In general, natural products exist in their most thermodynamically stable form. Therefore, final stage-reaction conditions leading to thermodynamic equilibrium often facilitate the production of the desired natural products. On the other hand, syntheses of contra-thermodynamic natural products pose greater challenges, as the thermodynamic bias should be overcome. Herein, we present the synthesis of contra-thermodynamic securinega alkaloid securingine B, derived from the more thermodynamically stable isomer secu’amamine D. Harnessing the disparity in triplet energy between two natural products, we have established a photochemical equilibrium favoring securingine B. Conversely, secu’amamine D was reformed from securingine B under thermodynamic equilibrium conditions. Inspired by these observations, we devised a novel type of photoswitching platform by introducing a push-pull system to the securinega framework. By leveraging this new photoswitching scaffold, we have developed a securingine B-inspired photochromic material and, subsequently, exploited it as a photoresponsive chiral dopant.

中文翻译：

---

securingine B 的合成使光响应材料设计成为可能


一般来说，天然产物以其热力学上最稳定的形式存在。因此，导致热力学平衡的最后阶段反应条件通常有助于产生所需的天然产物。另一方面，反热力学天然产物的合成带来了更大的挑战，因为应该克服热力学偏差。在此，我们提出了逆热力学 securinega 生物碱 securingine B 的合成，该化合物源自热力学稳定性更高的异构体 secu'amamine D。利用两种天然产物之间三重态能量的差异，我们建立了有利于 securingine B 的光化学平衡。相反，在热力学平衡条件下，secu'amamine D 是从 securingine B 重组而来的。受到这些观察结果的启发，我们通过在 securinega 框架中引入推挽系统，设计了一种新型的光开关平台。通过利用这种新的光开关支架，我们开发了一种受 B 启发的光致变色材料，随后将其用作光响应手性掺杂剂。