Date of Award

Spring 1994

Degree Type

Thesis - Restricted

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Donaldson, William A.

Abstract

Nucleophilic attack on coordinated polyenes is a well known organotransition metal chemistry reaction. However, while some coordinated polyenes have been studied extensively, others, due to a relative apparent lack of synthetic usefulness, have not. One such neglected complex is trimethylenemethane iron tricarbonyl. For synthetic organometallic methodology to be useful, it is necessary that the metal moiety can be easily complexed to the'desired organic ligand and, after further reaction of the orgnometallic complex, easily decomplexed, yielding the desired organic product. Generally, metal 'complexation is not a problem but decomplexation proves to be more difficult. In the case of diene-Fe(CO)3 complexes, the metal moiety can be relatively easily decomplexed via oxidative elimination using mild oxidative conditions, reductive photochemical decomplexation, or nucleophilic attack on the comples followed by reductive elimination. Decomplexation of TMMFe( CO)3, on the other hand, has, until recently, lacked such a facile method. It has been suggested that (TMM) Fe (CO)3 complexes are electron poor, leading to the speculation that they should be susceptible to nucleophilic attack. Research based on this assumption has reported that indeed the TMM ligand can be liberated via nucleophilic attack on its iron complex followed by electrophilic work up, yielding olefins. A study to expand the range of nucleophiles possible for nucleophilic attack and electrophiles possible for electrophilic work up has been undertaken. A novel route to the formation of two carbon carbon bonds in one pot has been developed. Initial studies have also been reported on substituted (TMM) Fe (CO)3 complexes and an investigation into nucleophilic attack on the allyl substituted (TMM)Fe(CO) 3 complex has been conducted. The reactivity of the cross-conjugated pentadienyl cation with nucleophiles is reported. Formation of a ketone complex via this route has been achieved for the first time. Initial steps toward the formal synthesis of sulcatol via the crossconjugated pentadienyl cation are described.

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