State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650201, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2021 Dec 15;143(49):20622-20627. doi: 10.1021/jacs.1c11265. Epub 2021 Dec 6.
The first total syntheses of bisdehydrotuberostemonine D () and putative bisdehydrotuberostemonine E (), two novel pyrrole alkaloids, along with the synthesis of bisdehydrotuberostemonine () have been completed in 12-13 steps. Our strategy harnesses the power of transition-metal-catalyzed reactions employing Ir, Ru, and Pd, in particular Ir-catalyzed asymmetric allylation of aldehydes, two distinct protocols recently developed by Carreira and Krische, respectively. The threefold use of Ir catalysis, first in the stereodivergent construction of two contiguous stereocenters at C (9,10) and then in rapid formation of the two γ-butyrolactone motifs, enabled the route's efficiency. Through this work, the originally assigned structure of bisdehydrotuberostemonine E () should be revised as 18α-bisdehydrotuberostemonine D ().
首次全合成了双去氢千里光碱 D () 和假定的双去氢千里光碱 E ()，这两种新型吡咯生物碱，以及双去氢千里光碱 ()。该合成路线共 12-13 步，采用了铱、钌和钯等过渡金属催化反应，特别是利用 Ir 催化的醛不对称烯丙基化反应，这两种方法分别由 Carreira 和 Krische 最近开发。三次使用 Ir 催化，首先在 C (9,10) 立体发散地构建两个连续的立体中心，然后快速形成两个 γ-丁内酯基序，使路线效率得以提高。通过这项工作，最初分配给双去氢千里光碱 E () 的结构应该修订为 18α-双去氢千里光碱 D ()。
