Achieving Challenging Synthesis Based on Triazole-Gold Catalysis

在化学系化学合成（SYN）项目的支持下，南佛罗里达大学的石晓东将开发新的方法来制造氮杂核糖，并使用具有独特结构特征的金催化剂（称为三唑）在大环结构中连接炔。氮杂硼是类苯分子，两个相邻的碳原子被一个氮原子和一个硼原子取代。这种结构变化赋予了这些分子重要的生物学特性，但也使它们的制备具有挑战性。大环炔也难以构建，但具有宝贵的生物偶联和仿生应用。Shi博士和他的团队正在研究开发的金催化剂，以促进新方法轻松获取更多种类的这些重要但具有挑战性的化合物。金催化剂的三唑部分将用于调节反应性。这些研究将为本科生和研究生提供最先进的化学合成方面的重要培训，并支持为STEM研究的下一代科学家做准备。此外，施博士正在南佛罗里达大学为坦帕地区的学生组织一年一度的以学生为导向的研究会议，以促进STEM教育，进一步加强佛罗里达州的教育使命。金催化剂在各种环异构化过程中具有良好的合成用途，但新的配体支架有可能在新的方向上扩大这些应用。石晓东和他在南佛罗里达大学的研究小组已经确定，三唑配体赋予金催化剂的关键性质，有助于促进新的反应。在本项目中，优化了三唑金催化剂用于合成氮杂硼的炔基氨基硼烷的硼氢化反应，并将研究用于合成大环炔的催化剂。还将进行机制研究，以了解三唑基序在支持这些转变中的作用。补充合成研究也在进行中，以将最初的催化产物转化为增值的合成目标。这些活动支持培养多样化的研究生和本科生群体，并提供所需的合成替代品，以支持这些有趣的目标化合物的实际、大规模合成，以进一步探索药物化学研究和材料科学。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Synthesis (SYN) Program in the Division of Chemistry, Xiaodong Shi of the University of South Florida will develop new ways to make azaborines and to link alkynes in large ring structures using gold catalysts with a unique structural characteristic called a triazole. Azaborines are benzene-like molecules where two adjacent carbon atoms have been replaced a nitrogen and a boron atom. This structural change gives these molecules important biological properties but makes them challenging to prepare. Large ring alkynes are also difficult to construct but have valuable bioconjugate and biomimetic applications. The gold catalysts being developed by Dr. Shi and his team are being studied to facilitate new ways to easily access a larger variety of these important but challenging compounds. The triazole portion of the gold catalyst will be used to tune this reactivity. These studies will provide undergraduate and graduate students important training in state-of-art chemical synthesis and supporting the preparation of next generation scientist in STEM research. In addition, Dr. Shi is organizing an annual student-oriented research meeting at the University of South Florida for students in the Tampa area to bolster STEM education and further enhance the educational mission of the state of Florida.Gold catalysts have well-established synthetic utility in a variety of cycloisomerization processes, but new ligand scaffolds have the potential to broaden these applications in new directions. Xiaodong Shi and his research group at U. South Florida have determined that triazole ligands impart key properties on gold catalysts that help facilitate novel reactions. In the current project, triazole gold catalysts are being optimized for the hydroboration of alkynyl amino boranes for the synthesis of azaborines and will be investigated for the synthesis of macrocyclic alkynes. Mechanistic studies will also be pursued to understand the role of the triazole motif in supporting these transformations. Complementary synthetic studies are also ongoing to convert the initial catalytic products to value-added synthetic targets. These activities are supporting the training of a diverse group of graduate and undergraduate students and providing needed synthetic alternatives to support practical, large scale synthesis of these interesting target compounds for their further exploration in medicinal chemistry research and in materials science.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.