Combination of Reactions and Separations for New Organic Synthesis

有机合成的目的是高效地生产有用的有机化合物。有机化学家倾向于关注反应的效率和合成策略的能力。然而，重要的是要认识到，合成的总效率也受到以纯形式分离和分离产物的能力的限制。尽管已经做出了大量的努力来开发新的高效反应，但开发普遍适用于各种结构类型的化合物的策略性分离方案是非常必要的。本研究的目的是开发一种新的策略分离方案和反应组合，以提高有机合成的能力。我们将重点放在酸碱提取上，发现2-吡啶基二甲基硅基是一种有效的相标记。将TAG引入有机分子可以通过硅氢化和与2-吡啶硅基甲基锂的反应很容易地完成。碳金属化反应(Mizoroki-Heck反应)也可用于合成标记化合物。TAG的去除可以通过Tamao氧化和Hiyama交叉偶联反应来完成。有了TAG，我们开发了以多样性为导向的生物活性化合物的合成，如三苯氧胺类四取代烯烃。我们还开发了新的方法来构建扩展的π电子系统，这些系统显示出有趣的光物理性质，如光致发光。通过在Mizoroki-Heck反应和交叉偶联反应中使用双官能团和三官能团的芳基卤化物，合成了独特的扩展π电子体系的聚合物和树枝状大分子。

The purpose of organic synthesis is to produce useful organic compounds with high efficiency. Organic chemists have tended to focus on the efficiency of reactions and competence of synthetic strategies. It is important to recognize, however, that total efficiency of synthesis is also limited by the ability to separate and isolate products in a pure form. Although substantial efforts have been made to develop new efficient reactions, it is highly necessary to develop strategic separation protocols that are generally applicable for various structural types of compounds. The purpose of this research is developing a new combination of strategic separation protocol and reactions to enhance the ability of organic synthesis.We focused on acid-base extraction and found that 2-pyridyldimethylsilyl group serves as an effective phase tag for this purpose. The introduction of the tag to organic molecules can be easily accomplished by hydrosilylation and the reaction with 2-pyridylsilylmethyllithium. Carbometallation (Mizoroki-Heck reaction) to alkenylpyrilylsilane and alkynylpyridylsilane can also be utilized for the synthesis of tagged compounds. The removal of the tag can be accomplished by Tamao oxidation and Hiyama cross-coupling reaction.With the tag in hand, we have developed diversity oriented synthesis of biologically active compounds such as tamoxifen type tetrasubstituted olefins. We also developed new methods for the construction of extended π-electron systems, which exhibit interesting photophysical properties such as photo luminescence. By using difunctional and trifunctional aryl halides in Mizoroki-Heck reactions and cross-coupling reactions, unique polymers and dendrimers of extended π-electron systems were synthesized.