Michael S. Holden

The Pechmann reaction

A solid acid-catalyzed version of the Pechmann reaction for the synthesis of coumarins is described. The Pechmann reaction is a multiple-transformation process which is not a part of the normal organic chemistry curriculum. However, each transformation (hydroxyalkylation, transesterification, dehydration) is one that can be understood by students, and by applying the known mechanisms in sequence, the correct product can be predicted.

In situ generation of (C5H5)Fe(C6H5O)

Abstract The iron complex 1 / 1′ was formed cleanly upon treatment of CpFe(2-trimethylsilylethoxybenzene) hexafluorophosphate with tetrabutyl ammonium fluoride. Reaction with a number of electrophiles led to good yields of the O -substituted arenes.

An iron-mediated approach to o-aryloxyanisoles

The monomethoxylation of (1,2-dichlorobenzene)cyclopentadienyliron hexafluorophosphate, followed by phenoxylation utilizing a variety of variously substituted phenols, is shown to be an effective method for the synthesis of o-aryloxyanisole complexes.

Iron-Mediated Synthesis of t-Butyl-N-(Arlyoxy)Carbamates

Abstract The anion of t-butyl-N-hydroxycarbamate displaces halogens from (η6-haloarene)(η5-cyclopentadienyliron) salts. The resulting complexes are demetallated by photolysis in sunlight to generate t-butyl-N-(aryloxy)carbamates.

Al2O3-mediated deacetylation of CpFe(ethyl-2-phenylacetoacetate) hexafluorophosphate

Abstract Passage of the title compound through a short column of Al 2 O 3 induces deacetylation to form CpFe(ethyl-2-phenylacetate) hexafluorophosphate. This compound is shown to react with base to generate the stabilized enolate, which is dideuteriated or dimethylated upon quenching with excess D 2 O or CH 3 I.