College of Pharmacy, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, Korea.
J Org Chem. 2020 Apr 3;85(7):4795-4806. doi: 10.1021/acs.joc.0c00017. Epub 2020 Mar 24.
Herein, we report the asymmetric total syntheses of inthomycin antibiotics containing a methylene-interrupted oxazolyl-triene motif. Utilizing the α,β-unsaturated aldehyde as a common intermediate, all three inthomycins A-C were divergently synthesized. The asymmetric ynone reduction provided an -configured secondary alcohol as in the natural products with high enantioselectivity. The geometrically different triene units for each inthomycin were stereoselectively established via methyl cuprate conjugate addition, isomerization of the α,β-unsaturated aldehyde intermediate, and stereoretentive cross-coupling reactions.
在此，我们报告了含有亚甲基中断的噁唑基-三烯骨架的英替米星抗生素的不对称全合成。利用α,β-不饱和醛作为共同中间体，我们对三种英替米星 A-C 进行了发散合成。不对称的炔酮还原反应提供了一个 -构型的仲醇，与天然产物具有很高的对映选择性。每个英替米星的几何不同的三烯单元通过甲基铜叶立德的共轭加成、α,β-不饱和醛中间体的异构化以及立体保留的交叉偶联反应来立体选择性地建立。
