近日，中国科学技术大学张清伟团队研究了H-膦酰胺的对映选择性合成。相关论文发表在2025年11月23日出版的《德国应用化学》杂志上。

手性富集的含杂原子H-膦酸酯化合物将亲核的H–P(O)基团与可取代的亲电杂原子基团相结合，赋予其固有的两亲性，使其成为构建磷(V)立体中心化合物的强大平台——这类结构在不对称合成、药物和材料科学领域日益重要。然而，其对映选择性合成仍是一项重大挑战。

研究组首次报道了H-磷酰胺酸酯的高对映选择性合成。这些双官能、构型稳定的化合物可实现立体专一性的H–P(O)转化，获得多样的P–C、P–N、P–O和P–S键，而氨基则提供了正交的二次修饰位点。这些反应特性确立了H-磷酰胺酸酯作为模块化合成多种磷(V)立体中心化合物的通用且高效平台的地位。

附：英文原文

Title: Enantioselective Synthesis of H-Phosphinamidates

Author: Kang Ding, Jing-Jing Xue, Jia-Xin Zou, Qing-Wei Zhang, Bo Su

Issue&Volume: 2025-11-23

Abstract: Enantioenriched heteroatom-containing H-phosphoryl compounds unite a nucleophilic H–P(O) moiety with an electrophilic, substitutable heteroatom group, endowing them with inherent ambiphilicity and making them powerful platforms for constructing P(V)-stereogenic molecules—structures of growing significance in asymmetric synthesis, pharmaceuticals, and materials science. Yet their enantioselective synthesis has remained a significant challenge. Here we report the first highly enantioselective synthesis of H-phosphinamidates. These bifunctional, configurationally stable compounds enable stereospecific H–P(O) transformations to access diverse P–C, P–N, P–O, and P–S linkages, while the amino group offers an orthogonal handle for secondary derivatization. These reactivity features establish H-phosphinamidates as a versatile and general platform for the modular synthesis of structurally diverse P(V)-stereogenic compounds.

DOI: 10.1002/anie.202522534

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202522534