复旦大学张俊良团队报道了铜催化芳基硼氧胺在亚胺上不对称加成催化合成亚胺酰胺。相关研究成果发表在2024年6月20日出版的《美国化学会杂志》。

磺酰胺在药物和农业化学中的应用已被证明是不对称转化。然而，它们的不对称催化合成方法很少被探索。

该文报道了通过Cu催化剂和新开发的Xuphos配体催化芳基硼酸与亚磺酰胺的对映选择性加成。一系列手性芳基磺酰胺可以很容易地在一步中获得。

该方案使磺酰胺能够立体特异性转化为磺酰亚胺基氟化物、磺酰亚胺和磺酰亚胺酯。DFT计算揭示了反应途径，迁移插入是对映体的决定步骤。亚磺酰基胺的氧原子和配体中的C–H键之间的非共价相互作用，对于对映选择性控制至关重要。

附：英文原文

Title: Catalytic Asymmetric Synthesis of Sulfinamides via Cu-Catalyzed Asymmetric Addition of Aryl Boroxines to Sulfinylamines

Author: Yixiang Shi, Yin Yuan, Jianhui Li, Junfeng Yang, Junliang Zhang

Issue&Volume: June 20, 2024

Abstract: The application of sulfinamides has been witnessed in medicinal and agrochemistry with employment in asymmetric transformations. However, methods for their asymmetric catalytic synthesis have rarely been explored. Herein, the catalytic enantioselective addition of aryl boroxines to sulfinylamines via Cu catalyst and the newly developed Xuphos ligand were reported. A series of chiral aryl sulfinamides can be readily accessed in one step. This protocol enables the stereospecific transformation of sulfinamides to sulfonimidoyl fluorides, sulfonimidamides, and sulfonimidate esters. DFT calculations have revealed the reaction pathway, and the migratory insertion is the enantio-determining step. The noncovalent interaction between the oxygen atom of sulfinylamines and the C–H bonds in the ligand is crucial for enantioselectivity control.

DOI: 10.1021/jacs.4c03473

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c03473