Transition metal-catalysed enol formation from allylic alcohols : Isomerisation, C−C and C−F bond formations


This thesis describes the isomerisation of allylic alcohols into enols and enolates catalysed by transition metal complexes. The transformation has been used to prepare both unsubstituted and α-substituted carbonyl compounds. Significant attention has been given to the mechanistic aspects of the reactions.

In the first part of this thesis, an environmentally benign procedure for the redox isomerisation of allylic alcohols into ketones is described. The reaction takes place in water and at room temperature using a cationic rhodium complex in combination with water-soluble phosphines. A variety of allylic alcohols could be isomerised in high yields using this procedure.

The second part describes the combination of an allylic alcohol isomerisation with a C−C bond formation, catalysed by a rhodium complex. In this way, allylic alcohols were coupled with aldehydes and N-tosyl imines forming aldol and Mannich-type products. In addition, homoallylic and bishomoallylic alcohols were for the first time isomerised into the corresponding enolates and coupled using this methodology.

In the third part of this thesis, the isomerisation of allylic alcohols was coupled with a C−F bond formation using an iridium complex and electrophilic fluorinating reagents. This novel transformation was used to convert allylic alcohols into single regioisomers of α-fluoroketones. The reaction is tolerant to air and water and takes place at room temperature.

All of the reactions described take place under mild conditions, are operationally simple, and utilise catalysts formed in situ from commercially available metal complexes and ligands.

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