Title: Anaerobic Heteroatom Transfer Reactions Promoted by Photoexcited 1,3-Dipoles
Abstract:
Heteroatom units, such as carbonyls, alcohols, and amines, are prevalent motifs in many medicinally important compounds. Methods to incorporate these important functional groups at the expense of hydrocarbons rely on the use of non-commercial heteroatom transfer agents, precious transition metals, and/or costly engineered enzymes. Also, these methods often require exogenous oxidants to promote the C–heteroatom bonding event, which greatly limits substrate scope. Our laboratory focuses on the employment of economical 1,3-dipoles as versatile reagents that can serve as the hydrocarbon activator and the heteroatom atom source for the heteroatom incorporation of aliphatic systems under benign visible-light irradiation. Our contributions involve the cleavage of alkenes leading to valuable carbonyl derivatives and the direct C–H oxidation of hydrocarbons via anaerobic oxygen-atom transfer from photoexcited nitroarenes. Using photoexcited azoxys, an anaerobic nitrogen atom transfer event can occur leading to the aziridination of alkenes. Mechanistic studies reveal that the 1,3-dipoles are the sole photo-absorbing species, which leads to the formation of diradical intermediates that are responsible for heteroatom transfer events.
Bio:
Marvin Parasram was born and raised in The Bronx, New York. He received his B.S. in Chemistry in 2010 from Stony Brook University. Later that year, he joined Prof. Vladimir Gevorgyan’s group at the University of Illinois at Chicago for his doctoral studies, where he was involved in developing novel Pd-catalyzed synthetic methodologies. In 2017, he joined Prof. Abigail G. Doyle’s Group at Princeton University as a National Institutes of Health Postdoctoral Scholar, where he worked on the development of Ni/Photoredox catalyzed methods. In Fall 2020, he began his independent career at New York University as an Assistant Professor of Chemistry.
Keywords: photochemistry, organic chemistry, diradicals