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Conversion of (1-heterodiene)tricarbonyliron(0) complexes into (2-aminohomodiene)tricarbonyliron(0) complexes
Treatment of (1-azadiene)tricarbonyliron(0) complex 1 with lithiated amines leads to attack at a metal carbonyl and the formation of formamides, whereas complexes 2 and 3 undergo deprotonation of the methyl group at C-2 followed by a rearrangement to form (2-aminohomodiene)tricarbonyliron(0) complexes 8 or 10 in good yield.
Ackland, Mark J.,Danks, Timothy N.,Howells, Mark E.
p. 691 - 694
(1996)
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Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
Zhang, Yanmeng,Zhang, He,Gao, Ke
supporting information
p. 8282 - 8286
(2021/10/25)

Preparation method of formamide compound
The invention belongs to CO. 2 The invention relates to the technical field of activation conversion and related chemistry, and provides a preparation method of a formamide compound, which uses carbon dioxide. The amide compound and phenylsilane are used as raw materials, and the formamide compound is synthesized under the action of the nano porous palladium catalyst. The invention mainly provides a novel simple catalytic system and utilizes CO. 2 C1 The catalytic system has the advantages of mild reaction conditions, simple experiment operation, good functional group compatibility and the like. Because carbon dioxide is abundant, cheap and easily available and renewable C1 , The invention has great application value and social economic benefits.
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Paragraph 0047-0050

(2021/10/27)

Recyclable Oxofluorovanadate-Catalyzed Formylation of Amines by Reductive Functionalization of CO2 with Hydrosilanes
An efficient method has been developed for the reductive amination of CO2 by using readily available and recyclable oxofluorovanadates as catalysts. Various amines are transformed into the desired N-formylated products in moderate to excellent yields at room temperature in the presence of phenylsilane. Mechanistic studies based on in situ infrared spectroscopy suggest a reaction pathway initiated through F?Si interactions. The activated phenylsilane allows for CO2 insertion to produce phenylsilyl formate, which undergoes attack by the amine to generate the target product.
Wu, Shanxuan,Huang, Zijun,Jiang, Xiaolin,Yan, Fachao,Li, Yuehui,Du, Chen-Xia
p. 1763 - 1766
(2021/03/01)

Alcohol promoted N -methylation of anilines with CO2/H2over a cobalt catalyst under mild conditions
N-Methylation of amines with CO2/H2 to N-methylamines over non-noble metal catalysts is very interesting but remains challenging. Herein, we present an alcohol (e.g., ethanol) promoted strategy for the N-methylation of anilines with CO2/H2 with high efficiency under mild conditions (e.g., 125 °C), which is achieved over a cobalt catalytic system composed of Co(OAc)2·4H2O, triphos and Sn(OTf)2. This catalytic system has a broad substrate scope and is tolerant toward a wide range of anilines and N-methyl anilines, and a series of N,N-dimethyl anilines were obtained in high yields. Mechanism investigation indicates that the alcohol solvent shifts the equilibrium of CO2 hydrogenation by forming an alkyl formate, which further reacts with the amine to produce N-formamide, and Sn(OTf)2 promotes the deoxygenative hydrogenation of N-formamides to afford N-methylamines. This is the first example of the N-methylation of amines with CO2/H2 over a cobalt catalytic system, which shows comparable performance to the reported Ru catalysts and may have promising applications.
Han, Buxing,Ke, Zhengang,Li, Ruipeng,Liu, Zhimin,Tang, Minhao,Wang, Huan,Zeng, Wei,Zhao, Yanfei
p. 9147 - 9153
(2021/11/30)

Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines
The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role.
Brückner, Angelika,Dai, Xingchao,Kreyenschulte, Carsten,Rabeah, Jabor,Shi, Feng,Wang, Xinzhi
p. 16889 - 16895
(2021/09/25)

Nickel-Catalyzed Amination of Aryl Chlorides with Amides
A nickel-catalyzed amination of aryl chlorides with diverse amides via C-N bond cleavage has been realized under mild conditions. A broad substrate scope with excellent functional group tolerance at a low catalyst loading makes the protocol powerful for synthesizing various aromatic amines. The aryl chlorides could selectively couple to the amino fragments rather than the carbonyl moieties of amides. Our protocol complements the conventional amination of aryl chlorides and expands the usage of inactive amides.
Li, Jinpeng,Huang, Changyu,Wen, Daheng,Zheng, Qingshu,Tu, Bo,Tu, Tao
supporting information
p. 687 - 691
(2021/01/09)

A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.
Leong, Bi-Xiang,Teo, Yeow-Chuan,Condamines, Cloe,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
p. 14824 - 14833
(2020/12/21)

