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Title: Stereocontrolled synthesis of 1,5-stereogenic centres through three-carbon homologation of boronic esters
Author: Unsworth, Phillip J.
ISNI:       0000 0004 5916 5694
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2015
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A three carbon homologation of pinacol boronic esters has been developed. The procedure consists of a one pot Matteson homologation/alkylation followed by a palladium catalysed rearrangement from the branched to the linear allylic boronic ester. The procedure allows for the synthesis of a broad range of disubstituted and trisubstituted allylic boronic esters with high E selectivity. Combining this methodology with lithiation-borylation allows for the synthesis of carbon chains bearing 1,5-stereogenic centres and its utility has been demonstrated in a formal synthesis of (+ )-jasplakinolide. The palladium catalysed reactivity of allylic boronic esters has been further explored by coupling with a range of different nucleophiles. Allylic boronic esters have been successfully coupled with carbon, oxygen and nitrogen based nucleophiles giving products with high E selectivity and high linear to branched ratios. Work has also been carried out towards developing a carbenoid which can be used for a reagent controlled homologation of a boronic ester introducing oxygen functionality. Various carbenoids have been prepared however none could be successfully applied to a reagent controlled homologation reaction
Supervisor: Aggarwal, Varinder K. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available