Abstract
N,N-Dialkyl amides such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), are common polar solvents, finds application as a multipurpose reagent in synthetic organic chemistry. They are cheap, readily available and versatile synthons that can be used in a variety of ways to generate different functional groups. In recent years, many publications showcasing, excellent and useful applications of N,N-dialkyl amides in amination (R-NMe2), formylation (R-CHO), as a single carbon source (R-C), methylene group (R-CH2), cyanation (R-CN), amidoalkylation (-R), aminocarbonylation (R-CONMe2), carbonylation (R-CO) and heterocycle synthesis appeared. This chapter highlights important developments in the employment of N,N-dialkyl amides in the synthesis of heterocycles and functionalization of acyclic systems. Although some review articles covered the application of DMF and/or DMA in organic functional group transformations, there is no specialized review on their application in the synthesis of cyclic and acyclic systems.
Keywords
- amination
- amidation
- amidoalkylation
- aminocarbonylation
- cyanation
- dialkyl amides
- formylation
- heterocycles
1. Introduction
The great advantage of DMF, DMA and other
A non-exhaustive seminal review by Muzart [1], highlighted different roles of DMF inorganic synthesis covered literature up to 2009, another comprehensive review by Ding and Jiao appeared in 2012 [12] which covered aspects of DMF as a multipurpose precursor in various reactions. Further, specialized review by Batra et al. [13], and other reviews dealing with recent applications of DMF and DMA as a reagent [14] and triple role of DMF as a catalyst, reagent and stabilizer also appeared [15].
In this book chapter we summarized developments on applications of DMF and DMA in reactions such as amination (R-NMe2) [16], formylation (R-CHO) [17, 18], as a single carbon source (R-C), methylene group (R-CH2) [19], carbonylation (R-CO), as well as newer reactions such as amidoalkylation (-CH2N(CH3)-C(〓O)CH3-R) [20], metal catalyzed aminocarbonylation (R-CONMe2) [21], cyanation (R-CN) [22, 23], and formation heterocycles, took place during the past few decades and up to October 2019. Heterocycles are important compounds finding excellent applications as useful materials and medicinally important compounds. Thus unlike other reviews appeared on this subject [1, 12, 13, 14, 15], we provided special emphasis on synthesis of heterocyclic compounds and reactions involving DMF and DMA. Thus, first part of this book chapter will cover synthesis of construction of cyclic system, especially heterocycles, the next part will cover the formation of open chain compounds. Although DMF can serve as a reagent in organic reactions such as Friedel-Crafts [24] and Vilsmeier-Haack [25] reactions the actual reagent is derivative of DMF, hence we did not cover such subjects. We hope this book chapter will stimulate further research interest on the application of DMF and DMA in organic synthesis.
2. DMF and DMA as synthon in synthesis of heterocycles
2.1 Construction of pyridine ring
Guan and co-workers reported synthesis of symmetrical pyridines from ketoxime carboxylates using DMF as a one carbon source in the presence of ruthenium catalyst and NaHSO3 as an additive (Figure 2). A series of ketoxime acetates
A possible mechanism for the reaction was proposed. Oxidation of DMF by Ru(II) gives an iminium species
Su et al., reported cyclisation of 4-(phenylamino)-2
The reaction proceeded smoothly with electron-donating and electron-withdrawing substituents on the aniline ring and the expected products were obtained in good yields. A plausible mechanism was proposed by the author in. Initially, DMF is converted into iminium ion
In 2015, Deng and co-workers reported the Ru catalyzed multi-component reaction of acetophenones
In this reaction DMF, in the presence of Ru/O2 catalyst, acted as a single carbon source. For better understanding of reaction mechanism, several control experiments were carried out [28] (Figure 4). Acetophenone was converted into a methyl ketene intermediate
2.2 Construction of pyrimidine ring
Jiang and co-workers developed the first example of employing
The desired product was obtained in good yield under the optimal reaction condition Pd(TFA)2 (5 mol%), Xantphos (5 mol%) and 70% TBHP (3.0 equiv) in 1.0 mL DMF at 120°C. Benzamidine salts containing electron-releasing or electron-withdrawing group on the benzene ring gave their desired product in moderate to good yield. Addition of radical scavenger, such as TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl), BHT (2,6-di-tert-butyl-4-methylphenol), and DPE (1,1-diphenylethylene) led to no desired product formation, which indicates the radical pathway is involved in this transformation [29].
Xiong et al., reported a general and highly selective method for annulation of amidines
This is an efficient copper catalyzed synthesis of quinazolines
In 2017, Fan et al., reported an efficient method for the synthesis of pyrimidines
2.3 Construction of quinazolinone ring
In 2016, Das et al., reported Pd/Ag catalyzed direct carbonylation of sp2C-H bonds of
The reaction was examined using different metal catalyst systems such as Pd-Ag, Cu-Ag, Co-Ag, Ni-Ag and finally Pd-Ag catalytic system was found to be suitable for this transformation [32]. When labeled DMF (CO18) was used as the solvent it has been found that product found not to contain O18. From these results, it can be concluded that incorporated carbonyl group is coming from the methyl group of DMF. Reaction under argon instead of oxygen lead to the poor yield, which indicates “O” atom is coming from oxygen environment.
