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Article

Oxidative N-Formylation of Secondary Amines Catalyzed by Reusable Bimetallic AuPd–Fe3O4 Nanoparticles

by
Sabyuk Yang
,
Ahra Cho
†,
Jin Hee Cho
† and
Byeong Moon Kim
*
Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 08826, Korea
*
Author to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Nanomaterials 2021, 11(8), 2101; https://doi.org/10.3390/nano11082101
Submission received: 12 July 2021 / Revised: 9 August 2021 / Accepted: 16 August 2021 / Published: 18 August 2021
(This article belongs to the Special Issue Synthesis of Nanocomposites and Catalysis Applications)
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Abstract

:
Bimetallic catalysts are gaining attention due to their characteristics of promoting reactivity and selectivity in catalyzed reactions. Herein, a new catalytic N-formylation of secondary amines using AuPd–Fe3O4 at room temperature is reported. Methanol was utilized as the formyl source and 1.0 atm of O2 gas served as an external oxidant. The bimetallic catalyst, consisting of Au and Pd, makes the reaction more efficient than that using each metal separately. In addition, the catalyst can be effectively recycled owing to the Fe3O4 support.

Graphical Abstract

1. Introduction

Formamide groups are important in organic chemistry because of their abundance in natural products or utility as a valuable intermediate in synthesis (Scheme 1a), and pharmaceuticals (Scheme 1b) [1]. For example, this moiety is found in N-formylloline, an alkaloid produced by grass [2], and acts as an intermediate in biochemical processes, such as methanogenesis [3]. Some examples of formamide-containing drugs are benfotiamine (diabetic neuropathy) [4], leucovorin (toxic effects of methotrexate and pyrimethamine) [5], vincristine (anticancer) [6], and fursultiamine (thiamine deficiency) [7]. Considering the prevalence and importance of the formamide functionality, many researchers have developed efficient methods for attaching a formyl group to an amine [8,9,10]. One of the most direct methods to synthesize formamides is the direct N-formylation of amines with a formate ester, organosilicon reagent, formic acid or cyanide [8,9,11,12,13,14]. However, this process generates halide byproducts, and more environmentally friendly methods using green formyl sources have been actively pursued [15,16,17].
Among formyl sources, methanol is an ideal C1 source because of its availability and ecofriendly properties compared with other reagents [18,19]. It is one of the most popular C1 sources in organic reactions, such as methylation [20,21,22,23,24], formylation [25,26,27], and methoxylation [28,29,30], forming C–C, C–N, and C–O bonds, respectively. Therefore, developing a new catalytic route for the synthesis of formamides with methanol as a sustainable building block would be a valuable addition to the synthetic toolbox.
Currently, there are a handful of catalytic N-formylation reactions of amines with methanol in the literature (Scheme 2). Both homogeneous and heterogeneous catalysts have been widely used for this transformation. Homogeneous catalysts are one of the most popular tools, owing to their high reactivities (Scheme 2a) [31,32,33]. For example, Glorius and coworkers reported the N-formylation of amines catalyzed by the Ru–NHC catalyst in 2013 [34]. In 2017, the Milstein group achieved the acceptorless dehydrogenative coupling of methanol and amines using a manganese catalyst [35]. Hong and coworkers reported the N-formylation of amines with methanol in the presence of ruthenium catalysts in 2015 and 2019 [36,37]. In addition to these representative examples, various transition metal catalysts have been employed in N-formylation [38,39,40,41,42,43,44]. However, despite their merits, homogeneous catalysts are generally difficult to recover and show low stability compared to heterogeneous catalysts. Therefore, heterogeneous catalysts have been considered as alternatives because of their recyclability and ease of handling (Scheme 2b) [26,45,46,47]. Au-containing heterogeneous catalysts have often been employed as highly efficient catalysts for the oxidation of alcohols and their coupling reactions with other reactants [48,49,50,51].
For example, in 2009, Sakurai and coworkers reported the N-formylation of anilines using Au nanoclusters stabilized by poly(N-vinylpyrrolidone) (Au:PVP) [52]. In the same year, Ishida et al. developed the N-formylation of benzylamine using supported Au nanoparticles, such as Au/NiO or Au/Al2O3 [53]. Using hydrogen peroxide as an oxidant, Reddy developed the room-temperature N-formylation of amines using a copper catalyst [54]. In 2013, the reaction of aliphatic amines using AuNPore under 1.0 atm of O2 gas was developed by Tanaka et al. [55]. However, most of these reactions require high temperatures or high O2 gas pressures. Therefore, the development of a simple experimental procedure under relatively mild conditions is still required.
Based on our continuous efforts toward the development of metal nanoparticle–Fe3O4 catalysts, such as Pd–Fe3O4 [56], we developed a series of heterogeneous transition metal nanocatalysts for efficient organic transformations [57,58,59,60,61,62]. In particular, bimetallic combinations of various transition metals on an Fe3O4 support have been very useful catalysts for efficient, selective organic transformations [63,64,65,66,67]. Because Au nanoparticle catalysts have been widely used in a variety of oxidative reactions, we prepared bimetallic AuPd–Fe3O4 nanoparticle catalysts for selective redox reactions and developed the efficient reductive amination of nitroarenes and aldehydes [65] and oxidative conversion of 5-hydroxymethylfurfural to furan-2,5-dimethylcarboxylate [66].
Herein, we report a new and efficient protocol for secondary amine N-formylation through methanol oxidation, using AuPd–Fe3O4 as a reusable catalyst (Scheme 2c). Methanol serves not only as the formylating agent, but also as the solvent, and the reaction proceeds at room temperature under 1.0 atm of O2 gas as an external oxidant.

2. Materials and Methods

All commercially available chemicals were used as received without further purification. HAuCl4·3H2O (+49% Au basis) and PdCl2 (99% purity) were purchased from Alfa Aesar (Ward Hill, MA, USA). N-methyl-1-phenylmethanamine and polyvinylpyrrolidone (PVP) were purchased from Sigma-Aldrich (St. Louis, MO, USA). Cesium hydroxide monohydrate was purchased from Acros Organics (Pittsburgh, PA, USA). Fe3O4 NPs were purchased from DK nano technology (Beijing, China).

