中国科学技术大学黄汉民团队近日实现了自适应动态动力学分辨率使手性诱导随环尺寸而改变。相关论文于2025年6月23日发表在《自然-化学》杂志上。

动态动力学分辨（DKR）是一种有效的手性诱导策略，可将底物外消旋物的两种对映体转化为相同的光学富集产物。通常，产物的绝对构型应由手性催化剂决定。

研究组报告了一种适应性DKR策略，通过充分利用非对映氨基烷基环钯化配合物的动态相互转化，形成具有高立体化学选择性的多种氮杂环。值得注意的是，这种创新的自适应DKR模型通过改变环化产物的环尺寸，实现了具有相同手性二膦连接钯催化剂的相邻立体中心绝对构型的改变。此外，以自适应DKR工艺为关键手性锻造和支架建立步骤，实现了简洁高效的马提尼酸全合成，进一步证明了该策略的有效性。

附：英文原文

Title: Adaptive dynamic kinetic resolution enables alteration of chiral induction with ring sizes

Author: Yu, Bangkui, Huang, Yao, Zhang, Haocheng, Huang, Hanmin

Issue&Volume: 2025-06-23

Abstract: Dynamic kinetic resolution (DKR) is an efficient chiral induction strategy that transforms both enantiomers of the substrate racemates into the same optically enriched product. Typically, the absolute configurations of the products should be determined by the chiral catalyst. Here we report an adaptive DKR strategy that forges diverse azapolycycles with high stereochemical selectivities by taking full advantage of the dynamic interconversion of diastereomeric aminoalkyl cyclopalladated complexes. Notably, this innovative adaptive DKR model achieves alterations of absolute configurations at the contiguous stereocentres with the same chiral diphosphine-ligated palladium catalyst by changing the ring sizes of the annulation products. Moreover, a concise and efficient total synthesis of martinellic acid was carried out by using the adaptive DKR process as the key chirality forging and scaffold establishment step, which further demonstrated the efficacy of this strategy.

DOI: 10.1038/s41557-025-01850-8

Source: https://www.nature.com/articles/s41557-025-01850-8