State Key Laboratory of Bioengineering Reactor, Shanghai Key Laboratory of New Drug Design, and School of Pharmacy, East China University of Science and Technology , 130 Mei-long Road, Shanghai 200237, China.
Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131-0001, United States.
Org Lett. 2018 Feb 16;20(4):1195-1199. doi: 10.1021/acs.orglett.8b00118. Epub 2018 Feb 7.
A strategy for the facile construction of the chiral quinolinylmethanolic structure, a core featured in cinchona alkaloids, is reported. A new reactivity is harnessed by TfOH-promoted chemoselective activation of α-C-H over O-H bond in quinolinylmethanols. The new reactivity is successfully engineered with an iminium catalysis in a synergistic manner to create a powerful conjugate addition-cyclization cascade process for synthesis of chiral quinoline derived γ-butyrolactones in good yields and with good to excellent enantioselectivities. The method enables the first total synthesis of natural product broussonetine in three steps.
报道了一种在手性喹啉甲醇结构（金鸡纳生物碱的核心特征）构建方面的简易策略。三氟甲磺酸促进的α-C-H 相对于 O-H 键的化学选择性活化，利用了一种新的反应性。新的反应性通过亚胺催化以协同的方式成功设计，从而为手性喹啉衍生的γ-丁内酯的合成创建了强大的共轭加成-环化级联反应过程，以良好的收率和良好到优秀的对映选择性得到产物。该方法能够三步实现天然产物布鲁松丁的首次全合成。
