Photochemical generation and chemistry of α-Acetoxycarbene

Author (Your Name)

Jonathan Mann, Colby College

Date of Award

2002

Document Type

Honors Thesis (Open Access)

Department

Colby College. Chemistry Dept.

Advisor(s)

Dasan M. Thamattoor

Second Advisor

Thomas W. Shattuck

Abstract

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. Energy minimizations at the B3LYP/6-31G* level of theory located a singlet minimum that is significantly lower in energy than the corresponding triplet.

Keywords

Carbenes (Methylene compounds), Photochemistry, ?-Acetoxycarbene

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