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Title: Partial asymmetric synthesis in the Reformatsky reaction
Author: Wise, Elizabeth John
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 1966
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Partial asymmetric synthesis during the Reformatsky reaction has been studied in order to ascertain what factors may be of importance in determining the degree of asymmetric synthesis, and which of the two enantiomeric B-hydroxy-acids is obtained in excess. [equation] Various carbonyl compounds were treated with (-)-menthyl bromoacetate, and with (+)- or (-)-bornyl bromoacetate; the products were completely hydrolysed to furnish the P-hydroxy-acids, which were examined polarimetrically In general, replacement of (-)-menthyl by (-)-bornyl led to an excess of the opposite enantiomer of the B-hydroxy-acid; however, with cyclohexyl phenyl ketone or with o-methylbenzophenone a predominance of the same enantiomer was obtained irrespective of which ester was used. Attempts were made to correlate the configuration of B-cyclohexyl-B-hydroxy-B-phenylpropionic acid and of B-hydroxy-B-phenyl-B(o-tolyl)---propionic acid with that of cyclohexyl-phenylcarbincl and of ethylphenylcarbinol respectively. (+)-B-Cyclohexyl-B-hydroxypropionic acid was shown to be the (R)-form, by correlation with (+)-B-hydroxy-B-phenylpropionic acid. It was confirmed that (+)-B-hydroxy-B-phenylbutyric acid was the (S)-form, by correlation with (-)-B-phenylbutyric acid. The results obtained have been discussed with particular reference to the stereochemistry and mechanism of the Reformatsky reaction. A hypothesis is proposed in which the configuration of the B-hydroxy-acid formed in excess is related to the stereochemistry of the dissymmetric group (R).
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available