通过硫自由基催化作用介导对映选择性环加成反应的二硫键桥联肽。
Disulfide-Bridged Peptides That Mediate Enantioselective Cycloadditions through Thiyl Radical Catalysis.
机构信息
Department of Chemistry , Yale University , 225 Prospect Street , New Haven , Connecticut 06520 , United States.
出版信息
Org Lett. 2018 Mar 16;20(6):1621-1625. doi: 10.1021/acs.orglett.8b00364. Epub 2018 Mar 5.
Abstract
An enantioselective vinylcyclopropane ring-opening/cycloaddition cascade is described. The active thiyl radical catalysts are generated in situ via UV light-promoted homolysis of cystine-based dimers. Amide-functionalization of the peptide at the 4-proline position is essential for effective asymmetric induction. Stereochemical communication is dependent on steric interactions with this substituent that are enforced by H-bonding to the peptide backbone.
摘要
本文描述了一种对映选择性的乙烯基环丙烷开环/环加成级联反应。通过胱氨酸二聚体的紫外光促进均裂原位生成活性硫自由基催化剂。在 4-脯氨酸位置对肽进行酰胺官能化对于有效不对称诱导是必不可少的。立体化学通讯取决于与该取代基的立体相互作用，这种相互作用通过与肽主链的氢键而得到加强。
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