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Title: Applications of known and novel primary phosphines and their corresponding phosphacycle derivatives
Author: Sibbald, Connor
ISNI:       0000 0004 5367 0964
Awarding Body: University of Newcastle Upon Tyne
Current Institution: University of Newcastle upon Tyne
Date of Award: 2014
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The fearsome reputation of primary phosphines, with many considered toxic, pyrophoric and sometimes even explosive, has meant that these versatile compounds are often underused in synthetic chemistry. There is however a limitied number of air-stable examples in the literature, whose air-stability has either been accounted for by steric factors or for reasons that could not be explained. Recently (S)-1a and (R)-1b have been prepared and they are considered to be air-stable due to electronic effects of the 1,1’- binaphthyl backbone. In Chapter 2 of this work we report the synthesis of the valuable precursors (S)-1a and (R)-1b in improved yields and in multigram quantities using palladium-catalysed crosscouplings producing a reliable and convenient method for the synthesis of these 1,1’- binapthyl based primary phosphines. The functionalization of the primary phosphine precursors (S)-1a and (R)-1b has been explored, examining the novel phosphetane analogues in Chapter 3 and phospholane analogues in Chapter 4. The σ-donor and π-acceptor properties of these ligands have been investigated through their coordination to selenium, platinum and rhodium. The dynamic behaviour of the ligands at palladium and platinum has been examined by NMR spectroscopy and X-ray analysis. An investigation into the performance of the ligands in asymmetric catalysis, including palladium-catalysed cross-couplings and rhodium-catalysed hydroformylations, has also been conducted An examination into the range of aryl carbon-phosphorus bond forming techniques has also been carried out in the pursuit of novel ortho-substitued diprimary phosphines from arylbromides in Chapter 5. These user-freindly diprimary phosphines have then been successfully functionalised into ortho-substituted bisphospholane ligands and tested a rhodium-catalysed hydrogenation reaction, matching the performance of DuPhos.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available