Routes to highly substituted thiophenol derivatives

Syntheses of highly substituted thiophenol derivatives that incorporate steric bulk into the ligand framework via ortho and para tert-butyl substituents are reported. S-Benzyl and trityl protection were investigated and the effects of substituents on the Newman–Kwart rearrangement of the thiocarbamate discussed. Single crystal X-ray structures are reported for three compounds and demonstrate the role of hydrogen bonding in stabilising the thiophenol to oxidation.