Beyond a solvent:triple roles of dimethylformamide in organic chemistry-part 2

DMF as stabilizer

It was disclosed that DMF also can act as a stabilizer in some reactions. In this regard, synthesis of DMF-stabilized metal nanoclusters and nanoparticles were reported. Copper (Cu), iridium (Ir), gold (Au), palladium (Pd), silver (Ag), and Fe₂O₃ nanoparticles are stabilized with DMF molecules through interaction of amido groups of DMF with NCs

In addition, DMF usually serves as a solvent in the formation of peptide-bonds DMF dissolves amino acids and coupling reagents and does not react with piperidine, but this reagent can jeopardize peptide synthesis by decomposition into formaldehyde (HCHO) and dimethylamine (HNMe₂).

Worthy of mention is that on the basis of published reports by NIOSH (The National Institute for Occupational Safety and Health), DMF is readily absorbed through the skin or by inhalation or ingestion. This chemical is a potent liver toxin. DMF is also known to cause constipation, abdominal pain, vomiting and nausea, headache, weakness, dizziness, skin problems, and alcohol intolerance.

The development of DMF

The solvent effect of DMF on the efficiency and solvation of anions was reviewed by Parker in 1962 Other significant functions of DMF, such as being utilized as a ligand, reducing agent, and dehydrating agent were reported by Muzart and coworkers in 2009. In addition, recent developments in the applications of DMF in the area of nitrilation, amination, formylation, aminocarbonylation, and amidation, as well as its reaction with arynes was reviewed in 2012; thus, these are not deliberated herein. As a matter of fact, the goal of this report is to disclose other roles of this unique chemical as reagent, catalyst, and stabilizer which have not been comprehensively reviewed. Herein, we try to provide an accessible reference and attract the attention of chemists and stir up their interest in using DMF in organic synthesis and trying to open other new gateway for more applications of this extraordinary compound as a unique and multipurpose chemical. We also frequently used DMF as an efficient solvent in our laboratory

Conclusion

Being thoughtful about this remarkable chemical, this article underscores recent progress in exploiting DMF as a privileged chemical, thanks to its structure. It is a multipurpose compound besides being an effective polar solvent. It acts as a reagent in various reactions such as formylation, amination, aminocarbonylation, amidation, and nitrilation, as well as reactions with arynes. Particularly, employment of DMF as a precursor in nitrilation and formylation reactions have seen important developments. It is noteworthy that in some reactions other amides can be used as precursors as well. With the concern in green and sustainable chemistry, it can be anticipated that application of DMF as a precursor will continue to develop in organic synthesis. Moreover, the development of new catalytic systems with increased reactivity will have important consequences for the practical utilization of DMF as a catalyst. Mechanistic studies in both reported reactions and future developments of novel reactions were conducted. Moreover, applications of DMF as a stabilizer were also discussed. In summary, in this review the main achievements on usage of DMF as a reagent, catalyst, and stabilizer have been summarized and discussed. We hope that it is sufficiently impressive and thorough that it will attract the attention of synthetic organic chemists and will initiate further developments in the applications of DMF beyond being just a polar solvent because it can be so much more with a little innovation.