Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Mansfield Road, Oxford, OX1 3TA, U.K.
J Am Chem Soc. 2017 Dec 13;139(49):17755-17758. doi: 10.1021/jacs.7b10956. Epub 2017 Nov 27.
The first enantioselective synthesis of (-)-himalensine A has been achieved in 22 steps. The synthesis was enabled by a novel catalytic, enantioselective prototropic shift/furan Diels-Alder (IMDAF) cascade to construct the ACD tricyclic core. A reductive radical cyclization cascade was utilized to build the B ring, and end-game manipulations featuring a molecular oxygen mediated γ-CH oxidation, a Stetter cyclization to access the pendant cyclopentenone, and a highly chemoselective lactam reduction delivered the natural product target.
首次实现了（-）-喜马拉雅辛 A 的对映选择性全合成，共 22 步。该合成方法通过新颖的催化对映选择性质子迁移/呋喃 Diels-Alder（IMDAF）级联反应来构建 ACD 三环核心。采用还原自由基环化级联反应构建 B 环，最后通过分子氧介导的γ-CH 氧化、Stetter 环化引入侧环烯酮、以及高度选择性的内酰胺还原等操作完成天然产物目标分子的构建。
