Li Xijian, Peng Siyu, Li Li, Huang Yong
Key Laboratory of Chemical Genomics, Peking University, Shenzhen Graduate School, Shenzhen 518055, China.
Nat Commun. 2015 Apr 21;6:6913. doi: 10.1038/ncomms7913.
Electron-rich dienes have revolutionized the synthesis of complex compounds since the discovery of the legendary Diels-Alder cycloaddition reaction. This highly efficient bond-forming process has served as a fundamental strategy to assemble many structurally formidable molecules. Amino silyloxy butadienes are arguably the most reactive diene species that are isolable and bottleable. Since the pioneering discovery by Rawal, 1-amino-3-silyloxybutadienes have been found to undergo cycloaddition reactions with unparalleled mildness, leading to significant advances in both asymmetric catalysis and total synthesis of biologically active natural products. In sharp contrast, this class of highly electron-rich conjugated olefins has not been studied in non-cycloaddition reactions. Here we report a simple synthesis of tetrasubstituted 1-silyloxy-3-aminobutadienes, a complementarily substituted Rawal's diene. This family of molecules is found to undergo a series of intriguing chemical transformations orthogonal to cycloaddition reactions. Structurally diverse polysubstituted ring architectures are established in one step from these dienes.
自从传奇的狄尔斯-阿尔德环加成反应被发现以来，富电子二烯彻底改变了复杂化合物的合成。这种高效的成键过程已成为组装许多结构复杂分子的基本策略。氨基硅氧基丁二烯可以说是最具反应活性的可分离和可储存的二烯物种。自拉瓦尔开创性发现以来，人们发现1-氨基-3-硅氧基丁二烯能以无与伦比的温和性进行环加成反应，这在不对称催化和生物活性天然产物的全合成方面都取得了重大进展。与之形成鲜明对比的是，这类高度富电子的共轭烯烃尚未在非环加成反应中得到研究。在此，我们报道了一种简单的合成四取代1-硅氧基-3-氨基丁二烯的方法，它是拉瓦尔二烯的互补取代物。人们发现这类分子会发生一系列与环加成反应正交的有趣化学转化。从这些二烯出发，一步就能构建出结构多样的多取代环结构。
