荷兰格罗宁根大学Ben L. Feringa小组发现，通过对二硫键进行非共价控制也可以实现立体发散的手性转移。这一研究成果于2022年2月4日发表在国际顶尖学术期刊《美国化学会杂志》上。

课题组发现，氢键在控制二硫键的手性和实现立体发散手性转移中起着至关重要的作用。溶液中S-S···H-N氢键的形成可促进构象适应，实现分子内手性转移，而C=O···H-N氢键的形成可导致超分子手性转移，形成反向平行的螺旋自组装固态结构。对同手性氨基酸砌块中编码的结构信息的依赖性，揭示了通过非共价手性传递可获得令人吃惊的动态立体化学空间。

据介绍，控制动态立体化学是一个重要的挑战，因为它不仅是蛋白质结构和功能的内在基础，而且还经常支配超分子系统和自组装。通常，二硫键在蛋白质中表现出立体发散行为；然而，手性信息如何传递到二硫键此前仍然不清楚。

附：英文原文

Title: Stereodivergent Chirality Transfer by Noncovalent Control of Disulfide Bonds

Author: Qi Zhang, Stefano Crespi, Ryojun Toyoda, Romain Costil, Wesley R. Browne, Da-Hui Qu, He Tian, Ben L. Feringa

Issue&Volume: February 4, 2022

Abstract: Controlling dynamic stereochemistry is an important challenge, as it is not only inherent to protein structure and function but often governs supramolecular systems and self-assembly. Typically, disulfide bonds exhibit stereodivergent behavior in proteins; however, how chiral information is transmitted to disulfide bonds remains unclear. Here, we report that hydrogen bonds are essential in the control of disulfide chirality and enable stereodivergent chirality transfer. The formation of S–S···H–N hydrogen bonds in solution can drive conformational adaption to allow intramolecular chirality transfer, while the formation of C=O···H–N hydrogen bonds results in supramolecular chirality transfer to form antiparallel helically self-assembled solid-state architectures. The dependence on the structural information encoded in the homochiral amino acid building blocks reveals the remarkable dynamic stereochemical space accessible through noncovalent chirality transmission.

DOI: 10.1021/jacs.1c10000

Source: https://pubs.acs.org/doi/10.1021/jacs.1c10000