New Vistas in Porphyrinoid Chemistry: Corrolazine Synthesis and Reactivity

Johns Hopkins University, Baltimore MD

Investigators

Abstract

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.