Recent Uses of N,N-Dimethylformamide and N,N-Dimethylacetamide as Reagents

N,N-Dimethylformamide and N,N-dimethylacetamide are multipurpose reagents which deliver their own H, C, N and O atoms for the synthesis of a variety of compounds under a number of different experimental conditions. The review mainly highlights the corresponding literature published over the last years.


Introduction
The organic, organometallic and bioorganic transformations are extensively carried out in N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc). These two polar solvents are not only use for their dissolution properties, but also as multipurpose reagents. They participate in a number of processes and serve as a source of various building blocks giving one or more of their own atoms (Scheme 1).

Introduction
The organic, organometallic and bioorganic transformations are extensively carried out in N,Ndimethylformamide (DMF) or N,N-dimethylacetamide (DMAc). These two polar solvents are not only use for their dissolution properties, but also as multipurpose reagents. They participate in a number of processes and serve as a source of various building blocks giving one or more of their own atoms (Scheme 1). In 2009, one of us reviewed the different roles of DMF, highlighting that DMF is much more than a solvent [1]. Subsequently, this topic has been documented by the teams of Jiao [2] and Sing [3]. For of a book devoted to solvents as reagents in organic synthesis, we wrote a chapter summarizing the Scheme 1. Fragments from DM (R = H or Me) used in synthesis.
In 2009, one of us reviewed the different roles of DMF, highlighting that DMF is much more than a solvent [1]. Subsequently, this topic has been documented by the teams of Jiao [2] and Sing [3].
Cycloadditions leading to symmetrical tetrasubstituted pyridines using the Me group of DMF as the CH source have been carried out using either ketoxime carboxylates with Ru catalysis (Equation (7)) [41], or arones with both iodine and ammonium persulfate mediation (Equation (8)) [42].
Cycloadditions leading to symmetrical tetrasubstituted pyridines using the Me group of DMF as the CH source have been carried out using either ketoxime carboxylates with Ru catalysis (Equation (7)) [41], or arones with both iodine and ammonium persulfate mediation (Equation (8)) [42]. 2,4-Diarylpyridines were also synthetized from Ru-catalyzed reaction of acetophenones with ammonium acetate and DMF as source of the N and CH atoms, respectively (Equation (9)) [43].

CH2 Fragment
The coupling of indoles or imidazo[1,2-a]pyridines to afford heterodiarylmethanes with DMF as the methylenating reagent occurred in fair to high yields with a Cu I catalyst associated to t-BuOOH [51] or K2S2O8 [52] (Equations (19)- (21)). Use of DMAc was less efficient.

CH 2 Fragment
The coupling of indoles or imidazo[1,2-a]pyridines to afford heterodiarylmethanes with DMF as the methylenating reagent occurred in fair to high yields with a Cu I catalyst associated to t-BuOOH [51] or K 2 S 2 O 8 [52] (Equations (19)- (21)). Use of DMAc was less efficient.

CH2 Fragment
The coupling of indoles or imidazo[1,2-a]pyridines to afford heterodiarylmethanes with DMF as the methylenating reagent occurred in fair to high yields with a Cu I catalyst associated to t-BuOOH [51] or K2S2O8 [52] (Equations (19)- (21)). Use of DMAc was less efficient.
A Mannich reaction leading to β-amino ketones with DMF as the formaldehyde source has been reported in the presence of t-BuOOH and catalytic amounts of an N-heterocyclic carbene, SnCl2 and NEt3 (Equation (23)) [11].

