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Synthesis of P-Stereogenic Bisphosphine Ligands: Application as Hemi-labile Ligands in the Asymmetric Pauson-Khand Reaction

Haji-Cheteh, Chehasnah (2010) Synthesis of P-Stereogenic Bisphosphine Ligands: Application as Hemi-labile Ligands in the Asymmetric Pauson-Khand Reaction. MSc by research thesis, University of York.

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Abstract

The synthesis of new P-stereogenic ligands and investigation of their use in a Co-catalysed asymmetric Pauson-Khand reaction has been carried out. The ligands were synthesised by asymmetric lithiation of a phosphine sulfide or a phosphine borane using alkyllithium/()-sparteine complexes, trapping with Ph2PCl or t-Bu2PCl and treatment with BH3•Me2S or sulfur. This gave P-stereogenic bisphosphines. To afford highly enantioenriched ligands, the bisphosphines were recrystallised to increase the enantiomeric ratio up to 99:1 er. After borane deprotection of the bisphosphines using DABCO, hemi-labile ligands A and B were obtained. These hemi-labile ligands contain a phosphorus lone pair as a strong coordinating group and a sulfur lone pair on the P=S group as a weak coordinating group. The sensitivity after deboronation to oxidation to the phosphine oxide was studied through 1H and 31P NMR spectra. To evaluate the new hemi-labile ligands, they were used as a coordinating ligand with Co2(CO)8 in a catalytic asymmetric intramolecular Pauson-Khand reaction of a 1,6-enyne to a cyclopentenone. The synthesis of new P-stereogenic ligands and investigation of their use in a Co-catalysed asymmetric Pauson-Khand reaction has been carried out. The ligands were synthesised by asymmetric lithiation of a phosphine sulfide or a phosphine borane using alkyllithium/()-sparteine complexes, trapping with Ph2PCl or t-Bu2PCl and treatment with BH3•Me2S or sulfur. This gave P-stereogenic bisphosphines. To afford highly enantioenriched ligands, the bisphosphines were recrystallised to increase the enantiomeric ratio up to 99:1 er. After borane deprotection of the bisphosphines using DABCO, hemi-labile ligands A and B were obtained. These hemi-labile ligands contain a phosphorus lone pair as a strong coordinating group and a sulfur lone pair on the P=S group as a weak coordinating group. The sensitivity after deboronation to oxidation to the phosphine oxide was studied through 1H and 31P NMR spectra. To evaluate the new hemi-labile ligands, they were used as a coordinating ligand with Co2(CO)8 in a catalytic asymmetric intramolecular Pauson-Khand reaction of a 1,6-enyne to a cyclopentenone.

Item Type: Thesis (MSc by research)
Keywords: asymmetric synthesis, P-stereogenic compounds
Academic Units: The University of York > Chemistry (York)
Depositing User: Miss Chehasnah Haji-Cheteh
Date Deposited: 23 Mar 2011 10:44
Last Modified: 08 Aug 2013 08:45
URI: http://etheses.whiterose.ac.uk/id/eprint/1218

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