Yu Bangkui, Huang Yao, Zhang Haocheng, Huang Hanmin
State Key Laboratory of Precision and Intelligent Chemistry and Department of Chemistry, University of Science and Technology of China, Hefei, P. R. China.
Nat Chem. 2025 Jun 23. doi: 10.1038/s41557-025-01850-8.
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.
动态动力学拆分（DKR）是一种高效的手性诱导策略，可将底物外消旋体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。在此，我们报告了一种适应性DKR策略，该策略通过充分利用非对映体氨基烷基环钯配合物的动态互变，以高立体化学选择性构建多种氮杂多环。值得注意的是，这种创新的适应性DKR模型通过改变环化产物的环大小，使用相同的手性双膦配体钯催化剂实现了相邻立体中心绝对构型的改变。此外，以适应性DKR过程作为关键的手性构建和骨架建立步骤，简洁高效地完成了马丁内利酸的全合成，进一步证明了该策略的有效性。
