Vitamin B12 has been of interest to researchers for many years, with no real progression or in depth analysis being made in the area of synthetically useful catalysis. The main concept for vitamin B12 catalysis originates from its role as a coenzyme in mammalian cells. Methylcobalamin and adenosylcobalamin, are involved in numerous catalytic reactions including isomerization, methylation and dehalogenation. This type of catalysis has been successfully translated into the laboratory and used in a small collection of reactions. Whereas most often reactions require the addition of toxic metals plus complex ligands into a cocktail of reagents, vitamin B12 in itself is a package deal. There are also drawbacks when employing cobalamin, these include solubility and the inability to fine-tune the catalyst properties via modifications. We envisage that cobyrinic acid derivatives may solve these problems. These derivatives still bear the advantages of vitamin B12, however their ability to be modified and manipulated into more useful catalysts trumps cobalamin. Furthermore, their capability of radical formation, a very powerful tool in organic chemistry, has also been well documented.

Therefore, the aim of this project is to examine the use of cobyrinic acid derivatives as catalysts for intermolecular radical addition of alkane bromides to olefins, an atypical reaction for this catalyst and will therefore bring knowledge to a lacking area of chemistry. In order to achieve this goal all aspects of the chosen model reaction will be examined closely, leaving no question unanswered. The information gained will enhance the repertoire of this exciting new tool in synthetic organic chemistry.

The project will examine cobyrinic acid derivatives in radical intermolecular addition to α,β- unsaturated compounds. (CN)(H2O)Cby(OMe)7 will be studied as the catalyst for a model reaction of benzyl bromide and n-butyl acrylate with a reducing agent, base and solvent. All aspects of the reaction will be optimized including: catalyst reduction, order of reagents’ addition, reaction temperature, halide type, base, solvent, catalyst type, influence of light and catalytic loading. This will give the desired product in high yields, in the shortest time, with the lowest catalytic loading and equimolar amount of substrates. Following a full breakdown of the model reaction the scope and limitations of the method will be learnt by examining activated and non-activated olefins as well as various organic halides and malonate substrates. The established methodology will be then utilized in known vitamin B12 catalyzed reactions in order to further confirm our superior catalysts. Furthermore, reported reactions involving cobalt and other metal catalysts will also be tested and compared.

The totality of the proposed work will allow for a full overview of cobyrinic acid catalysis. This will not only expand the wondrous world of vitamin B12 but also it will greatly contribute to metal catalysis. It will also demonstrate the potential of cobyrinic acid in radical promotion and their us in organic synthesis. The developed methods will eliminate the need for toxic metal catalysts, elaborate synthetic ligands, harsh reaction conditions and complex reaction mixtures. Utilizing cobyrinic acid will simplify complicated reactions and bring multicomponent reactions back to their simplest form, resulting in a general and easy procedure that can be enjoyed by all eager scientists.