SusChEM: CAREER: The Application of Visible Light Photocatalysis to Amine Synthesis

化学合成项目获得了CAREER奖，以支持阿肯色大学郑南教授的研究。氮自由基是合成上有用但未充分利用的亲电性氮源。该项目的目标是利用可见光光氧化还原条件下产生的氮自由基阳离子发展化学。有三个具体目标。首先，将环丙胺与炔、炔和二炔进行[3+2]环化，以获得1-氨基-2-环戊烯衍生物。用手性Ru络合物研究了环丙胺与炔[3+2]环的不对称变体。其次，使用反应性低得多的环丁苯胺，与炔、炔和二炔形成类似的[4+2]环，以合成1-氨基-2-环己烯衍生物。采用[4+2]环化法完成（±）hayayne的外消旋合成。在最后的目标中，将开发一种基于光催化级联反应的一般合成策略，以获得生物碱的阿库米胺族。由可见光驱动的有机反应是可持续化学的理想选择，因为它们利用充足的阳光，操作简单，并且通常具有高原子经济性。这个项目中的化学物质体现了可持续化学的原则。这些反应的产物是医药和材料工业中非常有用的合成中间体。此外，郑教授还将启动三个将研究与教学相结合的教育项目。这些项目的目标是改善学生在有机化学课程中的学习体验，并使他们接触到更有趣和更相关的药物设计和可持续化学等研究。第一个项目是开发3-D（三维）内容，以改善有机化学的教学方式。一些3D内容包括使用阿肯色大学化学与生物化学系蛋白质结构中心的计算/可视化设施来教授药物设计的一些基本概念，以及使用3D可视化系统来帮助学生更好地“了解”立体化学。第二项教育计画是在本研究的基础上，为高等本科有机实验室和有机化学II实验室设计新的实验。最后一个教学项目的重点是在有机化学II讲座中介绍可持续化学。

With this CAREER Award, the Chemistry Synthesis program is supporting the research of Professor Nan Zheng of the University of Arkansas. Nitrogen radical cations are synthetically useful yet underutilized electrophilic nitrogen sources. The goal of this project is to develop chemistry utilizing nitrogen radical cations generated under visible light photoredox conditions. There are three specific objectives. First, [3+2] annulation of cyclopropylanilines with alkynes, enynes, and diynes will be developed to provide 1-amino-2-cyclopentene derivatives. An asymmetric variant of the [3+2] annulation of cyclopropylanilines with alkynes will be investigated using a chiral Ru complex. Second, using much less reactive cyclobutylanilines, an analogous [4+2] annulation with alkynes, enynes, and diynes will be developed to synthesize 1-amino-2-cyclohexene derivatives. The [4+2] annulation method will be employed to complete a racemic synthesis of (±) hayayne. In the final objective, a general synthetic strategy based on a photocatalyzed cascade reaction will be developed for access to the akuammiline family of alkaloids.Organic reactions driven by visible light are ideal for sustainable chemistry, as they use abundant sunlight, are operationally simple, and often have high atom economy. The chemistries in this project embody the principles of sustainable chemistry. The products of the reactions are highly useful synthetic intermediates for the pharmaceutical and materials industries. In addition, Professor Zheng will initiate three educational projects that interweave his research with teaching. The goals of these projects are to improve the learning experience of the students in organic chemistry courses and expose them to researches such as drug design and sustainable chemistry that are more interesting and relevant to them. The first project is to develop 3-D (three-dimensional) contents to improve how organic chemistry is taught. Some of the 3-D contents include using the Computation/Visualization Facility in the Center for Protein Structure in the Department of Chemistry and Biochemistry at the University of Arkansas to teach some basic concepts of drug design as well as using a 3D visualization system to help the students "see" stereochemistry better. The second educational project involves designing new experiments for advanced undergraduate organic labs and organic chemistry II labs based on the proposed research. The last educational project focuses on introducing sustainable chemistry to organic chemistry II lectures.