title: Synthesis of amide-type fluoroalkene dipeptide isosteres by an intramolecular redox reaction.
abstract: We previously achieved NHC-mediated preparation of ester-type fluoroalkene dipeptide isosteres (ES-FADIs, 4) by an intramolecular redox reaction. In the present study, a cyanide ion-mediated reaction was successfully applied to the conversions of gamma,gamma-difluoro-alpha,beta-enoylsilane 1 or 2 to amide-type fluoroalkene isosteres (AM-FADIs, 5 or 6). The use of catalytic cyanide ion allowed synthesis of chiral auxiliary incorporated FADI 15b which was then subjected to a diastereoselective alpha-alkylation reaction to yield alpha-substituted FADIs 17. Furthermore, the presented amidation protocol was used for straightforward incorporation of FADI into peptidyl resin.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokushima, 1-78-1 Shomachi, Tokushima 770-8505, Japan.
authors.forename: Yoko
authors.initials: Y
authors.lastname: Yamaki
authors.forename: Akira
authors.initials: A
authors.lastname: Shigenaga
authors.forename: Jinglan
authors.initials: J
authors.lastname: Li
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Shimohigashi
authors.forename: Akira
authors.initials: A
authors.lastname: Otaka