Department of Chemistry, Sungkyunkwan University, Suwon, 16419, Korea.
Nat Commun. 2019 Feb 20;10(1):851. doi: 10.1038/s41467-019-08792-z.
The manipulation of the transition states of a chemical process is essential to achieve the desired selectivity. In particular, transition states of chemical reactions can be significantly modified in a confined environment. We report a catalytic reaction with remarkable amplification of stereochemical information in a confined water cage. Surprisingly, this amplification is significantly dependent on droplet size. This water-induced chirality amplification stems from the hydrophobic hydration effects, which ensures high proximity of the catalyst and substrates presumably at the transition state, leading to higher enantioselectivity. Flow and batch reactors were evaluated to confirm the generality of this water-induced chirality amplification. Our observation on efficient chiral induction in confined water cages might lead to an understanding of the chirality amplification in the prebiotic era, which is a key feature for the chemical evolution of homochirality.
对化学反应过渡态的操控对于实现所需的选择性至关重要。特别是，在受限环境中可以显著改变化学反应的过渡态。我们报告了一种在受限的水笼中具有显著放大立体化学信息的催化反应。令人惊讶的是，这种放大显著依赖于液滴尺寸。这种水诱导的手性放大源于疏水性水合作用，它确保了催化剂和底物的高度接近，推测在过渡态附近，从而导致更高的对映选择性。流动和分批反应器进行了评估，以确认这种水诱导的手性放大的普遍性。我们在手性诱导方面的观察结果可能会导致对手性放大在原始生命时代的理解，这是同源手性化学进化的关键特征。
