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Palladium catalysed asymmetric hydroxy- and alkoxycarbonylation of alkenes

Date
24/06/2015
Author
Durrani, Jamie T.
Supervisor
Clarke, Matt
Funder
Dr. Reddy's Chirotech Technology Ltd.
Engineering and Physical Sciences Research Council (EPSRC)
Keywords
Hydroxycarbonylation
Alkoxycarbonylation
Carbonylation
Asymmetric catalysis
Homogeneous catalysis
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Abstract
Palladium catalysed asymmetric hydroxy- and alkoxycarbonylation reactions of alkenes have the potential to deliver valuable chiral carboxylic acid and ester building blocks from cheap feedstocks: alkenes, carbon monoxide and water (alcohols in the case of alkoxycarbonylation). Despite the attractive nature of these reactions, extensive research has so far been unable to produce effective catalysts which are capable of controlling both regio- and enantioselectivity. Building on exciting recent results involving the use of highly enantioselective palladium catalysts derived from Phanephos-type ligands, this research focuses on paracyclophane-diphosphines and their use in asymmetric hydroxy- and alkoxycarbonylation reactions. An investigation into reaction conditions analysed several factors, including solvents, CO-pressure, acidic additives and halide sources, to provide optimal activity and selectivities. Two novel electron-poor paracyclophane-diphosphines and their mono- and di-palladium complexes were synthesised and shown to provide exceptional levels of regioselectivity while maintaining high levels of asymmetric induction. These are the first such examples of hydroxy- or alkoxycarbonylation catalysts to facilitate simultaneous control over both regio- and enantioselectivity. The most effective catalyst was used to promote the reactions of a selection of aryl alkenes and was shown to be tolerant of several different functional groups. A selection of non-symmetric paracyclophane-diphosphine ligands and their palladium complexes were also synthesised and assessed for their performance in hydroxy- and alkoxycarbonylation. We also report the use of Phanephos-type ligands to promote the highly enantioselective hydroxycarbonylation of N-(p-toluenesulfonyl)-3-pyrroline to deliver a chiral proline derivative in high ee.
Type
Thesis, PhD Doctor of Philosophy
Rights
Embargo Date: 2021-02-04
Embargo Reason: Thesis restricted in accordance with University regulations. Print and electronic copy restricted until 4th February 2021
Collections
  • Chemistry Theses
URI
http://hdl.handle.net/10023/6276

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