3. Results

3.1. Catalyst Characterization

The bimetallic AuPd–Fe3O4 catalyst was synthesized following a procedure previously developed in our laboratories [65]. Adding palladium(II) chloride (PdCl2) in ethylene glycol, gold(III) chloride trihydrate (HAuCl4·3H2O) in water, and aqueous sodium borohydride solution dropwise sequentially to a Fe3O4 solution in water and stirring under 60 °C for 5 h afforded AuPd–Fe3O4 nanoparticles. These were characterized by scanning electron microscopy (SEM, Figure S1) by JSM-7800F Prime (JEOL Ltd., Tokyo, Japan), energy-dispersive X-ray spectroscopy (EDS, Figures S2 and S3) by JSM-7800F Prime (JEOL Ltd., Tokyo, Japan), high-resolution transmission electron microscopy (HR-TEM, Figures S4 and S6) by JEM-3010 (JEOL Ltd., Tokyo, Japan), scanning transmission electron microscopy (STEM, Figure S5) by JEM-ARM200F (JEOL Ltd., Tokyo, Japan), and X-ray photoelectron spectroscopy (XPS, Figure S7) by AXIS SUPRA (Kratos Analytical Ltd., Manchester, UK). The binding energy peaks of Pd 3d in Pd–Fe3O4 were positioned at 339.8 and 334.6 eV, corresponding to Pd(0) species. Au 4f peaks appeared at 86.9 and 83.3 eV for Au–Fe3O4, indicating the presence of Au(0) species. For AuPd–Fe3O4, the Pd 3d peaks appeared at 339.6 and 334.3 eV and the Au 4f peaks appeared at 86.8 and 83.1 eV, slightly lower than those of the corresponding monometallic nanoparticles. This phenomenon appears to stem from the interaction of Pd and Au, changing the electronic structure because of the formation of an AuPd alloy [68,69,70,71]. The lowered binding energy of Au(0) is expected to result from the electron transfer from Pd to Au. However, the reason why the Pd(0) peak shifted to a slightly lower value is not fully understood. SEM, HR-TEM, and STEM images show that Au and Pd were successfully deposited as an alloy on the iron oxide support (Figure 1 and Figure 2a and Figure S5), with the Au and Pd atoms randomly distributed. AuPd–Fe3O4 X-ray diffraction (XRD) data obtained by D8 Advance (Bruker, Billerica, MA, USA) compared with those of both Au–Fe3O4 and Pd–Fe3O4 revealed that the AuPd–Fe3O4 is made up with Au−Pd bimetallic alloy dispersed on the Fe3O4 surface (Figure 2b and Figure S9). Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) data obtained by OPTIMA 8300 (Perkin-Elmer, Waltham, MA, USA) revealed that the AuPd–Fe3O4 nanoparticles (NPs) consist of 8.92 wt% Au and 5.19 wt% Pd at a molar ratio of 1.00:1.08 (Figure S8).

3.2. Reaction Optimization

Following successful preparation of AuPd–Fe3O4, we sought the optimum reaction conditions for the N-formylation of amines under oxidative conditions. We chose methanol as the formyl group source because it can be readily oxidized to formaldehyde, forming an hemiaminal upon reaction with an amine. We hypothesized that the resulting hemiaminal could be further oxidized to an N-formyl group under catalytic oxidation conditions with AuPd–Fe3O4 catalyst.
Because the formylation of amine by methanol requires the oxidation of methanol to an hemiaminal and subsequent dehydrogenation of the hemiaminal, an appropriate oxidant should be selected. Various oxidants have been used for alcohol oxidation [72,73,74]. O2 gas was chosen as the oxidizing agent to avoid chemical waste problems [75,76,77,78,79,80,81].
Initially, a primary amine, such as benzylamine, was mixed with 1.4 mol% of AuPd–Fe3O4 (2.8 mol% of total metal contents except for Fe) and methanol under 1.0 atm of O2 gas, but no N-benzylformamide product was detected, while the starting material remained. Subsequently, we added 3.0 equivalents of sodium hydroxide, which led to the formation of N-benzylformamide in 25% yield after 18 h. In addition, several unknown high-molecular-weight products, along with a small amount of benzonitrile, were detected from liquid chromatography-mass spectrometry (LC-MS) analysis of the crude mixture. These results suggest that the base plays an important role in the conversion of the amine substrate. According to a report from Mallat group [75], bases are known to facilitate hydrogen abstraction in alcohol dehydrogenation with Au catalysts. However, because the reaction of a primary amine did not yield a clean formylation product, we focused our attention on the formylation of secondary amines. Our first reaction of N-methyl-1-phenylmethanamine with methanol, in the presence of AuPd–Fe3O4 with sodium hydroxide as a base, yielded the desired N-benzyl-N-methylformamide in 65% NMR yield (Scheme 3).
Based on these initial findings, various reaction conditions were tested, and the results are presented in Table 1 and Tables S1– S3. Using N-methyl-1-phenylmethanamine (1a) as a standard substrate, we tested various reaction conditions with methanol as the formylating agent. Using only iron oxide as a catalyst and sodium hydroxide as a base resulted no progress of the reaction at all (entry 1). However, a reaction with 2.8 mol% Pd–Fe3O4 catalyst furnished N-benzyl-N-methylformamide (2a) at a 55% yield (entry 2). Reactions with other monometallic catalysts, such as Au–Fe3O4, showed low reactivity (entry 3). The use of the AuPd–Fe3O4 bimetallic catalyst afforded the product in 65% yield (entry 4). Without a base, the reaction was sluggish (entry 5). When the O2 balloon was replaced with an air balloon, the reactivity lowered to afford the desired product at only 43% yield (entry 6). By changing the base to cesium carbonate, we observed a yield similar to that of the reaction using sodium hydroxide (entry 7). However, other inorganic bases were not as effective as hydroxide bases. The reaction using cesium hydroxide monohydrate afforded 90% yield under the same conditions (entry 8). Furthermore, the reaction yield was maintained when the reaction was scaled up to 0.50 mmol (entry 9). The reaction was complete in 4 h when the substrate concentration was increased from 0.20 to 1.0 M, resulting in 89% yield (entry 10). A reaction using ethanol instead of methanol afforded the acetylated product in 42% yield (entry 11). The catalyst loading could be low as 0.40 mol% without significant loss of yield, which is translated to high turnover number (TON) (entry 12 and Table S3).
Knowing that hydroxide bases were effective, we performed further investigations with bases (Table 2 and Table S2). Without a base, only 14% yield of 2a was obtained (entry 1). Reactions employing LiOH·H2O and NaOH resulted in 60% and 65% yields, respectively, of the desired products (entries 2 and 3). The use of slightly stronger hydroxide bases, such as KOH or CsOH·H2O, ensured 75% and 91% yields, respectively (entries 4 and 5). However, carbonate bases were not as effective as hydroxide bases (entries 6 and 7). Reaction yields obtained with other bases, including KOtBu, K3PO4, and CsF, were moderate (entries 8–10). In summary, CsOH·H2O was the optimal base.

