Hubei Key Laboratory of Natural Medicinal Chemistry and Resource Evaluation, School of Pharmacy, Huazhong University of Science and Technology, 13 Hangkong Road, Wuhan, Hubei, 430030, China.
Department of Chemistry, Stanford University, Stanford, CA, 94305-5080, USA.
Angew Chem Int Ed Engl. 2020 Feb 10;59(7):2860-2866. doi: 10.1002/anie.201912948. Epub 2020 Jan 7.
A novel palladium-catalyzed Heck-type reaction of thiocarbamates has been designed to construct bridged seven-membered-ring systems that are otherwise challenging to prepare. Taking advantage of this newly developed method, enantioselective syntheses of lyconadins A-E (1-5), lycopecurine (6), and dehydrolycopecurine (7) have been realized in a divergent fashion. Our synthetic strategy also features an intramolecular cyclization of a N-chloroamine to forge the C6-N bond, a transannular Mannich-type reaction of a cyclic nitrone to stitch the C4 and C13 together, and a cyclocondensation to deliver the (dihydro-)pyridone motif.
一种新型的钯催化硫代氨基甲酸酯 Heck 型反应被设计用来构建桥环七元环体系，否则这是很难制备的。利用这种新开发的方法，以发散的方式实现了 lyconadins A-E（1-5）、lycopecurine（6）和 dehydrolycopecurine（7）的对映选择性合成。我们的合成策略还具有 N-氯胺的分子内环化以形成 C6-N 键、环状硝酮的跨环 Mannich 型反应以将 C4 和 C13 连接在一起以及环缩合以提供（二氢）吡啶酮基序的特点。
