The influence of solvent and steric hindrance on the conversion of thiolsulfinates to trisulfides with hexamethyldisilathiane was investigated and a new polar mechanism, based on acceleration of the reaction by polar solvents and by fluoride ions, was proposed. The mono and dialkylation of 2,2-disubstituted 1,3-dithiane-1-oxides was investigated. Whereas those derived from menthone form only one diastereomer which cannot be alkylated further, those derived from acetone form two diastereomers. Only one of them can be alkylated further. Dehydration of the diastereomeric tertiary alcohols derived from directed aldol-reaction of γ-butyrolactones and methyl ketones yields diastereomeric conjugated enes in high yield and d.e. Michael-addition of benzyl thiols to these gives good yields and d.e. of the Michael-adducts. Deprotection of PMB-protected thiols with concomitant formation of disulfides was achieved by bromine in methanol or CH2Cl2. A seven-membered cyclic disulfide which contains the carbon backbone of the Perophora viridis trisulfide, albeit with two stereocentres in the incorrect configuration, was prepared.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:542587 |
| Date | January 2010 |
| Creators | Fuchs, Christian |
| Publisher | Loughborough University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | https://dspace.lboro.ac.uk/2134/8577 |
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