Engineering Porphyrin Metal-Organic Framework Composites as Multifunctional Platforms for CO2Adsorption and Activation
As an effective solution toward the establishment of a sustainable society, the reductive transformation of CO2 into value-added products is certainly important and imperative. Herein, we report a porphyrin metal-organic framework composite Au@Ir-PCN-222, which is obtained through the in situ formation of Au nanoparticles in the coordination interspaces of Ir-PCN-222. Catalytic results show that Au@Ir-PCN-222 is highly efficient for CO2 reduction and aminolysis, giving rise to formamides in high yields and selectivities under room temperature and atmospheric pressure. Mechanistic studies disclose that the high efficiency of Au@Ir-PCN-222 is due to the synergistic catalysis of Au NPs and Ir-PCN-222, in which Au NPs can adsorb CO2 molecules on their surfaces and then increase the CO2 concentration in the cavities of the framework, and at the same time, Au NPs transfer electrons to Ir-porphyrin units and therefore increase the interactions with CO2 molecules.
Liu, Jiewei,Fan, Yan-Zhong,Zhang, Kun,Zhang, Li,Su, Cheng-Yong
p. 14548 - 14556
(2020/10/13)

Catalyst-free selective: N -formylation and N -methylation of amines using CO2 as a sustainable C1 source
We herein describe catalyst-free selective N-formylation and N-methylation of amines using CO2 as a sustainable C1 source. By tuning the reaction solvent and temperature, the selective synthesis of formamides and methylamines is achieved in good to excellent yields using sodium borohydride (NaBH4) as a sustainable reductant.
Zou, Qizhuang,Long, Guangcai,Zhao, Tianxiang,Hu, Xingbang
supporting information
p. 1134 - 1138
(2020/03/11)

Selective: N-formylation/N-methylation of amines and N-formylation of amides and carbamates with carbon dioxide and hydrosilanes: Promotion of the basic counter anions of the zinc catalyst
A catalyst composed of commercially available Zn(OAc)2 and 1,10-phenanthroline (phen) was effective in the N-formylation/N-methylation of amines using CO2 as the C1 source in the presence of hydrosilanes. An equimolar reaction of N-methylaniline with PhSiH3 under a CO2 atmosphere yielded the N-formylation product in 92% yield at 25 °C. Scale-up of the reaction using 10 mmol substrate was also successful in affording the desired product in 83% yield (1.1 g). This catalyst exhibits a high thermal stability and a turnover number (TON) of 385000 at 150 °C. In addition, the reaction of N-methylaniline in the presence of excess Ph2SiH2 produced N,N-dimethylaniline. Furthermore, our catalytic protocol was developed for the N-formylation of amides and carbamates, which have smaller pKa values and lower reactivities than the corresponding amines. The present Zn(OAc)2/phen catalyst was found to show versatility in the conversion of CO2 and amines into several functionalized organic chemicals under mild conditions. We propose that the basic counter anion (i.e., the acetate) of the catalyst activates both the Si-H and N-H bonds.
Zhang, Qiao,Lin, Xiao-Tao,Fukaya, Norihisa,Fujitani, Tadahiro,Sato, Kazuhiko,Choi, Jun-Chul
supporting information
p. 8414 - 8422
(2020/12/29)

UiO-66 as an efficient catalyst for N-formylation of amines with CO2 and dimethylamine borane as a reducing agent
The most effective way to make the best use of CO2, is the reductive formylation of amines, as formamides have many applications in industry. A new protocol has been developed for reductive N-formylation of amines with CO2 as a C1 carbon source and DMAB (Dimethylamine borane) as a reducing agent in the presence of Zr-containing metal–organic framework (MOF) as an efficient, heterogeneous recyclable catalyst. We used UiO-66 and UiO-66-NH2 as catalysts for N-formylation of amines and observed that both the catalyst performs equally. Therefore, we continued our studies with UiO-66 as a catalyst. The UiO-66 MOF shows good catalytic activity and affording the desired formamides in good to excellent yield. This catalytic system is very efficient for several amines including primary and secondary aliphatic cyclic and aromatic amines. Moreover, the prepared catalyst was recycled up to four recycled without a considerable decrease in catalytic activity.
Phatake, Vishal V.,Mishra, Ashish A.,Bhanage, Bhalchandra M.
supporting information

(2019/12/11)

Zinc Powder Catalysed Formylation and Urealation of Amines Using CO2 as a C1 Building Block?
Transformation of CO2 into valuable organic compounds catalysed by cheap and biocompatible metal catalysts is one of important topics of current organic synthesis and catalysis. Herein, we report the zinc powder catalysed formylation and urealation of amines with CO2 and (EtO)3SiH under solvent free condition. Using 2 molpercent zinc powder as the catalyst, a series of secondary amines, both the aromatic ones and the aliphatic ones, can be formylated into formamides. When primary aromatic amines were used as the substrates, the reactions produce urea derivatives. The electronic and steric effects from the substrates on the formylation and urealation reactions were observed and discussed. The recovery and reusability of zinc powder were investigated, showing the zinc powder can be reused in the formylation reaction without loss of catalytic activity. The analysis on the reactants/products mixture after filtering out the zinc powder showed the zinc concentration in the mixture is low to 1 ppm. The pathways for the formylation and urealation of amines with this catalytic system were also investigated, and related to the different substrates.
Du, Chongyang,Chen, Yaofeng
p. 1057 - 1064
(2020/06/30)

Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
supporting information
p. 5317 - 5324
(2020/09/17)

Graphene oxide: A convenient metal-free carbocatalyst for facilitating amidation of esters with amines
Herein, we report a graphene oxide (GO) catalyzed condensation of non-activated esters and amines, that can enable diverse amides to be synthesized from abundant ethyl esters forming only volatile alcohol as a by-product. GO accelerates ester to amide conversion in the absence of any additives, unlike other catalysts. A wide range of ester and amine substrates are screened to yield the respective amides in good to excellent yields. The improved catalytic activity can be ascribed to the oxygenated functionalities present on the graphene oxide surface which forms H-bonding with the reactants accelerating the reaction. Improved yields and a wide range of functional group tolerance are some of the important features of the developed protocol.
Patel, Khushbu P.,Gayakwad, Eknath M.,Shankarling, Ganapati S.
p. 2661 - 2668
(2020/02/20)

Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2
We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).
Li, Wen-Duo,Zhu, Dao-Yong,Li, Gang,Chen, Jie,Xia, Ji-Bao
supporting information
p. 5098 - 5104
(2019/11/03)

Selective formylation or methylation of amines using carbon dioxide catalysed by a rhodium perimidine-based NHC complex
Carbon dioxide can play a vital role as a sustainable feedstock for chemical synthesis. To be viable, the employed protocol should be as mild as possible. Herein we report a methodology to incorporate CO2 into primary, secondary, aromatic or alkyl amines catalysed by a Rh(i) complex bearing a perimidine-based NHC/phosphine pincer ligand. The periminide-based ligand belongs to a class of 6-membered NHC ligand accessed through chelate-assisted double C-H activation. N-Formylation and -methylation of amines were performed using a balloon of CO2, and phenylsilane as the reducing agent. Product selectivity between formylated and methylated products was tuned by changing the solvent, reaction temperature and the quantity of phenylsilane used. Medium to excellent conversions, as well as tolerance to a range of functional groups, were achieved. Stoichiometric reactions with reactants employed in catalysis and time course studies suggested that formylation and methylation reactions of interest begin with hydrosilylation of CO2 followed by reaction with amine substrates.
Lam, Raphael H.,McQueen, Caitlin M. A.,Pernik, Indrek,McBurney, Roy T.,Hill, Anthony F.,Messerle, Barbara A.
supporting information
p. 538 - 549
(2019/02/14)

Biomass-derived N-doped porous carbon: An efficient metal-free catalyst for methylation of amines with CO2
Developing green, efficient, and low-cost catalysts for methylation of N-H by using CO2 as the C1 resource is highly desired yet remains a significant challenge. Herein, N-doped porous carbons (NPCs) were designed, synthesized, and proved to be an excellent metal-free catalyst for CO2-participated methylation conversion. NPCs were prepared via the pyrolysis of a mixture of tannic acid and urea. Both theoretical calculation and experiment demonstrate that the N species especially pyridinic N and pyrrolic N within NPCs can work as Lewis basic sites for attacking CO2 to weaken the CO bonds and lower the molecule conversion barrier, facilitating the subsequent methylation of N-H to produce, for example, N,N-dimethylaniline. Besides, the unique porous structure can enrich CO2 and accelerate mass transfer, synergistically promoting the conversion of CO2. The optimized NPC(1/5) catalyst, integrating the porous structure and strong Lewis basicity, exhibits excellent catalytic activity for CO2-based methylation reaction under mild conditions (1 bar CO2, 75 °C). Our work, for the first time, demonstrates the feasibility of using NPCs to catalyze the methylation of amino compounds to produce N,N-dimethylamine by exploiting CO2 as the C1 resource.
Tang, Feiying,Wang, Liqiang,Liu, You-Nian
supporting information
p. 6252 - 6257
(2019/12/03)

TBSOTf-promoted versatile N-formylation using DMF at room temperature
Hydrazides and amines were N-formylated by DMF in the presence of tert-butyldimethylsilyl triflate (TBSOTf) at room temperature, in good to excellent yields.
Sakurai, Masayoshi,Kawakami, Rina,Kihara, Nobuhiro
supporting information
p. 1291 - 1294
(2019/04/10)