In 2015, Wu et al., reported C-H bond activation of arenes
The reaction was optimized using different oxidant and catalysts under different temperature condition and the desired product was obtained in good yield in the presence of Pd(OAc)2-K2S2O8 and DMF/TFA solvent system at 140°C under O2 atmosphere. When the reaction was conducted with 13CO-labeled DMF (
2.4 Construction of dihydropyrroline indolone ring
In 2017, Chang and coworkers reported metal, ligand free, base promoted cascade reaction of DMF with
2.5 Construction of acyl indole ring
Deng et al., reported a metal free approach for the synthesis of 3-acylindoles
To prove the synthetic utility of this transformation gram scale experiment was conducted under optimized condition, wherein the yield of the corresponding product decreased slightly. Control experiments revealed that DMF acts as carbon source and O2 is the source of the oxygen. When deuterium labeled DMF was used as solvent, the labeled product was observed. Meantime, to probe the source oxygen atom in the final product a reaction has implemented with 18O-DMF and only non-labeled product was obtained. Thus, author justified that O2 is the source of the oxygen atom in the final product [35].
2.6 Construction of benzothiazole ring
Liu et al., developed a methodology for the synthesis of
To understand the role of CO2 in this reaction, isotopic labeling reaction were carried out using 13CO2, the non-labeled benzothiazole was observed in excellent yield [36]. When this cyclization reaction was carried out using d7-DMF instead of DMF, deuterated benzothiazole was obtained. This experiment revealed that DMF served as the formylating reagent CO2 as the promoter.
2.7 Construction of benzimidazole ring
Yadav et al. developed a cost effective synthetic protocol with 100% conversion of o-nitroaniline to benzimidazole using DMF as in-situ source of dimethylamine and CO. Herein, DMF undergoes water gas shift reaction in the presence of CuFe2O4 as catalyst to produce hydrogen (Figure 13). It mainly involves two steps the reduction of o-nitroaniline
A possible mechanism was proposed by author. Thermal degradation of DMF in the presence of water provides CO, which undergoes water gas shift reaction in the presence of catalyst to release hydrogen gas. This H2 reduces nitro group to form amine group. The formation of o-phenylenediamine was confirmed with the help of GC-MS and HPLC analysis and compared with standard samples. Further, formylation of one of the amine groups took place in the presence CO, then intramolecular cyclisation takes place to give benzimidazole.
2.8 Construction of coumarin ring
Ohshita et al. developed method for the synthesis of coumarins
3. Amidation
Having covered literature on construction of cyclic system, especially heterocycles using DMF or DMA as a next part we cover literature on the formation of open chain compounds.
An excellent method to access benzamides
Similarly, Indolese et al. reported aminocarbonylation of aryl halides
Furthermore, Lee and co-workers demonstrated the same reaction between aryl bromides/iodides
Wang et al., reported a metal-free radical amidation of thiazoles and oxazoles
Wang et al., demonstrated direct amidation of alcohols
Feng and coworkers proposed green protocol for the synthesis of α-ketoamides
Similarly, the synthesis of α-ketoamides
In 2016, Xiao and his team developed a simple and efficient technique for the synthesis of amides
Similarly, Tortoioli and co-workers demonstrated one-pot synthesis of dialkyl amides under metal free condition through the reaction between benzoic acid and DMF in presence of propyl phosphonic anhydride (T3P) with acid additives [49]. This mild method has been applied to the synthesis of dihydrofolate reductase inhibitor, triazinate (Figure 21).
Bhat et al. reported direct carbamoylation of heterocycles
Bhisma et al. gave an efficient copper catalyzed synthesis of phenol carbamates
Phan and coworkers under oxidative condition synthesized organic carbamates
Yuan et al., synthesized S-phenyldialkylthiocarbamate
Kamal and coworkers proposed an efficient and greener methodology for the synthesis of selenocarbamates
Reddy and coworkers synthesized chiral symmetrical urea derivatives
3.1 Amination
Chang et al., reported that benzoxazoles
Interestingly, this method is also suitable for the optically active formamide, the desired product was obtained in better yield without racimization [56].
Li et al., gave a method for the synthesis of 2-aminoazole derivatives
Similarly, Yu et al., developed a decarbonylative coupling between azoles and formamides. The iron catalyzed direct C-H amination of azoles at C2 took place in the presence of formamides and amines as nitrogen source (Figure 29). Easily accessible iron (II) salts acted as Lewis acid which activated the C2 position of benzoxaoles
Peng and coworkers developed a facile and efficient route for one pot synthesis of 2-acyl-4-(dimethylamino)-quinazoline
Eycken et al. demonstrated a convenient microwave-assisted de-sulfitative dimethylamination of 5-chloro-3-(phenylsulfanyl)-2-pyrazinones
Hongting et al. developed an efficient, atom-economic and eco-friendly approach for synthesizing enamines
Li et al., developed hypervalent iodine mediated reaction between carboxylic acids
Liang and coworkers gave a simple and efficient one-pot multicomponent reaction of chalcones
Xia and coworkers proposed a simple and green approach for the synthesis of sulfonamides through t-BuOK mediated direct S-N bond formation from sodium sulfinates
Gong et al., reported a base-promoted amination of aromatic halides
3.2 Methylenation
In recent past several methods were developed for using DMF as a methylene source.
