Enantioselective sulfonylation reactions mediated by a tetrapeptide catalyst.
While Nature excels at performing selective modifications of complex polyfunctional molecules through the use of tailoring enzymes, synthetic chemistry has lagged behind in this regard. In prior work, we have applied a biomimetic approach to this problem, developing small peptides to achieve various group transfer reactions on polyol substrates with high enantio- or regioselectivity. The utility of sulfonates as synthetic building blocks and the scarcity of direct, selective methods for their preparation prompted our investigation into this area. In this article we report the development of a pi-methyl histidine-based tetrameric peptide that effects the desymmetrization of meso-1,3-diols through enantioselective (mono)sulfonylation. The catalyst exhibits structural similarities to another catalyst found to be effective in orthogonal group transfers, but results in modification of the enantiotopic alcohol. The practical and mechanistic implications of this discovery may extend beyond synthetic considerations and provide analogies to the diverse roles of histidine in enzyme active sites.
Fiori
Kristin Williams
KW
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107, USA.
Puchlopek
Angela L A
AL
Miller
Scott J
SJ
D000438:Alcohols / Q000737:chemistry; D002384:Catalysis; D006639:Histidine / Q000737:chemistry; D009842:Oligopeptides / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity; D013451:Sulfonic Acids / Q000737:chemistry*
D000438:Alcohols; D009842:Oligopeptides; D013451:Sulfonic Acids; D010758:Phosphorus; D006639:Histidine