Palladium-Catalyzed Solvent-Dependent Divergent Synthesis of Benzylformamides
A palladium-catalyzed carbonylative cascade procedure for the synthesis of benzylformamides from aryl halides has been developed. The properties of the solvent chosen play a decisive role on the selectivity of the outcomes. Non-coordinative solvent facilitates the coordination and insertion of CO to the amino-palladium intermediate which then provides the formamides products. While the use of coordinative solvent leads to the formation of amines. A series of functional groups, including ester, ketone, nitro and cyano, were well tolerated under our conditions. The corresponding benzylformamides products were prepared in moderate to good yields without further optimization. (Figure presented.).
Wu, Fu-Peng,Peng, Jin-Bao,Qi, Xinxin,Ying, Jun,Wu, Xiao-Feng
supporting information
p. 3412 - 3417
(2018/08/01)

Porous Organic Polymers with Built-in N-Heterocyclic Carbenes: Selective and Efficient Heterogeneous Catalyst for the Reductive N-Formylation of Amines with CO2
A series of porous organic polymers (POPs) based on N-heterocyclic carbene (NHC) building blocks has been prepared through an octacarbonyldicobalt complex [Co2(CO)8]-catalyzed trimerization of terminal alkyne groups. By changing the monomer ratio in the copolymerization, cross-linked POPs with tunable surface areas of 485–731 m2 g?1 and pore volumes of 0.31–0.51 cm3 g?1 were easily prepared. Compared with the analogues homogeneous NHC (SIPr) catalysts, the POPs exhibited an enhanced catalytic activity and high selectivity in the reductive functionalization of CO2 with amines. The extraordinary performance of the sample could be attributed to the combination of the gas enrichment (or storage) effect, enhanced in-pore concentrations of other substrates, and advantageous micropore structures of the porous polymers. Meanwhile, these catalysts can easily be separated and recycled from the reaction systems with only a slight loss of activity. This excellent catalytic performance and facile recycling of heterogeneous catalysts make them very attractive. These NHC-containing POPs may provide a new platform for catalytic transformations of CO2.
Lv, Hui,Wang, Wenlong,Li, Fuwei
p. 16588 - 16594
(2018/10/24)

Ethanol-mediated N-formylation of amines with CO2/H2 over cobalt catalysts
The CO2-involved synthesis of chemicals is of great significance from a green and sustainable point of view. Herein, we present an efficient Co-based catalytic system composed of a commercially available Co salt, the tetradentate phosphine ligand P-(CH2CH2PPh2)3, and a base, denoted as [Co]/PP3/base, for the synthesis of formamides via the formylation of amines with CO2/H2. It was indicated that the selectivity of products (i.e., formamide or methylamine) could be tuned to some extent via changing the solvent and the base. Using ethanol as the solvent, the Co(ClO4)2·6H2O/PP3/K2CO3 system showed high activity for the production of formamides, affording product yields of 82-95%, together with its broad substrate scope. Exploration of the reaction mechanism indicated that formamide was formed with HCOOH as the intermediate, while the methylamine byproduct was produced with HCHO as the intermediate via the hydrogenolysis of dialkylaminomethane.
Liu, Zhenghui,Yang, Zhenzhen,Ke, Zhengang,Yu, Xiaoxiao,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
p. 13933 - 13937
(2018/08/21)

Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
supporting information
p. 11395 - 11398
(2018/10/20)

N-formylation synthesis method taking CO2 as carbon source under mild condition
The invention provides an N-formylation synthesis method taking CO2 as a carbon source under a mild condition and belongs to the technical field of chemistry and chemical engineering. Under normal-temperature and normal-pressure conditions and in a solvent with a low boiling point, CO2 is used as a carbon source to realize N-formylation reaction of various amine type substrates. The N-formylationsynthesis method provided by the invention has the advantages that a reaction system takes sodium borohydride and ammonium sulfate as reaction reagents, and the CO2 is subjected to reduction under normal pressure to provide acyl, so that high-pressure hydrogen gas and toxic CO are not used and reaction conditions are mild; the sodium borohydride and the ammonium sulfate are cheap and easy to obtain and the economic applicability is high; a reagent is stable in the air and is convenient to operate; the organic solvent with the low boiling point is used and is easy to remove and a product is convenient to separate. A method for preparing formamide, provided by the invention, takes greenhouse gas, i.e., carbon dioxide, as a carbon source and has the advantages of relatively low cost, simplicity in operation and mild reaction conditions; the yield of the prepared formamide product is good and a green synthesis method is provided for N-acylation reaction.
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Paragraph 0026-0028; 0034-0038

(2018/11/03)

Ru@PsIL-Catalyzed Synthesis of N-Formamides and Benzimidazole by using Carbon Dioxide and Dimethylamine Borane
This work reports the synthesis and characterization of ruthenium nanoparticles (Ru NPs) supported on polymeric ionic liquids (PILs). This catalyst shows high catalytic activity towards the N-formylation of amines and synthesis of benzimidazoles from 1,2-diamines and carbon dioxide (CO2) by reductive dehydrogenation of dimethylamine borane. This methodology shows excellent functional group tolerance with broad substrate scope towards the synthesis of N-formamides and benzimidazoles. Interestingly, this protocol also provides the tandem reduction of 2-nitroamines and CO2 to synthesize benzimidazoles. It was proposed that the ionic liquid phase of the polymer plays pivotal roles such as assisting the stabilization of nanoparticles electrostatically, providing an ionic environment, and controlling the easy access of the substrates/reagents to the active sites. The developed methodology utilizes CO2 as a C1 source and water/ethanol as a green solvent system. Additionally, the catalyst was found to be recyclable in nature and shows five consecutive recycling runs without significant loss in its activity.
Saptal, Vitthal B.,Sasaki, Takehiko,Bhanage, Bhalchandra M.
p. 2593 - 2600
(2018/04/30)