Wang et al., developed a new method for the synthesis of vinylquinolines
Qian Xu and coworkers developed an eco-friendly iron-catalyzed benzylic vinylation which transfers the carbon atom in
Miura et al., demonstrated an effective way for α-methylenation of benzyl pyridines
Li et al., developed an iron-catalyzed α-methylenation of aryl ketones
In 2019, Wang et al., reported a one-pot procedure for the synthesis of 3-indolyl-3-methyl oxindoles
Liu and coworkers reported a method for the synthesis of diindolylmethane
In 2014, Xue and co-workers developed methylation of ketones
A possible mechanism was proposed as shown in Figure 44. Initially, persulfate oxidizes DMF to give a reactive iminium intermediate. The intermediate
3.3 Amidoalkylation
Li et al., reported direct oxidative thiolation of sp3 C-H bond next to a nitrogen atom
In this oxidative thiolation reaction, thiol group was successfully coupled with sp3 C-H bond of
It is noteworthy that various benzothiazole and a fipronil analogs could also be synthesized through this methodology (Figure 46) [73].
Stephenson et al., developed Friedel-Craft amidoalkylation of alcohols and electron rich arenes as potent nucleophile with alkyl amides
In this method inexpensive and efficient persulfate was used as oxidant for the construction of C-O and C-C bonds. Most of the time, photo catalysis provided better selectivity and good yields for the Friedel-Crafts reactions as compared with the thermolytic reaction conditions [74].
Li et al., gave a transition metal-free method for amidation of sp3 C-H bond in amides through cross dehydrogenative coupling process by using iodide anion as catalyst and TBHP as oxidant (Figure 48). It proceeds through free radical intermediate which is confirmed by TEMPO and the products has an potential bioactivity
In 2017, Chen and coworkers demonstrated copper-catalyzed C-N bond formation of triazoles
Zhu and Co-Workers discovered a new methodology for the synthesis of 2-amidoalkylated benzothiazole and 3-amidoalkyl substituted indolinone derivatives using
3.4 Cyanation
It is interesting to note that dialkylamides could undergo reaction to generate cycano group. In 2011 Ding et al., reported a novel and another kind of pathway to produce the aryl nitriles
Similarly, in 2015, Chen and co-workers developed a selective copper-catalyzed C3-cyanation of indole under an oxygen atmosphere with DMF as a safe CN source and as a solvent (Figure 51) [79].
Wang et al., demonstrated a copper catalyzed cyanation of indoles
Chang et al., reported a new approach for the synthesis of Aryl nitriles
Ushijima et al., reported the synthesis of aromatic nitriles
A possible mechanism for this reaction was given in Figure 54. When treated with ammonia, the iminium salt can be transformed into the aromatic imine. Then molecular iodine serves as an oxidizing agent and reacts with the aromatic imine to provide the corresponding aromatic
However, the need of highly electron-rich aromatics in the formation of aromatic
Followed by the treatment with molecular iodine in aqueous ammonia. Similarly, the same author reported synthesis of aryl nitriles from aryl bromides in the presence of Mg [84].
3.5 Formylation
Further, dialkylamides were also used as a formylation source. Wang et al., transformylated different amines, primary or secondary, aromatic or alkyl cyclic or linear, mono- or di-amine with DMF as formylation reagent to obtain corresponding formamides
The best part about the CeO2 catalyst is the strong basicity and medium water-tolerant acidity (Figure 56) [85].
In 2017, Jagtap and coworkers reported highly efficient Ni(II) metal complex catalyzing
The importance of this reactions are cost-effective, easily available starting material, high reactivity and inertness toward air and water [86].
Larsen et al., developed a convenient method for the synthesis of α,β-acetylenic aldehydes
Jeon and co-workers reported methyl benzoate
3.6 Hydrogenation
Dialkylamides have ability to acts as hydrogen source and it has been used in several functional group transformations. It is advantageous to use hydrogen gas
Hua et al. reported triruthenium dodecacarbonyl [Ru3(CO)12] catalyzed stereo divergent semi-hydrogenation of diaryl alkynes
Chan et al., reported a hydrogenation reaction catalyzed by cobalt porphyrins which hydrogenated C-C bond of [2.2] paracyclophane
In 2017, Liu and coworkers synthesized α-arylketothioamides
3.7 Carbonylation
Carbonylation is another important reaction in which the poisonous “CO” gas is generated from dialkylamides in the presence of suitable catalysts. Thus carbonylation reaction using dialkylamides is highly advantageous.
Gunanathan and coworkers developed a new mode of bond activation which is used effectively for the synthesis of simple and functionalized symmetrical and unsymmetrical urea derivatives from amines using DMF as CO source (Figure 63). Activation of N-H bond of amines by Ruthenium pincer complex and after that CO insertion from DMF with the liberation of hydrogen. Nucleophilicity of amines is essential for urea formation. The significance of this reaction occurs in an open condition, it avoids side products, doesn’t require any pressure setup [92].
Furthermore, Chen and co-workers reported a unique and highly effective method for the formation of imidazolinones
4. Conclusion
It is noteworthy that, the utilization of DMF as a precursor in heterocyclic synthesis was important development in the field of synthetic organic chemistry. With advent of new reagents, catalytic systems and need for development of efficient synthetic protocols it could be predicted that dialkyl amides will continue to find new applications in organic synthesis. So far dialkyl amides have been mainly utilized as a synthon through mono functionalization of one of the groups. Further, there is a lot of scope for its utilization as a difuctionalization, for example, alkyl group attached to carbonyl and nitrogen in DMA could be functionalized at both the ends simultaneously. Dialkyl amides due to low cost, ready availability and flexibility in reactivity, will continue to gain attention of synthetic chemists as a synthon, ligand, dehydrating agent and solvent. We appreciate all of the authors cited herein for their tremendous contributions that have developed this field. We hope that it is sufficiently impressive and thorough that it will increase the interest on organic chemistry and will initiate further developments in the applications of DMF/DMA beyond being just a polar solvent, because it can be used as substrates in several reactions such as formylation, amination, amidoalkylation, aminocarbonylation, amidation, and cyanation and it has been achieved under both metal-catalyzed and metal-free conditions. We believe this book chapter will make it easy for the synthetic chemists and invoke an idea about utility of dialkyl amides for some novel functional group transformations.