3.3. Effect of Alloy Bimetallic Catalyst vs. Combination of Two Metal Catalysts

To investigate the distinctive advantage of the bimetallic nanocatalyst, several control experiments were conducted (Table 3). Because we used 1.4 mol% of AuPd–Fe3O4 to obtain the optimum results with 1a, reactions with 2.8 mol% of either Au–Fe3O4 (entry 1) or Pd–Fe3O4 (entry 2) were performed under the standard reaction conditions to test the reactivity of each monometallic catalyst. The N-formylation reactions of N-methyl-1-phenylmethanamine, employing either Au or Pd catalysts, were not as efficient as that employing the AuPd catalyst (entry 4), giving 51% and 57% yields of 2a, respectively. To further investigate the alloy nanocatalyst, we examined the reactions of other substrates, such as N-methyl-1-(p-tolyl)methanamine, 1-(4-methoxyphenyl)-N-methylmethanamine, N-methyl-1-(3-nitrophenyl)methanamine, and 3-(methylaminomethyl)benzonitrile. With 2.8 mol% of Au–Fe3O4 (entry 1) or 2.8 mol% of Pd–Fe3O4 (entry 2), the reactions of secondary amines showed lower yields than those using AuPd–Fe3O4 (entry 4). These results indicate that both Au and Pd within the alloy catalyst contribute to product formation through a synergistic effect [82,83,84,85,86]. When we used 1.4 mol% each of both Au–Fe3O4 and Pd–Fe3O4, interestingly the reaction of N-methyl-1-phenylmethanamine afforded 90% yield of the desired product (entry 3). The fact that similar product yields were obtained from the reactions employing AuPd and the combination of the Au and Pd toward N-methyl-1-phenylmethanamine was an exception rather than a general trend, as can be seen in the reactions of various substituted N-methylarylmethanamines. Reactions of other substrates with both Au–Fe3O4 and Pd–Fe3O4 provided the corresponding products with much lower yields than those obtained with the bimetallic AuPd catalyst. To rule out the possibility of homogeneous catalysis with both Au and Pd leached out into the solution, we carried out a filtration experiment [59,60]. The solution from a reaction of N-methyl-1-phenylmethanamine with 1.4 mol% AuPd-Fe3O4 under the optimized condition after 0.5 h was filtered through a syringe filter. The filtrated solution was then stirred for 6 h under O2 atmosphere, and the progress of the reaction was checked. There was no further increase in the reaction yield. This result shows that the homogeneous solution did not drive the reaction further without the nanocatalyst, indicating that there is no catalysis from any homogeneous metal species. Next, we also tested the kinetics in the reaction of N-methyl-1-phenylmethanamine, employing either Au, Pd, a mixture of Au and Pd, or AuPd catalyst (Figure S14). The differences in the reaction rates indicate that there is a distinctive synergistic effect within the bimetallic catalyst, as the reaction employing this catalyst proceeded the fastest. Thus, considering both the product yields and the initial kinetics, there is an advantage in employing the bimetallic alloy catalyst, instead of using the monometallic catalysts separately.

3.4. Substrate Scope

Using the optimized condition, we tested the N-formylation of various secondary amines bearing substituted aromatic rings, using 0.25 M of substrate over 18 h (Scheme 4). From the reaction of unsubstituted N-methyl-1-phenylmethanamine, N-formylated product was obtained in 84% (2a). Substrates bearing a methyl group on the aromatic ring furnished a good product yield, regardless of its position (2b–2d). Reactivity was maintained in the case of a substrate with two methyl groups on the aromatic ring (2e). High yield (87%) was also observed from a sterically hindered substrate possessing methyl groups at positions 2 and 6 (2f) when the reaction was run at 0.20 M (0.20 mmol scale). The reactions of substrates possessing a strong electron-donating methoxy group resulted in good yields (81% and 83%, 2g and 2h, respectively). The reaction of N-methyl-1-(naphthalen-1-yl)methanamine also resulted in good yield (80%, 2i). When an electron-withdrawing group exists on the aromatic ring, good to moderate yields of the desired products were obtained (85%, 83%, 61% and 58% for 2l–2o, respectively). Reactions of substrates bearing fluorine(s) resulted in acceptable product yields (73% and 79% for 2j and 2k, respectively). Interestingly, reactions of amines with trifluoromethyl groups at the 3 or 4 position on the aromatic ring furnished good yields (85%, 83%, and 75% for 2l, 2m, and 2q, respectively) compared with other electron-deficient amines. Reactions of substrates possessing other electron-withdrawing substituents, such as nitro- or cyano- groups, yielded products with 61% and 58% yields (2n and 2o), respectively. In addition, the reaction of N-methylaniline resulted in the desired formylated product in 82% yield (2p). We confirmed that not only N-methylamines, but other N-alkyl-substituted secondary amines are also good substrates for the reaction, as shown in the case of 2q and 2r, with the reaction of N,N-dibenzylamine, resulting in 73% yield (2r). In the reactions of non-benzylic secondary alkylamines, products were obtained in moderate yields (55%, 57%, and 66%, 2s–2u, respectively). We hypothesized that the reactions could be run at higher concentrations and thus expedited. When reactions were conducted at 1.0 M, most were completed in 6–8 h instead of 18 h at 0.20 M. The reactions of several substrates maintained their yields at higher concentrations in shorter reaction times, and the results are shown in the (supporting information Table S6).

3.5. Mechanistic Investigation

Based on the results of optimization and the substrate scope investigation, we conducted several kinetic experiments and control experiments to probe the reaction mechanism (Figures S15 and S16, and Table S7). To summarize the results, the amine substrate (1) is consumed under oxidative condition in the presence of AuPd–Fe3O4 catalyst in methanol. The oxidation of methanol in the presence of the catalyst by the assistance of a base generates mostly HCHO and a small portion of HCO2Me, which rapidly react with an amine to furnish N-formamide (2). The formation of HCO2H from methanol was ruled out because almost no HCO2H was detected from the control oxidation of methanol. Both methanol and the resulting hemiaminal intermediate (3) are oxidized by the AuPd–Fe3O4 catalyst. These results are presented in Scheme 5.

3.6. Effect of Au:Pd Ratio and Various Supports

To further investigate the correlation between the Au:Pd ratio and the product yield, we synthesized catalysts with various Au:Pd ratios and tested them using 2.0 mol% of catalyst under the same reaction condition (Table 4 and Figure S10). The ~1:1 atomic ratio of Au and Pd was found to be the best combination. Additionally, to test the effect of iron oxide, we synthesized several AuPd catalysts with various supports for comparison (Tables S4 and S5 and Figure S13). AuPd on the iron oxide support showed the highest reactivity for N-formylation.