CH2 Fragment
The coupling of indoles or imidazo[1,2-a]pyridines to afford heterodiarylmethanes with DMF as the methylenating reagent occurred in fair to high yields with a Cu I catalyst associated to t-BuOOH [51] or K2S2O8 [52] (Equations (19)- (21)). Use of DMAc was less efficient.
A Mannich reaction leading to β-amino ketones with DMF as the formaldehyde source has been reported in the presence of t-BuOOH and catalytic amounts of an N-heterocyclic carbene, SnCl2 and NEt3 (Equation (23)) [11].
A Mannich reaction leading to β-amino ketones with DMF as the formaldehyde source has been reported in the presence of t-BuOOH and catalytic amounts of an N-heterocyclic carbene, SnCl 2 and NEt 3 (Equation (23)) [11]. The study of an unexpected reaction due to the oxidation of DMAc with aqueous t-BuOOH (Equation (24)) showed the formation of MeCONMe(CH2OH) and MeCON(CH2OH)2, these unusual species delivering the methylene group [12].
The study of an unexpected reaction due to the oxidation of DMAc with aqueous t-BuOOH (Equation (24)) showed the formation of MeCONMe(CH 2 OH) and MeCON(CH 2 OH) 2 , these unusual species delivering the methylene group [12]. The study of an unexpected reaction due to the oxidation of DMAc with aqueous t-BuOOH (Equation (24)) showed the formation of MeCONMe(CH2OH) and MeCON(CH2OH)2, these unusual species delivering the methylene group [12].
The study of an unexpected reaction due to the oxidation of DMAc with aqueous t-BuOOH (Equation (24)) showed the formation of MeCONMe(CH2OH) and MeCON(CH2OH)2, these unusual species delivering the methylene group [12].

NMe2 Fragment
This chapter is divided in sections corresponding to the type of function reacting with DM.

NMe 2 Fragment
This chapter is divided in sections corresponding to the type of function reacting with DM.

Alkenes
Hydrocarbonylation of terminal alkenes and norbornene followed by acyl metathesis with DM occurred under Pd catalysis, CO pressure and in the presence of ammonium chloride or N-methyl-2pyrrolidone hydrochloride (NMP·HCl) (Equations (32) and (33)) [54]. From alkenes, the selectivity towards linear and branched products depended on the catalytic system (Equation (32)). DMF and DMAc afforded similar results.

Alkylarenes
Oxidation of methylarenes and ethylarenes at 80 • C in DMF using catalytic amounts of both I 2 and NaOH [31] or n-Bu 4 NI [32] associated to aqueous t-BuOOH under air led to benzylic oxidation and incorporation of the NMe 2 fragment to afford benzamides (Equation (30)) or α-ketoamides (Equation (31)).

Alkenes
Hydrocarbonylation of terminal alkenes and norbornene followed by acyl metathesis with DM occurred under Pd catalysis, CO pressure and in the presence of ammonium chloride or N-methyl-2pyrrolidone hydrochloride (NMP·HCl) (Equations (32) and (33)) [54]. From alkenes, the selectivity towards linear and branched products depended on the catalytic system (Equation (32)). DMF and DMAc afforded similar results.

Alkenes
Hydrocarbonylation of terminal alkenes and norbornene followed by acyl metathesis with DM occurred under Pd catalysis, CO pressure and in the presence of ammonium chloride or N-methyl-2-pyrrolidone hydrochloride (NMP·HCl) (Equations (32) and (33)) [54]. From alkenes, the selectivity towards linear and branched products depended on the catalytic system (Equation (32)). DMF and DMAc afforded similar results. Molecules 2018, 23, x FOR PEER REVIEW 9 of 29

Acids
Copper, palladium and ruthenium catalysts associated to oxidants and DMF were used for the amidation of cinnamic acids [29] and carboxylic acids [55] (Equations (34) and (35)). N,N-Dimethylbenzamide was one of the products obtained from the Cu II -catalyzed oxidation of flavonol [56].
Metal-free conditions and DMF were used for: the amidation of acids promoted with propylphosphonic anhydride associated to HCl at 130 °C (Equation (36)) [15], the amination of acids employing a hypervalent iodine reagent at room temperature (Equation (37)) [35]. Mesityliodine diacetate was superior to the other hypervalent iodine reagents, while oxidants such as I2, t-BuOOH, NaIO4 or K2S2O8 did not mediate the amidation reaction [35].

Acids
Copper, palladium and ruthenium catalysts associated to oxidants and DMF were used for the amidation of cinnamic acids [29] and carboxylic acids [55] (Equations (34) and (35)). N,N-Dimethylbenzamide was one of the products obtained from the Cu II -catalyzed oxidation of flavonol [56].

