Subscribe to RSS
DOI: 10.1055/s-0029-1218499
Enantioselective Sulfonylation of Polyols
K. W. Fiori, A. L. A. Puchlopek, S. J. Miller*
Yale University, New Haven, USA
Publication History
Publication Date:
21 December 2009 (online)
Significance
The authors report a π-methyl histidine based tetrameric peptide catalyzed desymmetrization of polyols through enantioselective mono-sulfonylation. Two methods using different bases (NaHCO3 or 2,6-lutidine) were employed for the sulfonylation; in the presence of 5 mol% of tetrapeptide 1, various triols and diols can be selectively mono-sulfonated in good yield with high enantioselectivity. The structure of arene-sulfonyl chlorides affects the stereochemical outcome dramatically, in which para-nitrobenzenesulfonyl chloride (p-NsCl) gave an enantiomeric ratio of 97:3, but ortho-nitro- or para-methoxybenzenesulfonyl chloride only afforded er = 66:34 and 77.5:22.5, respectively. The chirality of the proline residue determines the absolute sense of asymmetric induction.