Acknowledgments
P.S thanks to UGC-RFSMS, New Delhi for the award of the fellowship for Ph.D.
References
- 1.
Muzart J. N ,N -dimethylformamide: Much more than a solvent. Tetrahedron. 2009;65 :8313-8323. DOI: 10.1016/j.tet.2009.06.091 - 2.
Dubey A, Upadhyay A, Kumar P. Pivaloyl chloride/DMF: A new reagent for conversion of alcohols to chlorides. Tetrahedron Letters. 2010; 51 :744-746. DOI: 10.1016/j.tetlet.2009.11.131 - 3.
Liu Y, He G, Chen K, Jin Y, Li Y, Zhu H. DMF-catalyzed direct and regioselective C-H functionalization: Electrophilic/nucleophilic 4-halogenation of 3-oxypyrazoles. European Journal of Organic Chemistry. 2011; 2011 :5323-5330. DOI: 10.1002/ejoc.201100571 - 4.
Rai A, Rai VK, Singh AK, Yadav LDS. [2 + 2] Annulation of aldimines with sulfonic acids: A novel one-pot cis -selective route to β-sultams. European Journal of Organic Chemistry. 2011;2011 :4302-4306. DOI: 10.1002/ejoc.201100628 - 5.
Gowda M, Pande S, Ramakrishna R, Prabhu K. Acylation of Grignard reagents mediated by N -methyl pyrrolidone: A remarkable selectivity for the synthesis of ketones. Organic & Biomolecular Chemistry. 2011;9 :5365-5368. DOI: 10.1039/C1OB05780D - 6.
Liu X, Li C, Xu J, Lv J, Zhu M, Guo Y, et al. Surfactant-free synthesis and functionalization of highly fluorescent gold quantum dots. Journal of Physical Chemistry C. 2008; 112 :10778-10783. DOI: 10.1021/jp8028227 - 7.
Kawasaki H, Yamamoto H, Fujimori H, Arakawa R, Inada M, Iwasaki Y. Surfactant-free solution synthesis of fluorescent platinum subnanoclusters. Chemical Communications. 2010; 46 :3759-3761. DOI: 10.1039/B925117K - 8.
Hyotanishi M, Isomura Y, Yamamoto H, Kawasaki H, Obora Y. Surfactant-free synthesis of palladium nanoclusters for their use in catalytic cross-coupling reactions. Chemical Communications. 2011; 47 :5750-5752. DOI: 10.1039/C1CC11487E - 9.
Yao W, Gong WJ, Li HX, Li FL, Gao J, Lang JP. Synthesis of DMF-protected Au NPs with different size distributions and their catalytic performance in the Ullmann homocoupling of aryl iodides. Dalton Transactions. 2014; 43 :15752-15759. DOI: 10.1039/C4DT01856G - 10.
Azuma R, Nakamichi S, Kimura J, Yano H, Kawasaki H, Suzuki T, et al. Solution synthesis of N ,N -dimethylformamide-stabilized iron-oxide nanoparticles as an efficient and recyclable catalyst for alkene hydrosilylation. ChemCatChem. 2018;10 :2378-2382. DOI: 10.1002/cctc.201800161 - 11.
Shanab FA, Sherif SM, Mousa SAS. Dimethylformamide dimethyl acetal as a building block in heterocyclic synthesis. Journal of Heterocyclic Chemistry. 2009; 46 (5):801-827. DOI: 10.1002/jhet.69 - 12.
Ding S, Jiao N. N ,N -dimethylformamide: A multipurpose building block. Angewandte Chemie, International Edition. 2012;51 :9226-9237. DOI: 10.1002/anie.201200859 - 13.
Batra A, Singh P, Singh KN. Cross dehydrogenative coupling (CDC) reactions of N ,N disubstituted formamides, benzaldehydes and cycloalkanes. European Journal of Organic Chemistry. 2016:4927-4947. DOI: 10.1002/ejoc.201600401 - 14.
Bras JL, Muzart J. Recent uses of N ,N -dimethylformamide andN ,N -dimethylacetamide as reagents. Molecules. 2018;23 :1939. DOI: 10.3390/molecules23081939 - 15.
Heravi MM, Ghavidel M, Mohamadkhani L. Beyond a solvent: triple roles of dimethylformamide in organic chemistry. RSC Advances. 2018; 8 :27832-27862. DOI: 10.1039/C8RA04985H - 16.
Kodimuthali A, Mungara A, Prasunamba PL, Pal M. A simple synthesis of aminopyridines: Use of amides as amine source. Journal of the Brazilian Chemical Society. 2010; 21 :1439-1445. DOI: 10.1590/S0103-50532010000800005 - 17.
Gu DW, Guo XX. Synthesis of N -arylcarboxamides by the efficient transamidation of DMF and derivatives with anilines. Tetrahedron. 2015;71 :9117-9122. DOI: 10.1016/j.tet.2015.10.008 - 18.
Chen C, Tan L, Zhou P. Approach for the synthesis of N -phenylamides from β-ketobutylanilides using dimethylformamide and dimethylacetamide as the acyl donors. Journal of Saudi Chemical Society. 2015;19 :327-333 - 19.
