Sahoo Manoj Kumar, Lee Jeong Woo, Lee Soochan, Choe Wonyoung, Jung Byunghyuck, Kwak Jaesung, Hong Sung You
Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea.
Department of Physics and Chemistry, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 42988, Republic of Korea.
JACS Au. 2024 Mar 25;4(4):1646-1653. doi: 10.1021/jacsau.4c00128. eCollection 2024 Apr 22.
Aryl fluorosulfates have emerged as versatile SuFExable substrates, harnessing the reactivity of the S-F bond. In this study, we unveil their alternative synthetic utility in nickel-catalyzed borylation via C-O bond activation. This method highlights mild reaction conditions, a broad substrate scope, and moderate functional group tolerance, rendering it a practical and appealing approach for synthesizing a diverse array of aryl boronate esters. Furthermore, computational analysis sheds light on the reaction pathways, uncovering the participation of LNi(0) and LNi(II)ArX species. This insight is supported by the P NMR reaction monitoring along with isolation and single-crystal X-ray structural elucidation of well-defined arylnickel(II) intermediates obtained from the oxidative addition of aryl fluorosulfates. A comprehensive investigation, merging experimental and computational approaches, deepens our understanding of the alternative reactivity of SuFExable substrates.
芳基氟硫酸盐已成为多功能的可进行硫氟交换反应的底物，利用了S-F键的反应活性。在本研究中，我们揭示了它们在镍催化的通过C-O键活化进行硼化反应中的另一种合成用途。该方法具有温和的反应条件、广泛的底物范围和适度的官能团耐受性，使其成为合成各种芳基硼酸酯的实用且有吸引力的方法。此外，计算分析揭示了反应途径，发现了LNi(0)和LNi(II)ArX物种的参与。通过P NMR反应监测以及对从芳基氟硫酸盐氧化加成得到的明确的芳基镍(II)中间体的分离和单晶X射线结构解析，证实了这一见解。将实验和计算方法相结合的全面研究，加深了我们对可进行硫氟交换反应的底物的替代反应活性的理解。