3.7. Recycling Test

Because heterogeneous catalysts are employed for easy recovery and reuse, the recyclability of AuPd–Fe3O4 was tested based on the optimized condition (Figure 3). In the recycling experiment with 1a, the catalytic activity was maintained without significant loss of yield. Based on our previous report [66], a strong base disintegrates the iron oxide support, resulting in poor recyclability. However, the catalytic activity was somehow maintained for 9 cycles. When the SEM and HR-TEM images of the catalyst after 10 cycles were examined, Au and Pd particles appeared to be significantly agglomerated (Figures S11 and S12). Additionally, the ICP-AES data of the used catalyst showed lower Au and Pd contents (wt%) (Figure S8). Therefore, considering the excess amount of strong base and oxidative environment that can be detrimental to the catalyst, our reaction system has some reusability advantages.

3.8. Gram Scale Reaction

We subsequently performed a gram-scale reaction (Scheme 6). At a 10 mmol scale, the reaction of 1r afforded 2r in 72% yield, demonstrating the viability of the reaction in organic synthesis.

4. Conclusions

In conclusion, we developed a novel catalytic system for the mild synthesis of formamides in good-to-moderate yields. Utilizing a reusable AuPd bimetallic nanocatalyst, we synthesized formamides at room temperature under atmospheric pressure of O2. The use of methanol as the formyl source, instead of toxic or polluting reagents, bodes well for sustainable organic synthesis. During the investigation of various catalysts, the bimetallic alloy AuPd–Fe3O4 catalyst proved to be superior to either of the monometallic catalysts. Based on the product yield and initial kinetics, there appears to be a synergistic effect between the Au and Pd during the reaction. The broad substrate scope could enlarge the N-formylation reaction library. The formamide yield was the highest when the Au:Pd ratio was ~1:1. In addition, the AuPd on the Fe3O4 support proved to be more effective than AuPd catalysts on other supports. Furthermore, the reaction was scalable to the gram scale. This new method avoids the requirements of high temperature and high pressure of O2 gas. Moreover, the good recyclability of the catalyst broadens the potential applications of the reaction.

Supplementary Materials

The following are available online at https://www.mdpi.com/article/10.3390/nano11082101/s1, Table S1: Catalyst screening, Table S2. Base screening, Table S3. Catalyst loading, Figure S1. SEM analysis, Figure S2. SEM-EDS analysis, Figure S3. EDS map spectrum, Figure S4. HR-TEM analysis, Figure S5. BF-STEM and HADDF-STEM analysis, Figure S6. Particle distribution of AuPd–NPs, Figure S7. XPS analysis, Figure S8. ICP-AES analysis, Figure S9. XRD analysis, Figure S10. SEM, EDS, and ICP-AES analysis of AuxPdy–Fe3O4, Figure S11. SEM analysis of recycled catalyst, Figure S12. HR-TEM analysis of recycled catalyst, Figure S13. SEM analysis of other AuPd–NPs, Table S4. ICP-AES of other AuPd–NPs, Table S5. Formylation data with other AuPd–NPs, Figure S14. Kinetic data of N-formylation, Table S6. Substrate scope under high substrate concentration, Figure S15. Determination of the methanol oxidation products, Figure S16. Initial kinetics of HCHO-DNPH generation, Table S7. Control experiments.

Author Contributions

Conceptualization, experimental methodology, catalytic study, and manuscript writing, S.Y.; products analysis, S.Y., A.C. and J.H.C.; supervision of the project and manuscript editing, B.M.K. All authors have read and agreed to the published version of the manuscript.

Funding

B.M.K. thanks the Nano Material Development Program (NRF-2012-M3A7B4049644) and the Mid-Career Researcher Program (NRF-2019-R1A2C1004173) for an NRF grant funded by MEST.