Mondal S, Samanta S, Santra S, Bagdi AK, Hajra A. N ,N -dimethylformamide as a methylenating reagent: Synthesis of heterodiarylmethanes via copper-catalyzed coupling between imidazo[1,2-a]pyridines and indoles/N ,N -dimethylaniline. Advanced Synthesis and Catalysis. 2016;358 :3633-3641. DOI: 10.1002/adsc.201600674 - 20.
Weng JQ, Xu WX, Dai XQ, Zhang JH, Liu XH. Alkylation reactions of benzothiazoles with N ,N -dimethylamides catalyzed by the two-component system under visible light. Tetrahedron Letters. 2019;60 :390-396. DOI: 10.1016/j.tetlet.2018.12.064 - 21.
Iranpoor N, Firouzabadi H, Rizi ZT, Erfan S. WCl6/DMF as a new reagent system for the phosphine-free Pd(0)-catalyzed aminocarbonylation of aryl halides. RSC Advances. 2014; 4 :43178-43182. DOI: 10.1039/C4RA04673K - 22.
Venu B, Vishali B, Naresh G, Kumar VV, Sudhakar M, Kishore R, et al. C-H bond cyanation of arenes using N ,N -dimethylformamide and NH4HCO3 as a CN source over a hydroxyapatite supported copper catalyst. Catalysis Science & Technology. 2016;6 :8055-8062. DOI: 10.1039/C6CY01536K - 23.
Kim J, Choi J, Shin K, Chang S. Copper-mediated sequential cyanation of aryl C-B and arene C-H bonds using ammonium iodide and DMF. Journal of the American Chemical Society. 2012; 134 :2528-2531. DOI: 10.1021/ja211389g - 24.
Mata EG, Suarez AG. Regioselective acylation of benzodioxin derivatives employing AlCl3-DMSO or AlCl3-DMF reagent in the Friedel-Crafts reaction. Synthetic Communications. 1997; 27 :1291-1300. DOI: 10.1080/00397919708003368 - 25.
Ahmed S, Boruah R. An efficient conversion for conjugated oximes into substituted pyridines under Vilsmeier conditions. Tetrahedron Letters. 1996; 37 :8231-8232. DOI: 10.1016/0040-4039(96)01909-0 - 26.
Zhao MN, Hui RR, Ren ZH, Wang YY, Guan ZH. Ruthenium-catalyzed cyclization of ketoxime acetates with DMF for synthesis of symmetrical pyridines. Organic Letters. 2014; 16 :3082-3085. DOI: 10.1021/ol501183z - 27.
Weng Y, Zhou H, Sun C, Xie Y, Su W. Copper-catalyzed cyclization for access to 6H-chromeno[4,3-b]quinolin-6-ones employing DMF as the carbon source. The Journal of Organic Chemistry. 2017; 82 :9047-9053. DOI: 10.1021/acs.joc.7b01515 - 28.
Bai B, Tang L, Huanga H, Deng GJ. Synthesis of 2,4-diarylsubstituted-pyridines through a Ru-catalyzed four component reaction. Organic & Biomolecular Chemistry. 2015; 13 :4404-4407. DOI: 10.1039/05c5ob00162e - 29.
Guo W, Liao J, Liu D, Li J, Ji F, Wu F, et al. A four-component reaction strategy for pyrimidine carboxamide synthesis. Angewandte Chemie. 2016; 128 :1-6. DOI: 10.1002/ange.201608433 - 30.
Lv Y, Li Y, Xiong T, Pu W, Zhang H, Sun K, et al. Copper-catalyzed annulation of amidines for quinazoline synthesis. Chemical Communications. 2013; 49 :6439-6644. DOI: 10.1039/c3cc43129k - 31.
Zheng LY, Guo W, Fan XL. Metal-free, TBHP-mediated, [3+ +2+ +1]-type intermolecular cycloaddition reaction: Synthesis of pyrimidines from amidines, ketones, and DMF through C(sp3)C-H activation. Asian Journal of Organic Chemistry. 2017; 6 :837-840. DOI: 10.1002/ajoc.201700105 - 32.
Rao DN, Rasheed SK, Das P. Palladium/silver synergistic catalysis in direct aerobic carbonylation of C(sp2)-H bonds using DMF as a carbon source: Synthesis of pyrido-fused quinazolinones and phenanthridinones. Organic Letters. 2016; 18 :3142-3145. DOI: 10.1021/acs.orglett.6b01292 - 33.
Chen J, Feng JB, Natte K, Wu X. Palladium-catalyzed carbonylative cyclization of arenes by C-H bond activation with DMF as the carbonyl source. Chemistry - A European Journal. 2015; 21 :16370-16373. DOI: 10.1002/chem.201503314 - 34.
Zhang Q, Song C, Huang H, Zhang K, Chang J. Cesium carbonate promoted cascade reaction involving DMF as a reactant for the synthesis of dihydropyrrolizino[3,2-b]indol-10ones. Organic Chemistry Frontiers. 2018; 5 :80-87. DOI: 10.1039/C7QO00771J - 35.
Wang JB, Li YL, Deng J. Metal-free activation of DMF by dioxygen: A cascade multiple-bond-formation reaction to synthesize 3-acylindoles from 2-alkenylanilines. Advanced Synthesis and Catalysis. 2017; 359 :3460. DOI: 10.1002/adsc.201700584 - 36.
Gao X, Yu B, Mei Q, Yang Z, Zhao Y, Zhang H, et al. Atmospheric CO2 promoted synthesis of N-containing heterocycles over B(C6F5)3 catalyst. New Journal of Chemistry. 2016; 40 :8282-8287. DOI: 10.1039/C6NJ01721E - 37.
