New Vistas in Porphyrinoid Chemistry: Corrolazine Synthesis and Reactivity

化学部化学合成（SYN）计划的这一奖项支持约翰霍普金斯大学化学系的大卫戈德堡教授的工作，以开发一类被称为corrolazines和corrolles的卟啉化合物的合成和反应性。这些分子被设计用于稳定高价过渡金属，包括高价金属-氧代物质。拟采用的卟啉配体将提供对这些物种的访问，允许在生物学相关和合成重要的过程中直接评估它们的反应性，例如氢原子转移和C-H键裂解。预期的研究结果应该产生新的机制信息的相关血红素和非血红素酶，并可能提供洞察为什么自然选择铁或锰的特定功能。获得的结构/功能相关性也应该有助于合成卟啉类氧化催化剂的设计和开发，本提案中描述的研究将为一系列金属酶和合成金属基催化剂的关键中间体提供新的知识。所获得的知识将促进我们对生物学催化过程的理解，并可能转化为新的，环境相容的，生物启发的催化剂，可用于工业重要性的氧化转化的发展。本科生和研究生将接受化学合成和机理方面的培训，以及更广泛的实验科学方法。该研究计划还包括与美国和国际机构的科学家积极合作。这些互动将为参与研究的学生提供更多的培训机会。计划在高中和大学一级开展外联方案，以扩大代表性不足的群体对自然科学的参与。

This award in the Chemical Synthesis (SYN) program of the Chemistry Division supports work by Professor David Goldberg of the Department of Chemistry of Johns Hopkins University to develop the synthesis and reactivity of a class of porphyrinoid compounds known as corrolazines and corroles. These molecules are designed to stabilize high-valent transition metals, including high-valent metal-oxo species. The porphyrinoid ligands to be employed will provide access to these species, allowing for their reactivity to be assessed directly in biologically relevant and synthetically important processes such as hydrogen-atom transfer and C-H bond cleavage. The anticipated findings should yield new mechanistic information of relevance to both heme and nonheme enzymes, and may provide insights into why Nature selects iron or manganese for a particular function. The structure/function correlations to be obtained should also aid in the design and development of synthetic porphyrinoid-based oxidation catalysts.The research described in this proposal will provide new knowledge regarding key intermediates proposed for a range of metalloenzymes and synthetic metal-based catalysts. The knowledge obtained will advance our understanding of catalytic processes in biology, and may translate into the development of new, environmentally compatible, bio-inspired catalysts that can be used in oxidative transformations of industrial importance. Undergraduate and graduate students will receive training in chemical synthesis and mechanism, and more broadly in the methods of experimental science. The research program also includes active collaborations with scientists at several U.S. and international institutions. These interactions will provide expanded training opportunities for students participating in the research. Outreach programs aimed at broadening the participation of underrepresented groups in the physical sciences are planned at the high school and university level.