Acids
Copper, palladium and ruthenium catalysts associated to oxidants and DMF were used for the amidation of cinnamic acids [29] and carboxylic acids [55] (Equations (34) and (35)). N,N-Dimethylbenzamide was one of the products obtained from the Cu II -catalyzed oxidation of flavonol [56].
Metal-free conditions and DMF were used for: the amidation of acids promoted with propylphosphonic anhydride associated to HCl at 130 °C (Equation (36)) [15], the amination of acids employing a hypervalent iodine reagent at room temperature (Equation (37)) [35]. Mesityliodine diacetate was superior to the other hypervalent iodine reagents, while oxidants such as I2, t-BuOOH, NaIO4 or K2S2O8 did not mediate the amidation reaction [35].
Metal-free conditions and DMF were used for: the amidation of acids promoted with propylphosphonic anhydride associated to HCl at 130 • C (Equation (36)) [15], -the amination of acids employing a hypervalent iodine reagent at room temperature (Equation (37)) [35]. Mesityliodine diacetate was superior to the other hypervalent iodine reagents, while oxidants such as I 2 , t-BuOOH, NaIO 4 or K 2 S 2 O 8 did not mediate the amidation reaction [35].
Treatment of arylacetic and cinnamic acids with base, sulfur and DMF at 100-120 °C led to decarboxylative thioamidation (Equations (38) and (39)) [7]. Inhibition of the process in the presence of TEMPO or BHT indicated a radical involvement in the transformations.
Various amides have been synthetized from aldehydes and DMF using t-BuOOH and a recyclable heterogeneous catalyst-a carbon-nitrogen embedded cobalt nanoparticle denoted as Co@C-N600 (Equation (41)) [33]. The same transformation of benzaldehydes was subsequently reported using Co/Al hydrotalcite-derived catalysts [58].
Treatment of arylacetic and cinnamic acids with base, sulfur and DMF at 100-120 • C led to decarboxylative thioamidation (Equations (38) and (39)) [7]. Inhibition of the process in the presence of TEMPO or BHT indicated a radical involvement in the transformations. Treatment of arylacetic and cinnamic acids with base, sulfur and DMF at 100-120 °C led to decarboxylative thioamidation (Equations (38) and (39)) [7]. Inhibition of the process in the presence of TEMPO or BHT indicated a radical involvement in the transformations.
Various amides have been synthetized from aldehydes and DMF using t-BuOOH and a recyclable heterogeneous catalyst-a carbon-nitrogen embedded cobalt nanoparticle denoted as Co@C-N600 (Equation (41)) [33]. The same transformation of benzaldehydes was subsequently reported using Co/Al hydrotalcite-derived catalysts [58].
Various amides have been synthetized from aldehydes and DMF using t-BuOOH and a recyclable heterogeneous catalyst-a carbon-nitrogen embedded cobalt nanoparticle denoted as Co@C-N600 (Equation (41)) [33]. The same transformation of benzaldehydes was subsequently reported using Co/Al hydrotalcite-derived catalysts [58].
Various amides have been synthetized from aldehydes and DMF using t-BuOOH and a recyclable heterogeneous catalyst-a carbon-nitrogen embedded cobalt nanoparticle denoted as Co@C-N600 (Equation (41)) [33]. The same transformation of benzaldehydes was subsequently reported using Co/Al hydrotalcite-derived catalysts [58]. Treatment of arylacetic and cinnamic acids with base, sulfur and DMF at 100-120 °C led to decarboxylative thioamidation (Equations (38) and (39)) [7]. Inhibition of the process in the presence of TEMPO or BHT indicated a radical involvement in the transformations.
Various amides have been synthetized from aldehydes and DMF using t-BuOOH and a recyclable heterogeneous catalyst-a carbon-nitrogen embedded cobalt nanoparticle denoted as Co@C-N600 (Equation (41)) [33]. The same transformation of benzaldehydes was subsequently reported using Co/Al hydrotalcite-derived catalysts [58].

Benzyl Amines
The recyclable Co/Al catalysts used above in DMF for the amidation of benzaldehydes also led to benzamides from benzylamines and t-BuOOH (Equation (45)). These transformations would involve benzaldehydes as intermediates [58].

Nitriles
NaOH mediated, at room temperature, the efficient reaction of the CN group of 4-oxo-2,4diphenylbutanenitrile with DMF to afford the corresponding γ-ketoamide (Equation (46)) [63]. Such compounds were also obtained from the domino reaction of chalcones with malononitrile and NaOH in DMF [63].