Data Availability Statement

Data are contained within the article or Supplementary Materials.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Gerack, C.J.; McElwee-White, L. Formylation of Amines. Molecules 2014, 19, 7689–7713. [Google Scholar] [CrossRef] [Green Version]
  2. Schardl, C.L.; Grossman, R.B.; Nagabhyru, P.; Faulkner, J.R.; Mallik, U.P. Loline alkaloids: Currencies of mutualism. Phytochemistry 2007, 68, 980–996. [Google Scholar] [CrossRef]
  3. Thauer, R.K. Biochemistry of methanogenesis: A tribute to Marjory Stephenson. Microbiology 1998, 144, 2377–2406. [Google Scholar] [CrossRef] [Green Version]
  4. Wada, T.; Takagi, H.; Minakami, H.; Hamanaka, W.; Okamoto, K.; Ito, A.; Sahashi, Y. A New Thiamine Derivative, S-Benzoylthiamine O-Monophosphate. Science 1961, 134, 195–196. [Google Scholar] [CrossRef] [PubMed]
  5. Forsch, R.A.; Rosowsky, A. A New One-Step Synthesis of Leucovorin from Folic Acid and of 5-Formyl-5,6,7,8-tetrahydrohomofolic Acid from Homofolic Acid Using Dimethylamine-Borane in Formic Acid. J. Org. Chem. 1985, 50, 2582–2583. [Google Scholar] [CrossRef]
  6. Ravina, E. The Evolution of Drug Discovery: From Traditional Medicines to Modern Drugs; Wiley-VCH: Weinheim, Germany, 2011; pp. 157–159. [Google Scholar]
  7. Lonsdale, D. Thiamine tetrahydrofurfuryl disulfide: A little known therapeutic agent. Med. Sci. Monit. 2004, 10, RA199–RA203. [Google Scholar] [PubMed]
  8. Olah, G.A.; Ohannesian, L.; Arvanaghi, M. Formylating Agents. Chem. Rev. 1987, 87, 671–686. [Google Scholar] [CrossRef]
  9. Bao, K.; Zhang, W.; Bu, X.; Song, Z.; Zhang, L.; Cheng, M. A novel type of N-formylation and related reactions of amines via cyanides and esters as formylating agents. Chem. Commun. 2008, 42, 5429–5431. [Google Scholar] [CrossRef]
  10. Ke, Z.; Zhang, Y.; Cui, X.; Shi, F. Supported nano-gold-catalyzed N-formylation of amines with paraformaldehyde in water under ambient conditions. Green Chem. 2016, 18, 808–816. [Google Scholar] [CrossRef]
  11. Blicke, F.F.; Lu, C.-J. Formylation of Amines with Chloral and Reduction of the N-Formyl Derivatives with Lithium Aluminum Hydride. J. Am. Chem. Soc. 1952, 74, 3933–3934. [Google Scholar] [CrossRef]
  12. Yale, H.L. Formylation of Amines with Phenyl Formate. J. Org. Chem. 1971, 36, 3238–3240. [Google Scholar] [CrossRef]
  13. Djuric, S.W. A Mild and Convenient Procedure for the N-Formylation of Secondary Amines Using Organosilicon Chemistry. J. Org. Chem. 1984, 49, 1311–1312. [Google Scholar] [CrossRef]
  14. Hosseini-Sarvari, M.; Sharghi, H. ZnO as a New Catalyst for N-Formylation of Amines under Solvent-Free Conditions. J. Org. Chem. 2006, 71, 6652–6654. [Google Scholar] [CrossRef] [PubMed]
  15. Reddy, P.G.; Kumar, G.D.K.; Baskaran, S. A convenient method for the N-formylation of secondary amines and anilines using ammonium formate. Tetrahedron Lett. 2000, 41, 9149–9151. [Google Scholar] [CrossRef]
  16. Bhojegowd, M.R.M.; Nizam, A.; Pasha, M.A. Amberlite IR-120: A Reusable Catalyst for N-Formylation of Amines with Formic Acid Using Microwaves. Chin. J. Catal. 2010, 31, 518–520. [Google Scholar] [CrossRef]
  17. Wang, Z.-G.; Lu, M. Highly efficient N-formylation of amines with ammonium formate catalyzed by nano-Fe3O4 in PEG-400. RSC Adv. 2014, 4, 1234–1240. [Google Scholar] [CrossRef]
  18. Keim, W. C1 Chemistry: Potential and developments. Pure Appl. Chem. 1986, 58, 825–832. [Google Scholar] [CrossRef] [Green Version]
  19. Natte, K.; Neumann, H.; Beller, M.; Jagadeesh, R.V. Transition-Metal-Catalyzed Utilization of Methanol as a C1 Source in Organic Synthesis. Angew. Chem. Int. Ed. 2017, 56, 6384–6394. [Google Scholar] [CrossRef]
  20. Grigg, R.; Mitchell, T.R.B.; Sutthivaiyakit, S.; Tongpenyai, N. Transition Metal-catalysed N-Alkylation of Amines by Alcohols. J. Chem. Soc. Chem. Commun. 1981, 12, 611–612. [Google Scholar] [CrossRef]
  21. Dang, T.T.; Ramalingam, B.; Seayad, A.M. Efficient Ruthenium-Catalyzed N-Methylation of Amines Using Methanol. ACS Catal. 2015, 5, 4082–4088. [Google Scholar] [CrossRef]
  22. Elangovan, S.; Neumann, J.; Sortais, J.-B.; Junge, K.; Darcel, C.; Beller, M. Efficient and selective N-alkylation of amines with alcohols catalysed by manganese pincer complexes. Nat. Commun. 2016, 7, 12641–12648. [Google Scholar] [CrossRef] [Green Version]
  23. Chen, Y. Recent Advances in Methylation: A Guide for Selecting Methylation Reagents. Chem. Eur. J. 2019, 25, 3405–3439. [Google Scholar] [CrossRef]
  24. Meng, C.; Liu, P.; Tung, N.T.; Han, X.; Li, F. N-Methylation of Amines with Methanol in Aqueous Solution Catalyzed by a Water-Soluble Metal–Ligand Bifunctional Dinuclear Iridium Catalyst. J. Org. Chem. 2020, 85, 5815–5824. [Google Scholar] [CrossRef]
  25. Yu, H.; Wu, Z.; Wei, Z.; Zhai, Y.; Ru, S.; Zhao, Q.; Wang, J.; Han, S.; Wei, Y. N-formylation of amines using methanol as a potential formyl carrier by a reusable chromium catalyst. Commun. Chem. 2019, 2, 15–21. [Google Scholar] [CrossRef] [Green Version]
  26. Nasrollahzadeh, M.; Motahharifar, N.; Sajjadi, M.; Aghbolagh, A.M.; Shokouhimehr, M.; Varma, R.S. Recent advances in N-formylation of amines and nitroarenes using efficient (nano)catalysts in ecofriendly media. Green Chem. 2019, 21, 5144–5167. [Google Scholar] [CrossRef]
  27. Pichardo, M.C.; Tavakoli, G.; Armstrong, J.E.; Wilczek, T.; Thomas, B.E.; Prechtl, M.H.G. Copper-Catalyzed Formylation of Amines by using Methanol as the C1 Source. ChemSusChem 2020, 13, 882–887. [Google Scholar] [CrossRef] [PubMed]
  28. Gowrisankar, S.; Neumann, H.; Beller, M. A Convenient and Practical Synthesis of Anisoles and Deuterated Anisoles by Palladium-Catalyzed Coupling Reactions of Aryl Bromides and Chlorides. Chem. Eur. J. 2012, 18, 2498–2502. [Google Scholar] [CrossRef]
