School of Chemical Science and Engineering, Tongji University, Shanghai, China.
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Composite Materials, Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, Shanghai, China.
Nat Commun. 2024 Nov 22;15(1):10130. doi: 10.1038/s41467-024-54481-x.
D-amino acids, found in excess in a minority of organisms and crucial for marine invertebrates, contrast with the more common L-amino acids in most life forms. The local prebiotic origin of D-amino acid enantiomeric excess in natural systems remains an unsolved conundrum. Herein, we demonstrate the formation of enantiomeric excess (ee) D-amino acids through photocatalytic reductive amination of α-keto acids on natural pyrite. Various amino acids with ee values in the range of 14.5-42.4%, are formed. The wavy arrangement of atoms on the surface of pyrite is speculated to lead to the preferential formation of D-amino acids. This work reveals the intrinsic asymmetric photocatalytic activity of pyrite, which could expand understandings on mechanism of asymmetric catalysis and chirality of inorganic crystals. Furthermore, it provides a plausible pathway for the prebiotic formation of D-amino acids, adding further evidence to the origin of D-amino acids enantiomeric excess in natural systems.
D-氨基酸在少数生物体中过量存在，对海洋无脊椎动物至关重要，与大多数生命形式中更为常见的 L-氨基酸形成对比。天然体系中 D-氨基酸对映体过量的局部前生物起源仍然是一个未解决的难题。在此，我们证明了通过天然黄铁矿上的光催化还原氨化反应α-酮酸形成对映体过量（ee）D-氨基酸。形成了 ee 值在 14.5-42.4%范围内的各种氨基酸。推测黄铁矿表面的原子波浪排列导致 D-氨基酸的优先形成。这项工作揭示了黄铁矿内在的不对称光催化活性，这可能扩展对不对称催化机制和无机晶体手性的理解。此外，它为前生物 D-氨基酸的形成提供了一种可能的途径，为天然体系中 D-氨基酸对映体过量的起源提供了更多证据。
