北京大学郭雪峰团队报道了通过手性诱导的旋转选择性单分子实时监控反应的立体化学。相关研究成果发表在2023年5月15日出版的国际知名学术期刊《自然—化学》。

立体化学在有机合成、生物催化和物理过程中发挥着重要作用。原位手性鉴定和不对称合成是一项非凡的任务，尤其是对于单分子系统。然而，超越大量分子的手性表征（这不可避免地导致系综平均），对于阐明分子的手性性质所引起的不同性质至关重要。

该文中，研究人员报道了在单个分子中迈克尔加成、质子转移和酮-烯醇互变异构过程中手性变化的直接监测。利用手性诱导的自旋选择性效应，通过单分子结的连续电流测量揭示了反应过程中原位手性的变化。高灵敏度的手性鉴定为研究对称性破坏反应提供了一种很有前途的工具，并揭示了手性诱导的自旋选择性效应本身的起源。

附：英文原文

Title: Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity

Author: Yang, Chen, Li, Yanwei, Zhou, Shuyao, Guo, Yilin, Jia, Chuancheng, Liu, Zhirong, Houk, Kendall N., Dubi, Yonatan, Guo, Xuefeng

Issue&Volume: 2023-05-15

Abstract: Stereochemistry has an essential role in organic synthesis, biological catalysis and physical processes. In situ chirality identification and asymmetric synthesis are non-trivial tasks, especially for single-molecule systems. However, going beyond the chiral characterization of a large number of molecules (which inevitably leads to ensemble averaging) is crucial for elucidating the different properties induced by the chiral nature of the molecules. Here we report direct monitoring of chirality variations during a Michael addition followed by proton transfer and keto–enol tautomerism in a single molecule. Taking advantage of the chirality-induced spin selectivity effect, continuous current measurements through a single-molecule junction revealed in situ chirality variations during the reaction. Chirality identification at a high sensitivity level provides a promising tool for the study of symmetry-breaking reactions and sheds light on the origin of the chirality-induced spin selectivity effect itself.

DOI: 10.1038/s41557-023-01212-2

Source: https://www.nature.com/articles/s41557-023-01212-2