Kratena Nicolas, Kaiser Maximilian, Naumov Kirill, Waxmann Martin, Gaertner Peter
Institute of Applied Synthetic Chemistry, TU Wien, Getreidemarkt 9, A-1060 Vienna, Austria.
JACS Au. 2025 Mar 3;5(3):1076-1082. doi: 10.1021/jacsau.5c00102. eCollection 2025 Mar 24.
Biomimetic synthesis can be an attractive approach to access complex natural products by addressing challenging structural features through cascade reactions, which are inferred through tangible biosynthetic hypotheses. In some instances, the originally proposed structure or biosynthetic path might be revised through synthesis. In this communication we report a short and efficient bioinspired synthesis of Alstoscholarinoids A and B, rearranged triterpenes from the tree. Salient features of the synthesis include a transannular aldol addition as well as a cascade consisting of a Schenck-Ene reaction, Hock rearrangement, and aldol addition. This culminated in a revision of the likely biosynthetic origin of Alstoscholarinoid A and a thorough exploration of the previously proposed intermediates.
仿生合成可以是一种通过级联反应解决具有挑战性的结构特征来获取复杂天然产物的有吸引力的方法，这些级联反应是通过切实可行的生物合成假设推断出来的。在某些情况下，最初提出的结构或生物合成途径可能会通过合成进行修正。在本通讯中，我们报道了一种简短而高效的受生物启发的合成方法，用于合成Alstoscholarinoids A和B，这是从该树中重排得到的三萜类化合物。该合成的显著特点包括分子内环化羟醛加成反应以及由申克-烯反应、霍克重排和羟醛加成反应组成的级联反应。这最终导致了对Alstoscholarinoid A可能的生物合成起源的修正以及对先前提出的中间体的深入探索。