Rasal KB, Yadav GD. One-pot synthesis of benzimidazole using DMF as a multitasking reagent in presence CuFe2O4 as catalyst. Catalysis Today. 2018; 309 :51-60 - 38.
Yoshida H, Ito Y, Ohshita J. Three-component coupling using arynes and DMF: Straightforward access to coumarins via ortho-quinone methides. Chemical Communications. 2011; 47 :8512-8514. DOI: 10.1039/c1cc11955a - 39.
Mori S, Shibuya M, Yamamoto Y. Ruthenium-catalyzed hydrocarbamoylative cyclization of 1,6-diynes with formamides. Chemistry Letters. 2017; 46 :2. DOI: 10.1246/cl.160961 - 40.
Hosoi K, Nozaki K, Hiyama T. Carbon monoxide free aminocarbonylation of aryl and alkenyl iodides using DMF as an amide source. Organic Letters. 2002; 4 :2849-2851. DOI: 10.1021/ol026236k - 41.
Schnyder A, Beller M, Mehltretter G, Nsenda T, Studer M, Indolese AF. Synthesis of primary aromatic amides by aminocarbonylation of aryl halides using formamide as an ammonia synthon. The Journal of Organic Chemistry. 2001; 66 (12):4311-4315. DOI: 10.1021/jo015577t - 42.
Ju J, Jeong M, Moon J, Jung HM, Lee S. Aminocarbonylation of aryl halides using a nickel phosphite catalytic system. Organic Letters. 2007; 9 (22):4615-4618. DOI: 10.1021/ol702058e - 43.
He T, Li H, Li P, Wang L. Direct amidation of azoles with formamides via metal-free C-H activation in the presence oftert -butyl perbenzoate. Chemical Communications. 2011;47 :8946-8948. DOI: 10.1039/C1CC13086B - 44.
Xu K, Hu Y, Zhang S, Zha Z, Wang Z. Direct amidation of alcohols with N-substituted formamides under transition-metal-free conditions. Chemistry - A European Journal. 2012; 18 :9793-9797. DOI: 10.1002/chem.201201203 - 45.
Gao L, Tang H, Wang Z. Oxidative coupling of methylamine with an aminyl radical: Direct amidation catalyzed by I2/TBHP with HCl. Chemical Communications. 2014; 50 :4085-4088. DOI: 10.1039/c4cc00621f - 46.
Fan W, Shi D, Feng B. TBAI-catalyzed synthesis of α-ketoamides via sp3 C-H radical/radical cross-coupling and domino aerobic oxidation. Tetrahedron Letters. 2015; 56 :4638-4641. DOI: 10.1016/j.tetlet.2015.06.021 - 47.
Mai WP, Wang HH, Li ZC, Yuan JW, Xiao YM, Yang LR, et al. n Bu4NI-catalyzed direct synthesis of a-ketoamides from aryl methyl ketones with dialkylformamides in water using TBHP as oxidant. Chemical Communications. 2012;48 :10117-10119. DOI: 10.1039/C2CC35279F - 48.
Bi X, Li J, Shi E, Wang H, Gao R, Xiao J. Ru-catalyzed direct amidation of carboxylic acids with N -substituted formamides. Tetrahedron. 2016;72 :8210-8214. DOI: 10.1016/j.tet.2016.10.043 - 49.
Bannwart L, Abele S, Tortoioli S. Metal-free amidation of acids with formamides and T3P. Synthesis. 2016; 48 (13):2069-2078. DOI: 10.1055/s-0035-1561427 - 50.
Mete TB, Singh A, Bhat RG. Transition-metal-free synthesis of primary to tertiary carboxamides: A quick access to prodrug-pyrazinecarboxamide. Tetrahedron Letters. 2017; 58 :4709-4712 - 51.
Ali W, Rout SK, Guin S, Modi A, Banerjee A, Pater BK. Copper-catalyzed cross dehydrogenative coupling of N ,N -disubstituted formamides and phenols: A direct access to carbamates. Advanced Synthesis and Catalysis. 2015;357 :515-522. DOI: 10.1002/adsc.201400659 - 52.
Phan NTS, Nguyen TT, Vu PHL. A copper metal-organic framework as an efficient and recyclable catalyst for the oxidative cross-dehydrogenative coupling of phenols and formamides. ChemCatChem. 2013; 5 :3068-3077. DOI: 10.1002/cctc.201300400 - 53.
Yuan YG, Guo SR, Xiang JN. Cu(OAc)2-catalyzed thiolation of acyl C-H bonds with thiols using TBHP as an oxidant. Synlett. 2013; 24 (4):443-448. DOI: 10.1055/s-0032-1318188 - 54.
Singh P, Batra A, Singh P, Kaur A, Singh KN. Oxidative C-Se coupling of formamides and diselenides by using aqueous tert -butyl hydroperoxide: A convenient synthesis of selenocarbamates. European Journal of Organic Chemistry. 2013:7688-7692. DOI: 10.1002/ejoc.201301248 - 55.
Kumar GS, Kumar RA, Kumar PS, Reddy NV, Kumar KV, Kantam ML, et al. Copper catalyzed oxidative coupling of amines with formamides: A new approach for the synthesis of unsymmetrical urea derivatives. Chemical Communications. 2013; 49 :6686-6688. DOI: 10.1039/C3CC42381F - 56.
