Date of Award
Honors Thesis (Open Access)
Colby College. Chemistry Dept.
Dasan M. Thamattoor
Thomas W. Shattuck
Efforts have been made at generating the parent α-acetoxycarbene from a non-nitrogenous precursor. Baeyer-Villiger oxidation of the ketone, 1-(1a,9b-dihydro-lHcyclopropa phenanthren-1-yl)-ethanone, available in two steps from phenanthrene, led to the ester, 1-(1 a,9b-dihydro-lH-cyclopropa[/]phenanthren-l-yl)-acetate, which is a photochemical precursor of the parent α-acetoxycarbene intermediate. Photolysis of the ester in cyclohexene afforded an isomeric mixture of endo and exo acetates resulting from the carbene adding to the α-bond. Photolysis of the ester in trans-3-hexene yielded a single trans-cis acetate, a product of the same cycloaddition process. The formation of methyl glyoxal, via the l,2-acyl shift of the carbene, is observed through its derivatives. Energy minimizations at the B3LYP/6-31G* level of theory located a singlet minimum that is significantly lower in energy than the corresponding triplet.
Carbenes (Methylene compounds), Photochemistry, ?-Acetoxycarbene
Recommended CitationMann, Jonathan, "Photochemical generation and chemistry of α-Acetoxycarbene" (2002). Honors Theses. Paper 154.
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