Department of Chemistry, University of Louisville, 40292, Louisville, Kentucky, United States.
Novartis Pharma AG, CH-4056, Basel, Switzerland.
ChemSusChem. 2021 Jul 6;14(13):2704-2709. doi: 10.1002/cssc.202100761. Epub 2021 Jun 1.
A reversible Van der Waals complex formation between the electron-deficient fluorinated aromatic ring and N,N-dimethylformamide (DMF) molecules followed by light irradiation resulted in charge transfer (CT) process. The complex was stabilized by ammonium formate and further decomposed to form the C-N bond. Control experiments revealed that the simultaneous S Ar pathway also contributes to product formation. This methodology is mild, metal-free, and effective for the amination of a variety of substrates. The reproducibility of this methodology was also verified on gram-scale reactions. The CT states were supported by control UV/Vis spectroscopy and computational studies.
在光照射下，缺电子的氟化芳环和 N,N-二甲基甲酰胺（DMF）分子之间形成了可逆的范德华复合物，随后发生了电荷转移（CT）过程。该复合物被甲酸铵稳定，并进一步分解形成 C-N 键。对照实验表明，同时的 S Ar 途径也有助于产物的形成。该方法温和、无金属且高效，可用于多种底物的胺化反应。该方法的重现性也在克级反应中得到了验证。CT 态得到了控制紫外/可见光谱和计算研究的支持。