DBU-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2 and Polymethylhydrosiloxane
We describe herein an efficient organocatalytic system for the selective N-methylation and N-formylation of amines with carbon dioxide (CO2) as a sustainable C1 feedstock and polymethylhydrosiloxane (PMHS) as a cost-effectvie reducing reagent. High-yielding N-methylation products are obtained with low catalyst loading (1%) of DBU. Selective N-formylation of amines is achieved using the same catalytic system at a lower reaction temperature. (Figure presented.).
Li, Gang,Chen, Jie,Zhu, Dao-Yong,Chen, Ye,Xia, Ji-Bao
supporting information
p. 2364 - 2369
(2018/05/07)

Selective Iron-Catalyzed N-Formylation of Amines using Dihydrogen and Carbon Dioxide
A family of iron(II) carbonyl hydride species supported by PNP pincer ligands was identified as highly productive catalysts for the N-formylation of amines via CO2 hydrogenation. Specifically, iron complexes supported by two different types of PNP ligands were examined for formamide production. Complexes containing a PNP ligand with a tertiary amine afforded superior turnover numbers in comparison to complexes containing a bifunctional PNP ligand with a secondary amine, indicating that bifunctional motifs are not required for catalysis. Systems incorporating a tertiary amine containing a PNP ligand were active for the N-formylation of a variety of amine substrates, achieving TONs up to 8900 and conversions as high as 92%. Mechanistic experiments suggest that N-formylation occurs via an initial, reversible reduction of CO2 to ammonium formate followed by dehydration to produce formamide. Several intermediates relevant to this reaction pathway, as well as iron-containing deactivation species, were isolated and characterized.
Jayarathne, Upul,Hazari, Nilay,Bernskoetter, Wesley H.
p. 1338 - 1345
(2018/02/14)

Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
p. 3615 - 3624
(2018/05/26)

Method for preparing N-formylated amine compounds
The invention discloses a method for preparation N-formylated amine compounds. In the method, the amine compounds and 1,3-dihydroxy acetone are taken as reaction raw materials reacting in a reactor for 2-48 hours at the reaction temperature of 0-100DEG C in a reaction medium in the presence of composite catalysts and oxidants, and the N-formylated amine compounds are obtained. The method is simpleand moderate in reaction conditions, cost can be reduced, target products can be obtained with high yield, and the catalysts used have high catalytic activity and are easy to be separated from a reaction system and reuses; the method is environment friendly during the whole process, the reaction raw materials are easy to be converted from biodiesel by-product propylene glycol, and use of glycerolis facilitated.
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Paragraph 0040; 0048; 0049

(2018/11/03)

Sulfated polyborate-catalyzed N-formylation of amines: a rapid, green and efficient protocol
Abstract: A rapid, green and efficient method for N-formylation reaction of various amines with formic acid in the presence of sulfated polyborate catalyst under solvent-free conditions has been described. The catalyst has the advantage of mild Bronsted as well as Lewis acid character. The catalyst is recyclable with no significant loss in catalytic activity. The present protocol is advantageous due to its solvent-free condition, short reaction time, high yields, easy workup and ability to tolerate a variety of functional groups.
Khatri, Chetan K.,Chaturbhuj, Ganesh U.
p. 2513 - 2519
(2017/11/06)

A capable cobalt nano-catalyst for the N-formylation of various amines and its biological activity studies
The Fe3O4 magnetic nanoparticles (Fe3O4 MNPs) were modified with 1,10-phenanthroline-5,6-diol and the relevant Co complex (Fe3O4@Phendiol@Co) synthesized as a nano-magnetic heterogeneous catalyst to be used for the N-formylation of various amines at room temperature under solvent-free conditions. Also, in order to find the better concept of the catalyst role, the N-formylation reaction was carried out by the use of ultrasound irradiation in the absence of the Co nano-catalyst and the results were compared. The catalyst characterized by different methods such as the elemental analysis (CHN), ICP, FT-IR, XRD, EDX, SEM, TEM, TG-DTA, VSM and XPS. In addition, the antioxidant and the antibacterial activities of the Fe3O4@Phendiol@Co nano-catalyst and its Phendiol ligand were in vitro screened by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging and disc diffusion methods. Results showed that they possess strong antioxidant activity (IC50; 0.182?±?0.006?mg/ml) and good antibacterial potential in comparison to standards.
Habibi, Davood,Heydari, Somayyeh,Afsharfarnia, Mina
(2017/10/06)

NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 as a new and reusable heterogeneous hybrid catalyst for efficient solvent-free formylation of amines
NaY zeolite functionalized by sulfamic acid/Cu(OAc)2 [NaY/SA/Cu(II)] was synthesized and used as a new, efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis. Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
Kazemi, Samira,Mobinikhaledi, Akbar,Zendehdel, Mojgan
p. 1767 - 1772
(2017/07/27)

An efficient reduction of N-substituted carbonylimidazolides into formamides by NaBH4
A novel, simple and versatile protocol was investigated for highly efficient synthesis of formamides through reducing N-substituted carbonylimidazolides by NaBH4 under mild reaction conditions. By this method, not only carboxylic acids or isocyanates, but also amines can readily access formamides with high yields.
Chen, Zhiyong,Cao, Yiming,Tian, Zeyu,Zhou, Xuan,Xu, Wenjin,Yang, Jia,Teng, Hanbing
p. 2166 - 2170
(2017/05/10)

Catalyst-free: N -formylation of amines using BH3NH3 and CO2 under mild conditions
The catalyst-free N-formylation of amines using CO2 as the C1 source and BH3NH3 as the reductant has been developed for the first time. The corresponding formylated products of both primary and secondary amines are obtained in good to excellent yields (up to 96% of isolated yield) under mild conditions.
Zhao, Tian-Xiang,Zhai, Gao-Wen,Liang, Jian,Li, Ping,Hu, Xing-Bang,Wu, You-Ting
supporting information
p. 8046 - 8049
(2017/07/22)

Synthesis of formamides containing unsaturated groups by: N -formylation of amines using CO2 with H2
Formamides have wide applications in the industry and have been synthesized using CO2 as a carbon source and H2 as a reducing agent. However, previous systems required a noble catalyst and high temperature to achieve high efficiency, and the substrate scope was mostly limited to saturated amines. The selective N-formylation of amines containing unsaturated groups using CO2 and H2 is challenging because the efficient catalysts for the N-formylation are usually very active for hydrogenation of the unsaturated groups. Herein, we achieved for the first time a selective and efficient N-formylation of amines containing unsaturated groups using CO2 and H2 with a Cu(OAc)2-4-dimethylaminopyridine (DMAP) catalytic system. The substrates were converted to the desired formamides, while the unsaturated groups, such as the carbonyl group, the CC bond, CN bond and the ester group remained. The main reason for the excellent selectivity of the Cu(OAc)2-DMAP catalytic system was that it was very active for the N-formylation reaction, but was not active for the hydrogenation of the unsaturated groups.
Liu, Hangyu,Mei, Qingqing,Xu, Qingling,Song, Jinliang,Liu, Huizhen,Han, Buxing
supporting information
p. 196 - 201
(2017/08/15)

Novel method for synthesizing N-substitute amide derivative
The invention discloses a novel method for synthesizing an N-substitute amide derivative. The novel method is characterized by comprising the steps that at the air atmosphere, no catalyst or alkali or other any additives are added, an organic amine compound shown in a formula (I) is adopted as a reaction substrate, a solvent shown in a formula (II) is adopted as an acylation reagent, an acylation reaction is performed under the reaction temperature of 120-150 DEG C to generate the N-substitute amide derivative shown in a formula (III), and the equation is shown in the description. The novel method has the advantages that environmental protection is achieved, and post-treatment and product separation are easy; the range of the substrate is wide, and the substrate can be primary amine and can also be secondary amine; the solvent can be amide and can also be carboxylic acid, and the solvent can be adopted as the acylation reagent to participate in the reaction; the reaction efficiency is high, and the majority of reactions can reach the quantified yield; water and air have no effect on the reaction, inert gas shielding is not needed, and operation is easy.
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Paragraph 0035; 0036; 0037; 0038; 0039; 0040-0041; 0107-0109

(2017/09/02)

Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions
Herein, formylation of structurally different amines and alcohols with ethyl formate was carried out in the presence of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)-encapsulated Fe3O4 nanoparticles as a heterogeneous, recyclable, and greatly efficient catalyst; this method provided the corresponding N-formyl compounds in good to excellent yields under solvent-free conditions. The magnetically catalytic system was recovered, by-passing the time-consuming filtration operation using an external magnet device. This procedure also increases the purity of the product and promises economic and ecological advantages. Furthermore, the recovery and reuse of the catalyst was demonstrated five times without detectable loss in the activity.
Taheri, Sepideh,Veisi, Hojat,Hekmati, Malak
p. 5075 - 5081
(2017/07/11)

Amide-ligand-controlled highly para-selective arylation of monosubstituted simple arenes with arylboronic acids
Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.
Luan, Yu-Xin,Zhang, Tao,Yao, Wei-Wei,Lu, Ke,Kong, Lu-Yao,Lin, Yu-Tong,Ye, Mengchun
supporting information
p. 1786 - 1789
(2017/02/15)

