Beyond a solvent: triple roles of dimethylformamide in organic chemistry

Abstract

N,N-Dimethylformamide (DMF) is frequently used as an aprotic solvent in chemical transformations in laboratories of academia as well as in those of chemical industry. In the present review, we will reveal that DMF is actually something much more than a solvent. It is a unique chemical since, as well as being an effective polar aprotic solvent, it can play three other important roles in organic chemistry. It can be used as a reagent, a catalyst, and a stabilizer.

Photoredox Catalysis of Aromatic β‐Ketoesters for in Situ Production of Transient and Persistent Radicals for Organic Transformation

“…170 ppm, ca. 3.8 mol % in 5.0 mL DMF based on 0.5 mmol 1 a ; Table S6) decomposed from DMF promoted this redox‐neutral reaction (Table S5 and Scheme S1) . On the basis of this observation, we propose that the formation of persistent ketyl radical A and transient α‐carbonyl radical B is dependent on the form of the aromatic β‐ketoester (Scheme ).…”

“…3.8 mol % in 5.0 mL DMF based on 0.5 mmol 1 a; Table S6) decomposed from DMF promoted this redox-neutral reaction (Table S5 and Scheme S1). [27] On the basis of this observation, we propose that the formation of persistent ketyl radical A and transient a-carbonyl radical B is dependent on the form of the aromatic b-ketoester (Scheme 1). Following elimination of a proton, anionic enol form can be oxidized to produce a-carbonyl radical B, and the eliminated proton can activate the keto form to generate ketyl radical A.…”

Copper‐Catalyzed Chemoselective 1,4‐Reductions: Sequential One‐Pot Synthesis of Esters

“…Finally, the intermediate C may react with the solvent DMF wherein DMF or with some transient species that present in the reaction mixture may act as the source of proton/hydrogen‐radical and regenerates the Cu + ion by the formation of 3 a . This may be attributed based on the fact that DMF is something more than a solvent …”

Revisiting Hydroxyalkylation of Phenols with Cyclic Carbonates

“…Indeed, DMF is known to slowly decompose into basic dimethylamine at elevated temperature. [16] To make a more detailed comparison, we presented kinetic profiles of selected control experiments in the span of 12 hours ( Figure 2), and the results clearly justified beneficial effects of TBAF and the temperature setting (170°C). We also investigated other sources of fluorides (KF and CsF) and different ammonium salts (TBAB and TBAI), but the outcomes were respectively inferior to that with TBAF · 3H 2 O.…”