Cho S, Kim J, Lee S, Chang S. Silver-mediated direct amination of benzoxazoles: Tuning the amino group source from formamides to parent amines. Angewandte Chemie International Edition. 2009; 48 :9127-9130. DOI: 10.1002/anie.200903957 - 57.
Li Y, Xie Y, Zhang R, Jin K, Wang X, Duan C. Copper-catalyzed direct oxidative C-H amination of benzoxazoles with formamides or secondary amines under mild conditions. The Journal of Organic Chemistry. 2011; 76 :5444-5449. DOI: 10.1021/jo200447x - 58.
Wang J, Hou JT, Wen J, Zhang J, Yu XQ. Iron-catalyzed direct amination of azoles using formamides or amines as nitrogen sources in air. Chemical Communications. 2011; 47 :3652-3654. DOI: 10.1039/c0cc05811d - 59.
Chen X, Yang Q, Zhou Y, Deng Z, Mao X, Peng Y. Synthesis of 4-(dimethylamino) quinazoline via direct amination of quinazolin-4(3 H )-one usingN ,N -dimethylformamide as a nitrogen source at room temperature. Synthesis. 2015;47 (14):2055-2062. DOI: 10.1055/s-0034-1380550 - 60.
Sharma A, Mehta VP, Eycken EVD. A convenient microwave-assisted desulfitative dimethylamination of the 2(1 H )-pyrazinone scaffold usingN ,N -dimethylformamide. Tetrahedron. 2008;64 :2605-2610. DOI: 10.1016/j.tet.2008.01.030 - 61.
Ruijie Z, Hongting S, Bo R, Yan F, Hao W, Yehua S, et al. An efficient and green approach to synthesizing enamines by intermolecular hydroamination of activated alkynes. Chemical Research in Chinese Universities. 2015; 31 (2):212-217. DOI: 10.1007/s40242-015-4388-8 - 62.
Zhang C, Yue Q, Xiao Z, Wang X, Zhang Q, Li D. Synthesis of O -aroyl-N ,N -dimethylhydroxylamines through hypervalent iodine-mediated amination of carboxylic acids withN ,N -dimethylformamide. Synthesis. 2017;49 (18):4303-4308. DOI: 10.1055/s-0036-1588460 - 63.
Wei E, Liu B, Lin S, Liang F. Multicomponent reaction of chalcones, malononitrile and DMF leading to γ-ketoamides. Organic & Biomolecular Chemistry. 2014; 12 :6389-6392. DOI: 10.1039/C4OB00971A - 64.
Bao XD, Rong X, Liu Z, Gu Y, Liang G, Xia Q. Potassium tert -butoxide-mediated metal-free synthesis of sulfonamides from sodium sulfinates andN ,N -disubstituted formamides. Tetrahedron Letters. 2018;50 :2853-2858. DOI: 10.1016/j.tetlet.2018.06.031 - 65.
Yang C, Zhang F, Deng GJ, Gon H. Amination of aromatic halides and exploration of the reactivity sequence of aromatic halides. The Journal of Organic Chemistry. 2019; 84 (1):181-190. DOI: 10.1021/acs.joc.8b02588 - 66.
Li Y, Guo F, Zha Z, Wang Z. Iron-catalyzed synthesis of 2-vinylquinolines via sp3 C-H functionalization and subsequent CN cleavage. Chemistry, An Asian Journal. 2013;8 :534-537. DOI: 10.1002/asia.201201039 - 67.
Lou SJ, Xu DQ, Shen DF, Wang YF, Liua YK, Xu ZY. Highly efficient vinylaromatics generation via iron-catalyzed sp3 C-H bond functionalization CDC reaction: A novel approach to preparing substituted benzo[α]phenazines. Chemical Communications. 2012;48 :11993-11995. DOI: 10.1039/C2CC36708D - 68.
Liu J, Yi H, Zhang X, Liu C, Liu R, Zhang G, et al. Copper-catalysed oxidative Csp3-H methylenation to terminal olefins using DMF. Chemical Communications. 2014; 50 :7636-7638. DOI: 10.1039/C4CC02275K - 69.
Li YM, Lou SJ, Zhou QH, Zhu LW, Zhu LF, Li L. Iron-catalyzed α-methylenation of ketones with N ,N -dimethylacetamide: An approach for α,β-unsaturated carbonyl compounds. European Journal of Organic Chemistry. 2015;2015 :3044-3047. DOI: 10.1002/ejoc.201500189 - 70.
Liu Y, Wang CL, Xia HM, Wang Z, Wang YF. Direct Csp3-H methylenation of 2-arylacetamides using DMF/Me2NH-BH3 as the methylene source. Organic & Biomolecular Chemistry. 2019; 17 :6153-6157. DOI: 10.1039/C9OB00875F - 71.
Pu F, Li Y, Song YH, Xiao J, Liu ZW, Wang C, et al. Copper-catalyzed coupling of indoles with dimethylformamide as a methylenating reagent. Advanced Synthesis and Catalysis. 2016; 358 :539-542. DOI: 10.1002/adsc.201500874 - 72.
Li Y, Xue D, Lu W, Wang C, Liu ZT, Xiao J. DMF as carbon source: Rh-catalyzed α-methylation of ketones. Organic Letters. 2014; 16 :66-69. DOI: 10.1021/ol403040g - 73.
Tang RY, Xie YX, Xie YL, Xiang JN, Li JH. TBHP-mediated oxidative thiolation of an sp3 C-H bond adjacent to a nitrogen atom in an amide. Chemical Communications. 2011; 47 :12867-12869. DOI: 10.1039/c1cc15397h - 74.
