Enamines and Dimethylamino Imines as Building Blocks in Heterocyclic Synthesis: Reactions of DMF‐DMA Reagent with Different Functional Groups

Abstract

N,N‐Dimethylformamide dimethyl acetal (DMF‐DMA) reagent can react with different functional groups of organic compounds. Enamines and dimethylamino imines are obtained, when the DMF‐DMA reagent is reacted with methylene, methyl and amino groups. These products are formed in the intermediate step in the synthesis of many hetero rings. These compounds are especially used as a starting material in the synthesis of heterostructures such as pyrimidine, pyridine, pyrazole, etc. Therefore, DMF‐DMA has been particularly prominent as a reagent in targeted synthesis and designs of many heterocyclic compounds. Herein, the reactions of DMF‐DMA reagent with different functional groups are categorized in four classes (methylene, methyl, amino, other groups) and the reactions of obtained enamine and dimethylamino imine compounds are investigated in detail such as nucleophilic addition, intramolecular cyclization or condensation reactions. The synthesis and continuation reactions of the enamine and dimethylamino imine compounds are also examined in terms of experimental conditions and reagents used.

A novel strategy for the functionalization and design of 4-methylene-4H-pyran merocyaninesviaenamination and 1,8-conjugate addition

“…We chose DMF-DMA as an active molecule for chemoselective transformation. 20 By testing the conditions, we tried to find a convenient approach for the divergent and scalable preparation of pyrans 2a and 3a (Table 1). The most difficult task included the modification of only one methyl group of substance 1a .…”

“…Also, pyrans bearing the fragments of N -unsubstituted barbituric and thiobarbituric acid gave mixtures of enamination and alkylation products at the amide moieties under different conditions. 20 It should be noted that the synthesis of pyrans 2 and 3 from starting material 1 can be easily scaled up and conducted in gram quantities to give products 2 and 3 for a further study of their chemical properties.…”

Metal/catalyst/alkyne/alkene‐free one‐pot synthesis of indolizines from 2‐(pyridin‐2‐yl)acetate, DMF‐DMA and α‐halomethylenes

“…DMF‐DMA [26] is masked aldehyde and one‐carbon synthon normally used for its reaction with amine/amide/active methylene group that forms corresponding amidines, which are useful for the synthesis of variety of heterocyclic compounds. Jalani et al have smartly manipulated such amidines by transforming into interesting and diverse heterocyclic systems [27].…”

“…Considering the importance of indolizines, alternative methods could be interesting and highly anticipated since, there are no reports on indolizine synthesis without the use of either catalysts (metal/acid/base) or alkyne/alkene. DMF-DMA [26] is masked aldehyde and one-carbon synthon normally used for its reaction with amine/ amide/active methylene group that forms corresponding amidines, which are useful for the synthesis of variety of heterocyclic compounds. Jalani et al have smartly manipulated such amidines by transforming into interesting and diverse heterocyclic systems [27].…”

Synthesis of Deuterated Heterocycles with Me2NCD(OMe)2 and Evaluation of the Products for Metabolism by Aldehyde Oxidase

“…Dimethylformamide dimethylacetal (DMF-DMA) and related compounds such as dimethylformamide diethylacetal and Bredereck's reagent have become well-established reagents for the introduction of one-carbon moieties in synthetic organic chemistry and have proven to be a powerful reagents for the construction of heterocyclic compounds. 7 We conducted a literature search to determine how deuterium-labeled formamide acetals had been previously prepared. Me 2 NCD(OMe) 2 returned three citations; 8−10 however, these documents did not describe the preparation or synthetic use of Me 2 NCD(OMe) 2 .…”