title: Thiolation of symmetrical and unsymmetrical diketopiperazines.
abstract: The introduction of sulfur units into a variety of symmetrical and unsymmetrical diketopiperazines (DKPs) is described. We investigated different thiolation methods utilizing several bases and electrophilic sulfur reagents, leading to monomethylthio-, bis(methylthio)-, and epithio-DKPs. Their formation proceeded diastereoselectively, facilitating the application in total syntheses of many thiodiketopiperazine (TDKP) natural products. Furthermore, possible side reactions as well as mechanistic studies and stereochemical structural assignments of the obtained products are given.
authors.affiliation: Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry, Fritz-Haber-Weg 6, D-76131, Karlsruhe, Germany.
authors.forename: Bettina M
authors.initials: BM
authors.lastname: Ruff
authors.forename: Sabilla
authors.initials: S
authors.lastname: Zhong
authors.forename: Martin
authors.initials: M
authors.lastname: Nieger
authors.forename: Stefan
authors.initials: S
authors.lastname: Bräse
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D054659:Diketopiperazines / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013455:Sulfur / Q000737:chemistry
chemical_list: D001688:Biological Products; D054659:Diketopiperazines; D013438:Sulfhydryl Compounds; D013455:Sulfur