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Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation
Published on: August 1, 2018
Enantioselective sulfonylation reactions mediated by a tetrapeptide catalyst
Kristin Williams Fiori1, Angela L A Puchlopek, Scott J Miller
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, CT 06520-8107, USA.
Nature Chemistry
|February 18, 2010
Summary
Researchers developed a novel peptide catalyst for selective modification of molecules. This biomimetic approach enables enantioselective sulfonylation of diols, advancing synthetic chemistry.
Area of Science:
- Synthetic Chemistry
- Biomimetic Chemistry
- Catalysis
Background:
- Nature utilizes tailoring enzymes for selective molecular modifications, a capability synthetic chemistry aims to replicate.
- Sulfonates are valuable synthetic building blocks, yet selective preparation methods are scarce.
- Previous work established biomimetic peptides for enantioselective group transfers on polyols.
Purpose of the Study:
- To develop a selective method for preparing sulfonates.
- To design a peptide catalyst for the desymmetrization of meso-1,3-diols.
- To explore biomimetic approaches for enantioselective functionalization.
Main Methods:
- Development of a tetrameric peptide catalyst based on pi-methyl histidine.
- Application of the catalyst for enantioselective (mono)sulfonylation of meso-1,3-diols.
- Structural and functional comparison with related catalysts.
Main Results:
- The peptide catalyst successfully achieved enantioselective desymmetrization of meso-1,3-diols.
- The catalyst selectively modified one enantiotopic alcohol in the diol substrate.
- Structural similarities were observed with catalysts used in orthogonal group transfers.
Conclusions:
- A novel pi-methyl histidine-based peptide catalyst enables enantioselective (mono)sulfonylation of meso-1,3-diols.
- This biomimetic catalyst offers a selective synthetic route to functionalized diols.
- The findings provide insights into histidine's role in enzyme active sites and synthetic catalysis.
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