Iridium-Catalyzed, Intramolecular Cyclization of Allylic Alcohols for Quaternary Center Synthesis

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Melissa Ramirez is awarded a FY21 Mathematical and Physical Sciences Ascending Postdoctoral Research (NSF MPS-Ascend) Fellowship to conduct a program of research and activities related to broadening participation by groups underrepresented in Chemistry at Cal Tech. The project being performed by Melissa Ramirez, entitled Iridium-Catalyzed, Intramolecular Cyclization of Allylic Alcohols for Quaternary Center Synthesis, is to be conducted under the guidance of mentoring scientist Brian M. Stoltz. This project is supported by the Office of Multidisciplinary Activities and the Chemistry Division in the Mathematical and Physical Sciences.This project supports the development of an iridium-catalyzed, iodine-mediated intramolecular cyclization of allylic alcohols, which would serve as enolate synthons to generate quaternary center-containing cyclohexenone and cycloheptenone building blocks. Computational analysis of the reaction mechanism and the key enantiodetermining step will guide the design of a chiral iridium catalyst for the development of an enantioselective variant of the reaction, which will be tested and developed experimentally. This work will establish guiding principles for the future design of novel ligands, enabling efficiency in high throughput experimental screening and providing a solution to the long-standing challenge of vicinal stereocenter formation via umpolung functionalization of allylic alcohols using iridium catalysis and hypervalent iodine chemistry. Dr. Ramirez will continue efforts in broadening participation through mentoring and by participating the Alliances for Graduate Education and the Professorate program at Caltech.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.