title: Synthesis of peptide thioesters via an N-S acyl shift reaction under mild acidic conditions on an N-4,5-dimethoxy-2-mercaptobenzyl auxiliary group.
abstract: An efficient method of peptide thioester synthesis is described. The reaction is based on an N-4,5-dimethoxy-2-mercaptobenzyl (Dmmb) auxiliary-assisted N-S acyl shift reaction after assembling a peptide chain by Fmoc-solid phase peptide synthesis. The Dmmb-assisted N-S acyl shift reaction proceeded efficiently under mildly acidic conditions, and the peptide thioester was obtained by treating the resulting S-peptide with sodium 2-mercaptoethanesulfonate. No detectable epimerization of the amino acid residue adjacent to the thioester moiety in the case of Leu was found. The reactions were also amenable to the on-resin preparation of peptide thioesters. The utility was demonstrated by the synthesis of a 41-mer peptide thioester, a phosphorylated peptide thioester and a 33-mer peptide thioester containing a trimethylated lysine residue.
authors.affiliation: Institute for Protein Research, Osaka University, Yamadaoka 3-2, Suita, Osaka 565-0871, Japan.
authors.forename: Ken'ichiroh
authors.initials: K
authors.lastname: Nakamura
authors.forename: Tomoki
authors.initials: T
authors.lastname: Kanao
authors.forename: Tomoya
authors.initials: T
authors.lastname: Uesugi
authors.forename: Toshiaki
authors.initials: T
authors.lastname: Hara
authors.forename: Takeshi
authors.initials: T
authors.lastname: Sato
authors.forename: Toru
authors.initials: T
authors.lastname: Kawakami
authors.forename: Saburo
authors.initials: S
authors.lastname: Aimoto
mesh_terms: D004952:Esters / Q000138:chemical synthesis* / Q000737:chemistry*; D010455:Peptides / Q000138:chemical synthesis* / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D014269:Trifluoroacetic Acid / Q000737:chemistry
chemical_list: D004952:Esters; D010455:Peptides; D013438:Sulfhydryl Compounds; D014269:Trifluoroacetic Acid