Dai C, Meschini F, Narayanam JMR, Stephenson CRJ. Friedel-Crafts amidoalkylation via thermolysis and oxidative photocatalysis. The Journal of Organic Chemistry. 2012;77 :4425-4431. DOI: 10.1021/jo300162c - 75.
Lao ZQ, Zhong WH, Lou QH, Li ZJ, Meng XB. KI-catalyzed imidation of sp3 C-H bond adjacent to amide nitrogen atom. Organic & Biomolecular Chemistry. 2012; 10 :7869. DOI: 10.1039/c2ob26430g - 76.
Deng X, Lei X, Nie G, Jia L, Li Y, Chen Y. Copper-catalyzed cross-dehydrogenative N2-coupling of NH-1,2,3-triazoles with N ,N -dialkylamides: N-amidoalkylation of NH-1,2,3-triazoles. The Journal of Organic Chemistry. 2017;82 :6163-6171. DOI: 10.1021/acs.joc.7b00752 - 77.
Wang J, Li J, Huang J, Zhu Q. Transition metal-free amidoalkylation of benzothiazoles and amidoalkylarylation of activated alkenes with N ,N -dialkylamides. The Journal of Organic Chemistry. 2016;81 :3017-3022. DOI: 10.1021/acs.joc.6b00096 - 78.
Ding S, Jiao N. Direct transformation of N ,N -dimethylformamide to CN: Pd-catalyzed cyanation of heteroarenes via C-H functionalization. Journal of the American Chemical Society. 2011;133 :12374-12377. DOI: 10.1021/ja204063z - 79.
Xiao J, Li Q, Chen T, Han LB. Copper-mediated selective aerobic oxidative C3-cyanation of indoles with DMF. Tetrahedron Letters. 2015; 56 :5937-5940. DOI: 10.1016/j.tetlet.2015.09.044 - 80.
Zhang L, Lu P, Wang Y. Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate. Organic & Biomolecular Chemistry. 2015; 13 :8322. DOI: 10.1039/c5ob01244a - 81.
Pawara AB, Chang S. Catalytic cyanation of aryl iodides using DMF and ammonium bicarbonate as the combined source of cyanide: A dual role of copper catalysts. Chemical Communications. 2014; 50 :448. DOI: 10.1039/c3cc47926a - 82.
Ushijima S, Togo H. Metal-free one-pot conversion of electron-rich aromatics into aromatic nitriles. Synlett. 2010; 7 :1067-1070. DOI: 10.1055/s-0029-1219575 - 83.
Ushijima S, Togo H. One-pot conversion of aromatic bromides and aromatics into aromatic nitriles. Synlett. 2010; 10 :1562-1566. DOI: 10.1055/s-0029-1219935 - 84.
Ishii G, Moriyama K, Togo H. Transformation of aromatic bromides into aromatic nitriles via formations of Grignard reagents and their DMF adducts. Tetrahedron Letters. 2011; 52 :2404-2406. DOI: 10.1016/j.tetlet.2011.02.110 - 85.
Wang Y, Wang F, Zhang C, Zhang J, Li M, Xu J. Transformylating amine with DMF to formamide over CeO2 catalyst. Chemical Communications. 2014; 50 :2438. DOI: 10.1039/c3cc48400a - 86.
Sonawane RB, Rasal NK, Jagtap SV. Nickel-(II)-catalyzed N-formylation and N-acylation of amines. Organic Letters. 2017; 19 :2078-2081. DOI: 10.1021/acs.orglett.7b00660 - 87.
Journet M, Cai D, Dimichele LM, Larsen RD. Highly efficient synthesis of α,β-acetylenic aldehydes from terminal alkynes using DMF as the formylating reagent. Tetrahedron Letters. 1998; 39 :6427-6428. DOI: 10.1016/S0040-4039(98)01352-5 - 88.
Yang D, Jeon HB. Convenient N-formylation of amines in dimethylformamide with methyl benzoate under microwave irradiation. Bulletin of the Korean Chemical Society. 2010; 31 (5):1424-1426. DOI: 10.5012/36 bkcs.2010.31.5.1424 - 89.
Li J, Hua R. Stereodivergent ruthenium-catalyzed transfer semihydrogenation of diaryl alkynes. Chemistry - A European Journal. 2011; 17 :8462-8465. DOI: 10.1002/chem.201003662 - 90.
Tam CM, To CT, Chan KS. Carbon-carbon σ-bond transfer hydrogenation with DMF catalyzed by cobalt porphyrins. Organometallics. 2016; 35 :2174-2177. DOI: 10.1021/acs.organomet.6b00434 - 91.
Liu W, Chen C, Zhou P. Concise access to α-arylketothioamides by redox reaction between acetophenones, elemental sulfur and DMF. ChemistrySelect. 2017; 2 :5532. DOI: 10.1002/slct.201700866 - 92.
Krishnakumar V, Chatterjee B, Gunanathan C. Ruthenium-catalyzed urea synthesis by N-H activation of amines. Inorganic Chemistry. 2017; 56 :7278-7284. DOI: 10.1021/acs.inorgchem.7b00962 - 93.
Zeng W, Wang E, Qiu R, Sohail M, Wu S, Chen FX. Oxygen-atom insertion of NHC-copper complex: The source of oxygen from N ,N -dimethylformamide. Journal of Organometallic Chemistry. 2013;743 :4448. DOI: 10.1016/j.jorganchem.2013.06.017