Photoassisted Charge Transfer Between DMF and Substrate: Facile and Selective N, N‐Dimethylamination of Fluoroarenes. Issue 13 (1st June 2021)

• Record Type: Journal Article
• Authors: Ansari, Tharique N.; Sharma, Sudripet; Bora, Pranjal P.; Ogulu, Deborah; Parmar, Saurav; Gallou, Fabrice; Kozlowski, Pawel M.; Handa, Sachin
• Is Part Of: ChemSusChem. Volume 14:Issue 13(2021)
• Page Start: 2704
• Page End: 2709
• Publication Date: 2021-06-01
• Subjects: charge transfer -- DMF -- N, N-dimethylamination -- polyfluoroarene -- Van der Waals complex; Green chemistry -- Periodicals; Sustainable engineering -- Periodicals; Chemistry -- Periodicals; Chemical engineering -- Periodicals; 660
• DOI: 10.1002/cssc.202100761
• Languages: English
• ISSNs: 1864-5631

Abstract

Abstract: 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 SN 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. Abstract : N, N ‐dimethylamination : Photoassisted cleavage of N, N ‐dimethylformamide (DMF) is explored for the N, N ‐dimethylamination of polyfluoroarenes. Computational studies reveal the formation of a reversible Van der Waals complex between the electron‐deficient fluorinated aromatic ring and DMF, which generate a charge transfer (CT) complex upon light irradiation. This complex decomposes and yields the desired amination product under mild conditions.