南京大学史壮志团队报道了镍催化下芳香硼酸与亚砜胺的不对称2,3加成反应。相关研究成果发表在2024年6月24日出版的国际学术期刊《美国化学会杂志》。

磺酰胺类化合物在有机合成中有着广泛的应用，其制备研究跨越了一个多世纪。尽管催化方法取得了进步，但在这些分子中创建硫立体中心仍然是一个重大挑战。

该文中，研究人员提出了一种有效而通用的方法，通过催化不对称芳基加成亚磺酰胺来合成各种S-手性亚磺酰胺。通过利用镍络合物作为催化剂，该工艺表现出令人印象深刻的对映选择性，并且可以在硫位结合各种芳基硼酸。所得的合成磺酰胺稳定且适应性强，可转化为各种含硫化合物。该研究还结合了详细的实验和计算研究，以阐明反应机理和影响对映选择性的因素。

附：英文原文

Title: Asymmetric 2,3-Addition of Sulfinylamines with Arylboronic Acids Enabled by Nickel Catalysis

Author: Longlong Xi, Xiaowu Fang, Minyan Wang, Zhuangzhi Shi

Issue&Volume: June 24, 2024

Abstract: Sulfinamides have been widely used in organic synthesis, with research on their preparation spanning more than a century. Despite advancements in catalytic methodologies, creating sulfur stereocenters within these molecules remains a significant challenge. In this study, we present an effective and versatile method for synthesizing a diverse range of S-chirogenic sulfinamides through catalytic asymmetric aryl addition to sulfinylamines. By utilizing a nickel complex as a catalyst, this process exhibits impressive enantioselectivity and can incorporate various arylboronic acids at the sulfur position. The resulting synthetic sulfinamides are stable and highly adaptable, allowing for their conversion to a variety of sulfur-containing compounds. Our study also incorporates detailed experimental and computational studies to elucidate the reaction mechanism and factors influencing enantioselectivity.

DOI: 10.1021/jacs.4c04050

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c04050