building blocks for the synthesis of oligo(phenylene vinylene)s (OPVs) and hybrid oligomers were prepared, and alternating Heck coupling and Horner-Wadswoth-Emmons (HWE) reactions were used to couple the building blocks. Model studies were carried out to optimize the reaction strategies. The products were made to bear aryl diazonium functionalities that allow them to be used as surface grafting moieties in hybrid silicon/molecule assemblies. A library of OPV and hybrid oligomer tetramers was synthesized using fluorous mixture synthesis (FMS). The fluorous tags, which are secondary amines bearing different numbers of fluorine atoms, were synthesized and used as phase tags in mixture synthesis. The tags and substrates were anchored together by triazene linkages. The mixture synthesis was monitored by analytical HPLC on a fluorous column, and isolation of final OPV and hybrid oligomer tetramers was achieved by preparative HPLC. At the end of the FMS, after demixing, the tagged products were detagged by cleaving the triazene linkage and generating a series of aryl diazonium compounds. The fluorous tags could be recovered and reused. The NMR spectra of the 1-aryl-3,3-dialkyltriazenes are discussed.
[结构：见正文] 制备了一系列用于合成聚对苯撑乙烯（OPV）和杂化低聚物的结构单元，并采用交替的Heck偶联反应和霍纳尔-沃兹沃思-埃蒙斯（HWE）反应来连接这些结构单元。进行了模型研究以优化反应策略。使产物带有芳基重氮官能团，使其能够用作硅/分子混合组装体中的表面接枝部分。使用氟相混合物合成（FMS）方法合成了一个OPV和杂化低聚物四聚体文库。合成了带有不同氟原子数目的仲胺形式的氟相标签，并将其用作混合物合成中的相标签。标签和底物通过三氮烯键连接在一起。通过在氟相柱上进行分析型高效液相色谱（HPLC）监测混合物合成过程，并通过制备型HPLC分离得到最终的OPV和杂化低聚物四聚体。在FMS结束时，分层后，通过切断三氮烯键并生成一系列芳基重氮化合物来去除标签。氟相标签可以回收并重复使用。讨论了1-芳基-3,3-二烷基三氮烯的核磁共振光谱。