  29. Dash, P.; Janni, M.; Peruncheralathan, S. Trideuteriomethoxylation of Aryl and Heteroaryl Halides. Eur. J. Org. Chem. 2012, 26, 4914–4917. [Google Scholar] [CrossRef]
  30. Baumann, M.; Baxendale, I.R. An overview of the synthetic routes to the best selling drugs containing 6-membered heterocycles. Beilstein J. Org. Chem. 2013, 9, 2265–2319. [Google Scholar] [CrossRef] [Green Version]
  31. Cole-Hamilton, D.J. Homogeneous Catalysis—New Approaches to Catalyst Separation, Recovery, and Recycling. Science 2003, 299, 1702–1706. [Google Scholar] [CrossRef]
  32. Hartwig, J.F.; Collman, J.P. Organotransition Metal Chemistry: From Bonding to Catalysis; University Science Books: Sausalito, CA, USA, 2010; pp. 546–549. [Google Scholar]
  33. Crabtree, R.H. Resolving Heterogeneity Problems and Impurity Artifacts in Operationally Homogeneous Transition Metal Catalysts. Chem. Rev. 2012, 112, 1536–1554. [Google Scholar] [CrossRef] [PubMed]
  34. Ortega, N.; Richter, C.; Glorius, F. N-Formylation of Amines by Methanol Activation. Org. Lett. 2013, 15, 1776–1779. [Google Scholar] [CrossRef]
  35. Chakraborty, S.; Gellrich, U.; Diskin-Posner, Y.; Leitus, G.; Avram, L.; Milstein, D. Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study. Angew. Chem. Int. Ed. 2017, 56, 4229–4233. [Google Scholar] [CrossRef]
  36. Kang, B.; Hong, S.H. Hydrogen Acceptor- and Base-Free N-Formylation of Nitriles and Amines using Methanol as C1 Source. Adv. Synth. Catal. 2015, 357, 834–840. [Google Scholar] [CrossRef]
  37. Choi, G.; Hong, S.H. Selective N-Formylation and N-Methylation of Amines Using Methanol as a Sustainable C1 Source. ACS Sustain. Chem. Eng. 2019, 7, 716–723. [Google Scholar] [CrossRef]
  38. Shekhar, A.C.; Kumar, A.R.; Sathaiah, G.; Paul, V.L.; Sridhar, M.; Rao, P.S. Facile N-formylation of amines using Lewis acids as novel catalysts. Tetrahedron Lett. 2009, 50, 7099–7101. [Google Scholar] [CrossRef]
  39. Pathare, S.P.; Sawant, R.V.; Akamanchi, K.G. Sulfated tungstate catalyzed highly accelerated N-formylation. Tetrahedron Lett. 2012, 53, 3259–3263. [Google Scholar] [CrossRef]
  40. Khojastehnezhad, A.; Rahimizadeh, M.; Moeinpour, F.; Eshghi, H.; Bakavoli, M. Polyphosphoric acid supported on silica-coated NiFe2O4 nanoparticles: An efficient and magnetically-recoverable catalyst for N-formylation of amines. C. R. Chim. 2014, 17, 459–464. [Google Scholar] [CrossRef]
  41. Kooti, M.; Nasiri, E. Phosphotungstic acid supported on silica-coated CoFe2O4 nanoparticles: An efficient and magnetically-recoverable catalyst for N-formylation of amines under solvent-free conditions. J. Mol. Catal. A Chem. 2015, 406, 168–177. [Google Scholar] [CrossRef]
  42. Baig, R.B.N.; Verma, S.; Nadagouda, M.N.; Varma, R.S. A photoactive bimetallic framework for direct aminoformylation of nitroarenes. Green Chem. 2016, 18, 1019–1022. [Google Scholar] [CrossRef]
  43. Luo, R.; Lin, X.; Chen, Y.; Zhang, W.; Zhou, X.; Ji, H. Cooperative Catalytic Activation of Si–H Bonds: CO2-Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions. ChemSusChem 2017, 10, 1224–1232. [Google Scholar] [CrossRef]
  44. Huang, Z.; Jiang, X.; Zhou, S.; Yang, P.; Du, C.-X.; Li, Y. Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2. ChemSusChem 2019, 12, 3054–3059. [Google Scholar] [CrossRef] [Green Version]
  45. Polshettiwar, V.; Varma, R.S. Green chemistry by nano-catalysis. Green Chem. 2010, 12, 743–754. [Google Scholar] [CrossRef]
  46. Polshettiwar, V.; Luque, R.; Fihri, A.; Zhu, H.; Bouhrara, M.; Basset, J.-M. Magnetically Recoverable Nanocatalysts. Chem. Rev. 2011, 111, 3036–3075. [Google Scholar] [CrossRef]
  47. Gawande, M.B.; Branco, P.S.; Varma, R.S. Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of sustainable methodologies. Chem. Soc. Rev. 2013, 42, 3371–3393. [Google Scholar] [CrossRef]
  48. Enache, D.I.; Edwards, J.K.; Landon, P.; Solsona-Espriu, B.; Carley, A.F.; Herzing, A.A.; Watanabe, M.; Kiely, C.J.; Knight, D.W.; Hutchings, G.J. Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Au-Pd/TiO2 Catalysts. Science 2006, 311, 362–365. [Google Scholar] [CrossRef]
  49. Hou, W.; Dehm, N.A.; Scott, R.W.J. Alcohol oxidations in aqueous solutions using Au, Pd, and bimetallic AuPd nanoparticle catalysts. J. Catal. 2008, 253, 22–27. [Google Scholar] [CrossRef]
  50. Chang, C.-R.; Long, B.; Yang, X.-F.; Li, J. Theoretical Studies on the Synergetic Effects of Au–Pd Bimetallic Catalysts in the Selective Oxidation of Methanol. J. Phys. Chem. C 2015, 119, 16072–16081. [Google Scholar] [CrossRef]
  51. Han, S.; Mullins, C.B. Surface Alloy Composition Controlled O2 Activation on Pd–Au Bimetallic Model Catalysts. ACS Catal. 2018, 8, 3641–3649. [Google Scholar] [CrossRef]
  52. Preedasuriyachai, P.; Kitahara, H.; Chavasiri, W.; Sakurai, H. N-Formylation of Amines Catalyzed by Nanogold under Aerobic Oxidation Conditions with MeOH or Formalin. Chem. Lett. 2010, 39, 1174–1176. [Google Scholar] [CrossRef]
  53. Ishida, T.; Haruta, M. N-Formylation of Amines via the Aerobic Oxidation of Methanol over Supported Gold Nanoparticles. ChemSusChem 2009, 2, 538–541. [Google Scholar] [CrossRef]
  54. Tumma, H.; Nagaraju, N.; Reddy, K.V. A facile method for the N-formylation of primary and secondary amines by liquid phase oxidation of methanol in the presence of hydrogen peroxide over basic copper hydroxyl salts. J. Mol. Catal. A 2009, 310, 121–129. [Google Scholar] [CrossRef]