Benzyl Amines
The recyclable Co/Al catalysts used above in DMF for the amidation of benzaldehydes also led to benzamides from benzylamines and t-BuOOH (Equation (45)). These transformations would involve benzaldehydes as intermediates [58].

Nitriles
NaOH mediated, at room temperature, the efficient reaction of the CN group of 4-oxo-2,4diphenylbutanenitrile with DMF to afford the corresponding γ-ketoamide (Equation (46)) [63]. Such compounds were also obtained from the domino reaction of chalcones with malononitrile and NaOH in DMF [63].

Benzyl Amines
The recyclable Co/Al catalysts used above in DMF for the amidation of benzaldehydes also led to benzamides from benzylamines and t-BuOOH (Equation (45)). These transformations would involve benzaldehydes as intermediates [58].

Nitriles
NaOH mediated, at room temperature, the efficient reaction of the CN group of 4-oxo-2,4diphenylbutanenitrile with DMF to afford the corresponding γ-ketoamide (Equation (46)) [63]. Such compounds were also obtained from the domino reaction of chalcones with malononitrile and NaOH in DMF [63].

Benzyl Amines
The recyclable Co/Al catalysts used above in DMF for the amidation of benzaldehydes also led to benzamides from benzylamines and t-BuOOH (Equation (45)). These transformations would involve benzaldehydes as intermediates [58].

Nitriles
NaOH mediated, at room temperature, the efficient reaction of the CN group of 4-oxo-2,4diphenylbutanenitrile with DMF to afford the corresponding γ-ketoamide (Equation (46)) [63]. Such compounds were also obtained from the domino reaction of chalcones with malononitrile and NaOH in DMF [63].
DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cucarbene complex and the borate salt depicted in Equation (51) [66].
DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cucarbene complex and the borate salt depicted in Equation (51) [66].
DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cucarbene complex and the borate salt depicted in Equation (51) [66].

C=O Fragment
With DMF as the CO surrogate, quinazolinones have been prepared at 140-150 °C via C(sp 2 )-H bond activation and annulation using Pd/C [67] or Pd(OAc)2 [8], in the presence of K2S2O8, CF3CO2H and O2 (Equation (53)), DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cu-carbene complex and the borate salt depicted in Equation (51)  or reaction of sodium sulfonates with N-iodosuccinimide and DMF pretreated with t-BuOK (Equation (48)) via, probably, sulfonyl iodides (Equation (49)) [65].
DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cucarbene complex and the borate salt depicted in Equation (51) [66].
DMF was also the oxygen source leading to an imidazolinone from the reaction with the Cucarbene complex and the borate salt depicted in Equation (51) [66].

C=O Fragment
With DMF as the CO surrogate, quinazolinones have been prepared at 140-150 • C via C(sp 2 )-H bond activation and annulation using Pd/C [67] or Pd(OAc) 2  or carbon dioxide-mediated cyclization of 2-aminobenzonitrile (Equation (54)) [50]. This latter reaction would involve a Vilsmeier-Haack type intermediate and did not occur with DMAc.

C=ONMe 2 Fragment
Potassium persulfate-promoted the reaction of pyridines with DMF to provide N,Ndimethylpicolinamides (Equation (59)) [71], while the oxidative carbamoylation of isoquinoline N-oxides, with also DMF, was catalyzed by Pd II in the presence of ytterbium oxide as base and tetrabutylammonium acetate, the latter mediating the N-O reduction (Equation (60)) [72].

C=ONMe2 Fragment
Potassium persulfate-promoted the reaction of pyridines with DMF to provide N,Ndimethylpicolinamides (Equation (59)) [71], while the oxidative carbamoylation of isoquinoline Noxides, with also DMF, was catalyzed by Pd II in the presence of ytterbium oxide as base and tetrabutylammonium acetate, the latter mediating the N-O reduction (Equation (60)) [72].

