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Title: Exploring and exploiting selectivity in rhodium-catalysed hydroacylation reactions
Author: Poingdestre, Sarah-Jane
ISNI:       0000 0004 2745 8302
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2012
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Chapter 1 is an overview of the key developments in rhodium-catalysed hydroacylation. The main focus of this chapter is the use of various chelation strategies for the stabilisation of key rhodium-acyl intermediates. In addition, the more recent emergence of regioselective hydroacylation processes has been highlighted. Chapter 2 discloses the branched-selective intermolecular hydroacylation of 1,3-dienes and S-chelating aldehydes to afford synthetically useful 1,5-dione products. The evaluation of a number of different phosphine ligands for this process identifies a correlation between ligand bite angle and reaction regioselectivity. Chapter 3 discusses the development of a linear-selective hydroacylation process for previously challenging alkyne substrates. This, in combination with a complementary branched-selective process, provides a ligand-controlled regioselectivity switch between the branched and linear pathways. Finally, Chapter 4 details efforts towards the development of multicomponent, tandem processes through exploitation of our synthetically useful branched hydroacylation adducts.
Supervisor: Willis, Michael Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Physical Sciences ; Chemistry & allied sciences ; Organic chemistry ; Organic synthesis ; Synthetic organic chemistry ; rhodium ; selectivity ; regioselectivity ; hydroacylation ; catalysis