  55. Tanaka, S.; Minato, T.; Ito, E.; Hara, M.; Kim, Y.; Yamamoto, Y.; Asao, N. Selective Aerobic Oxidation of Methanol in the Coexistence of Amines by Nanoporous Gold Catalysts: Highly Efficient Synthesis of Formamides. Chem. Eur. J. 2013, 19, 11832–11836. [Google Scholar] [CrossRef]
  56. Jang, Y.; Chung, J.; Kim, S.; Jun, S.W.; Kim, B.H.; Lee, D.W.; Kim, B.M.; Hyeon, T. Simple synthesis of Pd–Fe3O4 heterodimer nanocrystals and their application as a magnetically recyclable catalyst for Suzuki cross-coupling reactions. Phys. Chem. Chem. Phys. 2011, 13, 2512–2516. [Google Scholar] [CrossRef]
  57. Jang, Y.; Kim, S.; Jun, S.W.; Kim, B.H.; Hwang, S.; Song, I.K.; Kim, B.M.; Hyeon, T. Simple one-pot synthesis of Rh–Fe3O4 heterodimer nanocrystals and their applications to a magnetically recyclable catalyst for efficient and selective reduction of nitroarenes and alkenes. Chem. Commun. 2011, 47, 3601–3603. [Google Scholar] [CrossRef]
  58. Lee, J.; Chung, J.; Byun, S.; Kim, B.M.; Lee, C. Direct catalytic C–H arylation of imidazo [1,2-a]pyridine with aryl bromides using magnetically recyclable Pd–Fe3O4 nanoparticles. Tetrahedron 2013, 69, 5660–5664. [Google Scholar] [CrossRef]
  59. Chung, J.; Kim, J.; Jang, Y.; Byun, S.; Hyeon, T.; Kim, B.M. Heck and Sonogashira cross-coupling reactions using recyclable Pd–Fe3O4 heterodimeric nanocrystal catalysts. Tetrahedron Lett. 2013, 54, 5192–5196. [Google Scholar] [CrossRef]
  60. Byun, S.; Chung, J.; Jang, Y.; Kwon, J.; Hyeon, T.; Kim, B.M. Highly selective Wacker oxidation of terminal olefins using magnetically recyclable Pd–Fe3O4 heterodimer nanocrystals. RSC Adv. 2013, 3, 16296–16299. [Google Scholar] [CrossRef]
  61. Bae, I.H.; Lee, I.-H.; Byun, S.; Chung, J.; Kim, B.M.; Choi, T.-L. Magnetically Recyclable Pd-Fe3O4 Heterodimer Nanocrystals for the Synthesis of Conjugated Polymers via Suzuki Polycondensation: Toward Green Chemistry. J Polym. Sci. Pol. Chem. 2014, 52, 1525–1528. [Google Scholar] [CrossRef]
  62. Kwon, J.; Chung, J.; Byun, S.; Kim, B.M. Efficient Synthesis of Indole Derivatives via Tandem Cyclization Catalyzed by Magnetically Recoverable Palladium/Magnetite (Pd-Fe3O4) Nanocrystals. Asian J. Org. Chem. 2016, 5, 470–476. [Google Scholar] [CrossRef]
  63. Byun, S.; Song, Y.; Kim, B.M. Heterogenized Bimetallic Pd–Pt–Fe3O4 Nanoflakes as Extremely Robust, Magnetically Recyclable Catalysts for Chemoselective Nitroarene Reduction. ACS Appl. Mater. Interfaces 2016, 8, 14637–14647. [Google Scholar] [CrossRef]
  64. Jang, J.; Byun, S.; Kim, B.M.; Lee, S. Arylsilylation of aryl halides using the magnetically recyclable bimetallic Pd–Pt–Fe3O4 catalyst. Chem. Commun. 2018, 54, 3492–3495. [Google Scholar] [CrossRef]
  65. Cho, A.; Byun, S.; Kim, B.M. AuPd–Fe3O4 Nanoparticle Catalysts for Highly Selective, One-Pot Cascade Nitro-Reduction and Reductive Amination. Adv. Synth. Catal. 2018, 360, 1253–1261. [Google Scholar] [CrossRef]
  66. Cho, A.; Byun, S.; Cho, J.H.; Kim, B.M. AuPd–Fe3O4 Nanoparticle-Catalyzed Synthesis of Furan-2,5-dimethylcarboxylate from 5-Hydroxymethylfurfural under Mild Conditions. ChemSusChem 2019, 12, 2310–2317. [Google Scholar] [CrossRef]
  67. Cho, J.H.; Byun, S.; Cho, A.; Kim, B.M. One-pot, chemoselective synthesis of secondary amines from aryl nitriles using a PdPt–Fe3O4 nanoparticle catalyst. Catal. Sci. Technol. 2020, 10, 4201–4209. [Google Scholar] [CrossRef]
  68. Wang, R.; Wu, Z.; Chen, C.; Qin, Z.; Zhu, H.; Wang, G.; Wang, H.; Wu, C.; Dong, W.; Fan, W.; et al. Graphene-supported Au–Pd bimetallic nanoparticles with excellent catalytic performance in selective oxidation of methanol to methyl formate. Chem. Commun. 2013, 49, 8250–8252. [Google Scholar] [CrossRef]
  69. Zhu, X.; Guo, Q.; Sun, Y.; Chen, S.; Wang, J.-Q.; Wu, M.; Fu, W.; Tang, Y.; Duan, X.; Chen, D.; et al. Optimising surface d charge of AuPd nanoalloy catalysts for enhanced catalytic activity. Nat. Commun. 2019, 10, 1428–1438. [Google Scholar] [CrossRef] [Green Version]
  70. Ju, P.; Chen, J.; Chen, A.; Chen, L.; Yu, Y. N-Formylation of Amines with CO2 and H2 Using Pd–Au Bimetallic Catalysts Supported on Polyaniline-Functionalized Carbon Nanotubes. ACS Sustain. Chem. Eng. 2017, 5, 2516–2528. [Google Scholar]
  71. Wang, R.; Wu, Z.; Wang, G.; Qin, Z.; Chen, C.; Dong, M.; Zhu, H.; Fan, W.; Wang, J. Highly active Au–Pd nanoparticles supported on three-dimensional graphene–carbon nanotube hybrid for selective oxidation of methanol to methyl formate. RSC Adv. 2015, 5, 44835–44839. [Google Scholar] [CrossRef]
  72. Beller, M. The Current Status and Future Trends in Oxidation Chemistry. Adv. Synth. Catal. 2004, 346, 107–108. [Google Scholar] [CrossRef]
  73. Harit, H.; Hiran, B.L.; Joshi, S.N. Kinetics and Mechanism of Oxidation of Pimary Alcohols by Pyridinium Dichromate. Chem. Sci. Trans. 2015, 4, 49–58. [Google Scholar]
  74. Jana, S.; Thomas, J.; Gupta, S.S. Catalytic oxidation of alcohols using Fe-bTAML and NaClO: Comparing the reactivity of Fe(V)O and Fe(IV)O intermediates. Inorg. Chim. Acta 2019, 486, 476–482. [Google Scholar] [CrossRef]
  75. Mallat, T.; Baiker, A. Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts. Chem. Rev. 2004, 104, 3037–3058. [Google Scholar] [CrossRef]
  76. Punniyamurthy, T.; Velusamy, S.; Iqbal, J. Recent Advances in Transition Metal Catalyzed Oxidation of Organic Substrates with Molecular Oxygen. Chem. Rev. 2005, 105, 2329–2363. [Google Scholar] [CrossRef]
  77. Camellone, M.F.; Marx, D. Nature and Role of Activated Molecular Oxygen Species at the Gold/Titania Interface in the Selective Oxidation of Alcohols. J. Phys. Chem. C 2014, 118, 20989–21000. [Google Scholar] [CrossRef]
  78. Whiting, G.T.; Kondrat, S.A.; Hammond, C.; Dimitratos, N.; He, Q.; Morgan, D.J.; Dummer, N.F.; Bartley, J.K.; Kiely, C.J.; Taylor, S.H.; et al. Methyl Formate Formation from Methanol Oxidation Using Supported Gold–Palladium Nanoparticles. ACS Catal. 2015, 5, 637–644. [Google Scholar] [CrossRef]