C=ONMe2 Fragment
Potassium persulfate-promoted the reaction of pyridines with DMF to provide N,Ndimethylpicolinamides (Equation (59)) [71], while the oxidative carbamoylation of isoquinoline Noxides, with also DMF, was catalyzed by Pd II in the presence of ytterbium oxide as base and tetrabutylammonium acetate, the latter mediating the N-O reduction (Equation (60)) [72].
α-Ketoamides were obtained from the domino reaction of toluenes with DMF using (t-BuO) 2 , Cs 2 CO 3 and catalytic amounts of n-Bu 4 NI (Equation (64)) [75]. At 100 °C in DMF, Cu catalyst associated to t-BuOOH led to unsymmetrical ureas from 2oxindoles (Equation (65)) [76]. The peroxide would mediate the cleavage reaction, and was the oxygen source of the benzylic carbonyl. That resulted in a ketoamine which undergone the Cucatalyzed reaction with DMF/t-BuOOH, leading to the urea.

Cobalt porphyrins catalyzed the hydrogenation transfer from DMF to the C(sp 3 )-C(sp 3 ) bond of [2.2]paracyclophane (Equation
At 100 • C in DMF, Cu catalyst associated to t-BuOOH led to unsymmetrical ureas from 2-oxindoles (Equation (65)) [76]. The peroxide would mediate the cleavage reaction, and was the oxygen source of the benzylic carbonyl. That resulted in a ketoamine which undergone the Cu-catalyzed reaction with DMF/t-BuOOH, leading to the urea. At 100 °C in DMF, Cu catalyst associated to t-BuOOH led to unsymmetrical ureas from 2oxindoles (Equation (65)) [76]. The peroxide would mediate the cleavage reaction, and was the oxygen source of the benzylic carbonyl. That resulted in a ketoamine which undergone the Cucatalyzed reaction with DMF/t-BuOOH, leading to the urea.

H Fragment
Semihydrogenation of diaryl alkynes occurred under Ru (Equation (66)) [77] and Pd [78] catalysis with DMF and water as hydrogen source. At 100 °C in DMF, Cu catalyst associated to t-BuOOH led to unsymmetrical ureas from 2oxindoles (Equation (65)) [76]. The peroxide would mediate the cleavage reaction, and was the oxygen source of the benzylic carbonyl. That resulted in a ketoamine which undergone the Cucatalyzed reaction with DMF/t-BuOOH, leading to the urea.

RCNMe2 Fragment
Dihydropyrrolizino[3,2-b]indol-10-ones were isolated in fair to high yields from a Cs2CO3promoted domino reaction leading to the formation of three bonds with incorporation of the HCNMe of DMF. Such a reaction-type with incorporation of the MeCNMe also occurred in DMAc but with a low yield (Equation (73)) [26].

RCNMe 2 Fragment
Dihydropyrrolizino[3,2-b]indol-10-ones were isolated in fair to high yields from a Cs 2 CO 3promoted domino reaction leading to the formation of three bonds with incorporation of the HCNMe of DMF. Such a reaction-type with incorporation of the MeCNMe also occurred in DMAc but with a low yield (Equation (73)) [26].

RCNMe2 Fragment
Dihydropyrrolizino[3,2-b]indol-10-ones were isolated in fair to high yields from a Cs2CO3promoted domino reaction leading to the formation of three bonds with incorporation of the HCNMe of DMF. Such a reaction-type with incorporation of the MeCNMe also occurred in DMAc but with a low yield (Equation (73)) [26].
Stereoinversion of the secondary alcohols of a number of carbocyclic substrates was carried out via their triflylation followed by treatment with aqueous DMF (Equation (76)) and subsequent methanolysis [85]. A one pot stereoinversion process was reported.
The formyl group of DMF was involved in the triflic anhydride-mediated domino reaction depicted in Equation (77) [86].
Stereoinversion of the secondary alcohols of a number of carbocyclic substrates was carried out via their triflylation followed by treatment with aqueous DMF (Equation (76)) and subsequent methanolysis [85]. A one pot stereoinversion process was reported.
Stereoinversion of the secondary alcohols of a number of carbocyclic substrates was carried out via their triflylation followed by treatment with aqueous DMF (Equation (76)) and subsequent methanolysis [85]. A one pot stereoinversion process was reported.
The formyl group of DMF was involved in the triflic anhydride-mediated domino reaction depicted in Equation (77) [86].
The formyl group of DMF was involved in the triflic anhydride-mediated domino reaction depicted in Equation (77) [86].
The formyl group of DMF was involved in the triflic anhydride-mediated domino reaction depicted in Equation (77) [86].
The formyl group of DMF was involved in the triflic anhydride-mediated domino reaction depicted in Equation (77) [86].