Preparation method of the formamide
The invention relates to a preparation method of methanamide. The method uses formamide or its derivative and amine (primary or secondary amine) as reactants, which are subjected to amidomethylation in the presence of a catalyst to prepare methanamide. The method is characterized in that solid acidic metal oxide or precious metal loaded acidic metal oxide is used as the catalyst and the reaction is carried out efficiently under mild conditions. The reaction process is as follows: mixing formamide with certain concentration or its derivatives with primary or secondary amine and a certain amount of catalyst, placing the mixture into pressure vessel without adding or additionally adding other solvent, sealing, stirring at a temperature no less than 60 DEG C, and reacting for no less than 0.5 h to obtain the reaction product methanamide. The method has the advantages of simple preparation of the catalyst, easy separation process of the catalyst and product, repeated usage of the catalyst, high controllability of the reaction process, and yield of the product formamide reaching more than 95%.
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Paragraph 0037; 0038; 0052

(2017/07/01)

Iron-Catalyzed Amide Formation from the Dehydrogenative Coupling of Alcohols and Secondary Amines
The five-coordinate iron(II) hydride complex (iPrPNP)Fe(H)(CO) (iPrPNP = N[CH2CH2(PiPr2)]2) selectively catalyzes the dehydrogenative intermolecular coupling of alcohols and secondary amines to form tertiary amides. This is the most productive base-metal catalyst for dehydrogenative amidation reported to date, in some cases achieving up to 600 turnovers. The catalyst works well for sterically undemanding amines and alcohols or cyclic substrates and is particularly effective in the synthesis of formamides from methanol. However, the catalyst performance declines rapidly with the incorporation of large substituents on the amine or alcohol substrate. Variable-temperature NMR spectroscopic studies suggest that the catalyst resting state is an off-cycle iron(II) methoxide species, (iPrPN(H)P)Fe(H)(OCH3)(CO), resulting from addition of methanol across the Fe-N bond of (iPrPNP)Fe(H)(CO). This reversibly formed iron(II) methoxide complex is favored at mild temperatures but eliminates methanol upon heating.
Lane, Elizabeth M.,Uttley, Katherine B.,Hazari, Nilay,Bernskoetter, Wesley
p. 2020 - 2025
(2017/06/13)

Method for preparing carboxamide
The invention relates to a preparation method of methanamide. The method uses primary amine or secondary amine and CO as reactants, which are subjected to carbonylation reaction in the presence of a catalyst to prepare methanamide. The method is characterized in that precious metal loaded acidic metal oxide is used as the catalyst and the reaction is carried out efficiently under mild conditions. The reaction process is as follows: mixing primary amine or secondary amine with certain concentration with a certain amount of the catalyst, introducing CO, sealing, stirring at a temperature higher than 100 DEG C, and reacting for more than 2 h to obtain the methanamide. The method has the advantages of simple preparation of the catalyst, easy separation process of the catalyst and product, repeated usage of the catalyst, high controllability of the reaction process, and yield of the product formamide reaching more than 90%.
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Paragraph 0032; 0033

(2017/03/28)

Copper-catalyzed N-formylation of amines with CO2 under ambient conditions
We carried out work on N-formylation of amines with CO2 and PhSiH3 to produce formamides catalyzed by a copper complex. It was found that the Cu(OAc)2-bis(diphenylphosphino)ethane (dppe) catalytic system was very efficient for these kind of reactions at room temperature and 1 atm CO2 with only 0.1 mol% catalyst loading.
Zhang, Suqi,Mei, Qingqing,Liu, Hangyu,Liu, Huizhen,Zhang, Zepeng,Han, Buxing
p. 32370 - 32373
(2016/04/26)

Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkali-Metal carbonates
The formylation and methylation of amines with carbon dioxide and hydrosilanes are emerging yet important types of transformations for CO2. Catalytic methods effective for both reactions with wide substrate scopes are rare because of the difficulty in controlling the selectivity. Herein, we report that simple and readily available inorganic bases alkali-metal carbonates, especially cesium carbonatecatalyze both the formylation and methylation reactions efficiently under mild conditions. The selectivity can be conveniently controlled by varying the reaction temperature and silane. A “cesium effect” on both reactions was observed by comparing the catalytic activity of various alkali-metal carbonates. Combined experimental and computational studies suggested the following reaction mechanism: (i) activation of Si?H by Cs2CO3, (ii) insertion of CO2 into Si?H, (iii) formylation of amines by silyl formate, and (iv) reduction of formamides to methylamines.
Fang, Chi,Lu, Chunlei,Liu, Muhua,Zhu, Yiling,Fu, Yao,Lin, Bo-Lin
p. 7876 - 7881
(2018/05/23)

