Yamaki Yoko, Shigenaga Akira, Tomita Kenji, Narumi Tetsuo, Fujii Nobutaka, Otaka Akira
Graduate School of Pharmaceutical Sciences, The University of Tokushima, 1-78-1 Shomachi, Tokushima 770-8505, Japan.
J Org Chem. 2009 May 1;74(9):3272-7. doi: 10.1021/jo900134k.
(Z)-Fluoroalkene dipeptide isosteres (FADIs 16) have served as potential dipeptide mimetics possessing the substitution of fluoroalkenes for parent peptide bonds. Previously, we synthesized FADIs by reduction of gamma,gamma-difluoro-alpha,beta-enoates with organocoppers or SmI(2), which prompted us to use an intramolecular redox reaction mediated by N-heterocyclic carbenes (NHCs) for the preparation of FADIs. Instead of the enoates, gamma,gamma-difluoro-alpha,beta-enal 20 and gamma,gamma-difluoro-alpha,beta-enoylsilane 34 were converted to FADIs by an NHC-mediated intramolecular redox reaction, whereby aldehyde components reduced the allylic difluoride component in an S(N)2' manner with accompanying monodefluorination.
（Z）-氟代烯烃二肽类似物（FADIs 16）已作为潜在的二肽模拟物，其中氟代烯烃取代了母体肽键。此前，我们通过用有机铜或SmI(2)还原γ,γ-二氟-α,β-烯酸酯来合成FADIs，这促使我们使用由N-杂环卡宾（NHCs）介导的分子内氧化还原反应来制备FADIs。通过NHC介导的分子内氧化还原反应，γ,γ-二氟-α,β-烯醛20和γ,γ-二氟-α,β-烯酰基硅烷34取代烯酸酯转化为FADIs，其中醛组分以S(N)2'方式还原烯丙基二氟化物组分并伴随单脱氟。