RC and O Fragment
Arynes, which are easily obtained from, for example 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, undergone a [2 + 2] cyclization with DM giving a benzoxetene and its isomer, the orthoquinone methide (Scheme 3). Trapping of these intermediates provides various products, which

RC and O Fragment
Arynes, which are easily obtained from, for example 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, undergone a [2 + 2] cyclization with DM giving a benzoxetene and its isomer, the orthoquinone methide (Scheme 3). Trapping of these intermediates provides various products, which

H and NMe2 Fragment
The reaction of DMF with sodium and subsequent addition of terminal activated alkynes afforded the corresponding hydroamination compounds (Equation (94)) [99].

H and C=ONMe2 Fragment
Semicarbazides have been synthetized from additions, mediated with (t-BuO)2 and catalytic amounts of both NaI and PhCOCl, of the H and CONMe2 moieties of DMF to the extremities of the N=N bond of azoarenes (Equation (95)) [100]. The role of NaI and PhCOCl is not clear and, furthermore, exchange of NaI for imidazole led to formylhydrazines (Equation (96)) [100]. The corresponding acetylhydrazine was not formed in DMAc (Equation (96)). The (t-BuO)2/NaI/PhCOCl/DMF system led to the addition of H and CONMe2 to the N=C bond of Nbenzylideneaniline but with low yield (Equation (97)) [100].

H and NMe 2 Fragment
The reaction of DMF with sodium and subsequent addition of terminal activated alkynes afforded the corresponding hydroamination compounds (Equation (94)) [99].

H and NMe2 Fragment
The reaction of DMF with sodium and subsequent addition of terminal activated alkynes afforded the corresponding hydroamination compounds (Equation (94)) [99].

H and C=ONMe2 Fragment
Semicarbazides have been synthetized from additions, mediated with (t-BuO)2 and catalytic amounts of both NaI and PhCOCl, of the H and CONMe2 moieties of DMF to the extremities of the N=N bond of azoarenes (Equation (95)) [100]. The role of NaI and PhCOCl is not clear and, furthermore, exchange of NaI for imidazole led to formylhydrazines (Equation (96)) [100]. The corresponding acetylhydrazine was not formed in DMAc (Equation (96)). The (t-BuO)2/NaI/PhCOCl/DMF system led to the addition of H and CONMe2 to the N=C bond of Nbenzylideneaniline but with low yield (Equation (97)) [100].

H and C=ONMe 2 Fragment
Semicarbazides have been synthetized from additions, mediated with (t-BuO) 2 and catalytic amounts of both NaI and PhCOCl, of the H and CONMe 2 moieties of DMF to the extremities of the N=N bond of azoarenes (Equation (95)) [100]. The role of NaI and PhCOCl is not clear and, furthermore, exchange of NaI for imidazole led to formylhydrazines (Equation (96)) [100]. The corresponding acetylhydrazine was not formed in DMAc (Equation (96)). The (t-BuO) 2 /NaI/PhCOCl/DMF system led to the addition of H and CONMe 2 to the N=C bond of N-benzylideneaniline but with low yield (Equation (97)) [100].

H and C=ONMe2 Fragment
Semicarbazides have been synthetized from additions, mediated with (t-BuO)2 and catalytic amounts of both NaI and PhCOCl, of the H and CONMe2 moieties of DMF to the extremities of the N=N bond of azoarenes (Equation (95)) [100]. The role of NaI and PhCOCl is not clear and, furthermore, exchange of NaI for imidazole led to formylhydrazines (Equation (96)) [100]. The corresponding acetylhydrazine was not formed in DMAc (Equation (96)). The (t-BuO)2/NaI/PhCOCl/DMF system led to the addition of H and CONMe2 to the N=C bond of Nbenzylideneaniline but with low yield (Equation (97)) [100].

