Physical Sciences and Mathematics Commons^™

Photochemical Generation And Chemistry Of Α-Acetoxycarbene, Jonathan Mann

Honors Theses

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[1] 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. …