Solvent-promoted catalyst-free: N -formylation of amines using carbon dioxide under ambient conditions
An unprecedented catalyst-free formylation of amines using CO2 and hydrosilanes was developed. The solvent plays a vital role in promoting the interaction of amines with hydrosilanes and subsequent CO2 insertion, thus facilitating the simultaneous activation of N-H and Si-H bonds. Based on relevant mechanistic studies, a plausible mechanism involving a silyl carbamate intermediate is proposed.
Lv, Hui,Xing, Qi,Yue, Chengtao,Lei, Ziqiang,Li, Fuwei
supporting information
p. 6545 - 6548
(2016/06/01)

Chelating Bis(1,2,3-triazol-5-ylidene) Rhodium Complexes: Versatile Catalysts for Hydrosilylation Reactions
NHC-rhodium complexes (NHC=N-heterocyclic carbenes) have been widely used as efficient catalysts for hydrosilylation reactions. However, the substrates were mostly limited to reactive carbonyl compounds (aldehydes and ketones) or carbon-carbon multiple bonds. Here, we describe the application of newly-developed chelating bis(tzNHC)-rhodium complexes (tz=1,2,3-triazol-5-ylidene) for several reductive transformations. With these catalysts, the formal reductive methylation of amines using carbon dioxide, the hydrosilylation of amides and carboxylic acids, and the reductive alkylation of amines using carboxylic acids have been achieved under mild reaction conditions.
Nguyen, Thanh V. Q.,Yoo, Woo-Jin,Kobayashi, Shu
supporting information
p. 452 - 458
(2016/02/12)

An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions
A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO2 and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.
Nale, Deepak B.,Bhanage, Bhalchandra M.
p. 1413 - 1417
(2016/05/24)

Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions
This work reports an amine modified meso Al2O3@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO2) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al2O3@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO2 pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.
Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
p. 4872 - 4881
(2016/07/07)

Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions
A simple and efficient Au/Al2O3 catalyst was prepared by the co-precipitation method for the oxidative N-formylation of amines with paraformaldehyde. Under the optimized reaction conditions, excellent amine conversion and N-formamide selectivity can be obtained with up to 97% yield with water as the solvent under ambient conditions. This catalyst tolerated a wide range of primary amines and second amines, and it can be reused for at least five runs without obvious deactivation.
Ke, Zhengang,Zhang, Yan,Cui, Xinjiang,Shi, Feng
p. 808 - 816
(2016/02/12)

A Practical and General Base-Catalyzed Carbonylation of Amines for the Synthesis of N-Formamides
A highly practical and general base-catalyzed carbonylation of amines to the corresponding N-formamides has been realized. Cheap inorganic bases, including GroupIA and IIA metal hydroxides, alkoxides, carbonates, and phosphates, were effective catalysts for the transformation. In the presence of 10-40mol% of KOH or K2CO3, various amines were converted into the corresponding N-formamides in good-to-excellent yields using CO as the formylation reagents. Metal-free carbonylation: A simple and practical procedure for the catalytic carbonylation of amines has been developed (see scheme). In the presence of 10-40mol% of KOH or K2CO3, various amines have been converted into the corresponding N-formamides in good-to-excellent yields by using CO as the formylation reagent.
Li, Wanfang,Wu, Xiao-Feng
supporting information
p. 14943 - 14948
(2015/10/19)

Preparation of conformationally restricted β2,2- and β2,2,3-amino esters and derivatives containing an all-carbon quaternary center
β-Amino acids are routinely incorporated into peptidic drugs to increase their stability and to incur conformational biases. However, the synthesis of highly substituted β-amino acids still represents a great challenge. A new approach to their preparation is reported involving a Vilsmeier-Haack reaction with nonaromatic carbon nucleophiles. The highly challenging preparation of contiguous tertiary and all-carbon quaternary centers was successfully used to generate several β2,2,3-amino esters, such as derivatives of homoproline, homoalanine, and homopipecolinic esters.
Romanens, Alexandre,Blanger, Guillaume
supporting information
p. 322 - 325
(2015/01/30)

Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis(tzNHC) Rhodium Complexes
The reductive formylation of amines using CO2 and hydrosilanes is an attractive method for incorporating CO2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N-heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO2 and Ph2SiH2. A rhodium-based bis(tzNHC) complex (tz=1,2,3-triazol-5-ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible. Beyond the norm: Rhodium complexes bearing a strong electron-donating bis(1,2,3-triazol-5-ylidene) ligand were found to be excellent catalysts for the reductive formylation of amines with CO2 and Ph2SiH2 at ambient temperature. The catalyst system possesses a broad substrate scope which tolerates a variety of reducible functional groups and is suitable for the synthesis of bioactive compounds. Tf=trifuoromethanesulfonyl.
Nguyen, Thanh V. Q.,Yoo, Woo-Jin,Kobayashi
supporting information
p. 9209 - 9212
(2015/08/06)