C=ONMe2 and CH Fragment
Couplings between amidines, styrenes and fragments of two molecules of DMF in the presence of t-BuOOH and a Pd II catalyst provided pyrimidine carboxamides (Equation (100)) [105]. DMAc may also be the CH source as exemplified with the formation of the N,N-diethyl-2,4-diphenylpyrimidine-

C=ONMe2 and CH Fragment
Couplings between amidines, styrenes and fragments of two molecules of DMF in the presence of t-BuOOH and a Pd II catalyst provided pyrimidine carboxamides (Equation (100)) [105]. DMAc may also be the CH source as exemplified with the formation of the N,N-diethyl-2,4-diphenylpyrimidine-

C=ONMe 2 and CH Fragment
Couplings between amidines, styrenes and fragments of two molecules of DMF in the presence of t-BuOOH and a Pd II catalyst provided pyrimidine carboxamides (Equation (100)) [105]. DMAc may also be the CH source as exemplified with the formation of the N,N-diethyl-2,4diphenylpyrimidine-5-carboxamide when N,N-diethylformamide was the source of the amide moiety (Equation (101)).

C=ONMe2 and CH Fragment
Couplings between amidines, styrenes and fragments of two molecules of DMF in the presence of t-BuOOH and a Pd II catalyst provided pyrimidine carboxamides (Equation (100)) [105]. DMAc may also be the CH source as exemplified with the formation of the N,N-diethyl-2,4-diphenylpyrimidine-5-carboxamide when N,N-diethylformamide was the source of the amide moiety (Equation (101)).

Reducing or Stabilizing Agent
DMF is a powerful reducing agent of metal salts, hence its use for the preparation of metal colloids [106]. In wet DMF, PdCl2 led to carbamic acid and Pd(0) nanoparticles (Equation (102)) [107]. The latter have been associated with the metal-organic framework Cu2(BDC)2(DABCO) (BDC = 1,4benzenedicarboxylate), leading to a catalytic system with high activity and recyclability for the

Reducing or Stabilizing Agent
DMF is a powerful reducing agent of metal salts, hence its use for the preparation of metal colloids [106]. In wet DMF, PdCl 2 led to carbamic acid and Pd(0) nanoparticles (Equation (102)) [107]. The latter have been associated with the metal-organic framework Cu 2 (BDC) 2 (DABCO) (BDC = 1,4benzenedicarboxylate), leading to a catalytic system with high activity and recyclability for the aerobic oxidation of benzyl alcohols to aldehydes [108] and Suzuki-Miyaura cross-coupling reactions [107]. aerobic oxidation of benzyl alcohols to aldehydes [108] and Suzuki-Miyaura cross-coupling reactions [107].
Thermal decomposition of DMF leads to CO, which reacts with water under CuFe2O4 catalysis to produce hydrogen [113]. In the presence of 2-nitroanilines, this water gas shift reaction was part of a domino reaction involving the reduction of the nitro group followed by cyclisation into benzimidazoles using a CH from the NMe2 of DMF (Equation (108)) [113]. Such cyclisation is above documented under different experimental conditions (Equation (18)) [50].
Thermal decomposition of DMF leads to CO, which reacts with water under CuFe2O4 catalysis to produce hydrogen [113]. In the presence of 2-nitroanilines, this water gas shift reaction was part of a domino reaction involving the reduction of the nitro group followed by cyclisation into benzimidazoles using a CH from the NMe2 of DMF (Equation (108)) [113]. Such cyclisation is above documented under different experimental conditions (Equation (18)) [50].
Thermal decomposition of DMF leads to CO, which reacts with water under CuFe 2 O 4 catalysis to produce hydrogen [113]. In the presence of 2-nitroanilines, this water gas shift reaction was part of a domino reaction involving the reduction of the nitro group followed by cyclisation into benzimidazoles using a CH from the NMe 2 of DMF (Equation (108)) [113]. Such cyclisation is above documented under different experimental conditions (Equation (18)) [50].
Thermal decomposition of DMF leads to CO, which reacts with water under CuFe2O4 catalysis to produce hydrogen [113]. In the presence of 2-nitroanilines, this water gas shift reaction was part of a domino reaction involving the reduction of the nitro group followed by cyclisation into benzimidazoles using a CH from the NMe2 of DMF (Equation (108)) [113]. Such cyclisation is above documented under different experimental conditions (Equation (18)) [50].

Conclusions
This minireview highlights recent uses of DMF and DMAc as sources of building blocks in various reactions of the organic synthesis. We assume that new uses of these multipurpose reagents will be reported.