13831-00-0Relevant academic research and scientific papers
Chemoselective protection of thiols versus alcohols and phenols. The Tosvinyl group
Arjona, Odón,Medel, Rocío,Rojas, Jenny,Costa, Anna M.,Vilarrasa, Jaume
, p. 6369 - 6373 (2007/10/03)
The conjugate addition of aliphatic and aromatic thiols to ethynyl p-tolyl sulphone (tosylacetylene) has been managed to afford Tosvinyl derivatives chemoselectively (in the presence of oxygen nucleophiles) and stereoselectively (isomers Z) in practically quantitative yields. The conditions of choice are: catalytic amounts of Et3N (only 0.5-1.0 mol%), a reaction temperature around 0°C and, for the less acidic thiols, CF3CH2OH or CH3CN/CF3CH2OH as the solvent. Thus, N-Boc-Cys-OMe has been quantitatively protected as its S-Tosvinyl derivative in the presence of N-Boc-Ser-OMe and N-Boc-Tyr-OMe. This novel protecting group is stable to several basic and acidic conditions; its removal is achieved at rt by treatment with an excess of pyrrolidine or at 0°C with alkanethiolate ions.