  79. Tong, X.; Liu, Z.; Yu, L.; Li, Y. A tunable process: Catalytic transformation of renewable furfural with aliphatic alcohols in the presence of molecular oxygen. Chem. Commun. 2015, 51, 3674–3677. [Google Scholar] [CrossRef]
  80. Slot, T.K.; Eisenberg, D.; van Noordenne, D.; Jungbacker, P.; Rothenberg, G. Cooperative Catalysis for Selective Alcohol Oxidation with Molecular Oxygen. Chem. Eur. J. 2016, 22, 12307–12311. [Google Scholar] [CrossRef]
  81. Ray, R.; Chandra, S.; Maiti, D.; Lahiri, G.K. Simple and Efficient Ruthenium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen. Chem. Eur. J. 2016, 22, 8814–8822. [Google Scholar] [CrossRef]
  82. Jiang, H.-L.; Xu, Q. Recent progress in synergistic catalysis over heterometallic nanoparticles. J. Mater. Chem. 2011, 21, 13705–13725. [Google Scholar] [CrossRef]
  83. Singh, A.K.; Xu, Q. Synergistic Catalysis over Bimetallic Alloy Nanoparticles. ChemCatChem 2013, 5, 652–676. [Google Scholar] [CrossRef]
  84. Wang, S.; Zhang, D.; Ma, Y.; Zhang, H.; Gao, J.; Nie, Y.; Sun, X. Aqueous Solution Synthesis of Pt–M (M = Fe, Co, Ni) Bimetallic Nanoparticles and Their Catalysis for the Hydrolytic Dehydrogenation of Ammonia Borane. ACS Appl. Mater. Interfaces 2014, 6, 12429–12435. [Google Scholar] [CrossRef]
  85. Yu, H.; Tang, W.; Li, K.; Zhao, S.; Yin, H.; Zhou, S. Enhanced Catalytic Performance for Hydrogenation of Substituted Nitroaromatics over Ir-Based Bimetallic Nanocatalysts. ACS Appl. Mater. Interfaces 2019, 11, 6958–6969. [Google Scholar] [CrossRef]
  86. Wang, M.; Chen, D.; Li, N.; Xu, Q.; Li, H.; He, J.; Lu, J. Highly Efficient Catalysts of Bimetallic Pt–Ru Nanocrystals Supported on Ordered ZrO2 Nanotube for Toluene Oxidation. ACS Appl. Mater. Interfaces 2020, 12, 13781–13789. [Google Scholar] [CrossRef]
Nanomaterials 11 02101 sch001 550
Scheme 1. Formamide groups found in natural products and pharmaceuticals: (a) natural products; (b) pharmaceuticals.
Scheme 1. Formamide groups found in natural products and pharmaceuticals: (a) natural products; (b) pharmaceuticals.
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Scheme 2. N-Formylation of amines using methanol as a C1 source: (a) homogeneous catalysis; (b) heterogeneous catalysis; (c) This work.
Scheme 2. N-Formylation of amines using methanol as a C1 source: (a) homogeneous catalysis; (b) heterogeneous catalysis; (c) This work.
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Figure 1. (a) SEM and (b) HR-TEM image of AuPd–Fe3O4 catalyst.
Figure 1. (a) SEM and (b) HR-TEM image of AuPd–Fe3O4 catalyst.
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Figure 2. (a) STEM-EDS image and (b) XRD data of AuPd–Fe3O4 catalyst.
Figure 2. (a) STEM-EDS image and (b) XRD data of AuPd–Fe3O4 catalyst.
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Scheme 3. Initial observation of formamide under AuPd–Fe3O4.
Scheme 3. Initial observation of formamide under AuPd–Fe3O4.
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Scheme 4. Substrate scope of N-formylation1,2 1 Isolated yield. 2 1 (0.50 mmol), AuPd–Fe3O4 (1.4 mol%), CsOH·H2O (3.0 equiv), O2 (1.0 atm), methanol (2.0 mL), r. t., 18 h. 3 2.4 mol% of AuPd–Fe3O4 used. 4 The reaction was run at 0.20 mmol scale of 1f in methanol (1.0 mL).
Scheme 4. Substrate scope of N-formylation1,2 1 Isolated yield. 2 1 (0.50 mmol), AuPd–Fe3O4 (1.4 mol%), CsOH·H2O (3.0 equiv), O2 (1.0 atm), methanol (2.0 mL), r. t., 18 h. 3 2.4 mol% of AuPd–Fe3O4 used. 4 The reaction was run at 0.20 mmol scale of 1f in methanol (1.0 mL).
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Scheme 5. A plausible reaction pathway for N-formylation of amines.
Scheme 5. A plausible reaction pathway for N-formylation of amines.
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Figure 3. Results of recycling test.
Figure 3. Results of recycling test.
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Scheme 6. Gram scale reaction.
Scheme 6. Gram scale reaction.
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Table
Table 1. Screening data of the N-formylation of amine 1.
Table 1. Screening data of the N-formylation of amine 1.
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EntryCatalystBaseTON 2Yield 3
1Fe3O4NaOH0N. D. 4
2 5Pd–Fe3O4NaOH2055
3 6Au–Fe3O4NaOH925
4AuPd–Fe3O4NaOH2365
5AuPd–Fe3O4-514
6 7AuPd–Fe3O4NaOH1543
7AuPd–Fe3O4Cs2CO32569
8AuPd–Fe3O4CsOH·H2O3390 8
9 9AuPd–Fe3O4CsOH·H2O3392 (84 10)
10 11AuPd–Fe3O4CsOH·H2O3289
11 12AuPd–Fe3O4CsOH·H2O1542 13
12 14AuPd–Fe3O4CsOH·H2O8971
1 Reaction conditions: 1a (0.20 mmol), catalyst (1.4 mol%), base (3.0 equiv), O2 (1.0 atm), methanol (1.0 mL), r. t., 18 h. 2 Turnover number (TON) = mmol of product/mmol of total metal except Fe. 3 Determined from 1H NMR spectral analysis through the use of mesitylene as an internal standard. 4 N. D. = not detected. 5 Pd–Fe3O4 (2.8 mol%) was used as a catalyst. 6 Au–Fe3O4 (2.8 mol%) was used as a catalyst. 7 An air balloon was used instead of O2. 8 An average value of three runs (91%, 90%, and 88%). 9 Result with 1a (0.50 mmol) in MeOH (2.0 mL). 10 Yield of isolated product. 11 Result with 1a (1.0 mmol) in MeOH (1.0 mL), 4 h. 12 Ethanol (1.0 mL) was used instead of methanol. 13 Yield of 2a’. 14 Result with 0.40 mol% of catalyst.
Table
Table 2. Base screening of the N-formylation of amine 1.
Table 2. Base screening of the N-formylation of amine 1.
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EntryBaseYield 2EntryBaseYield 2
1-146K2CO354
2LiOH·H2O607Cs2CO369
3NaOH658KOt Bu69
4KOH759K3PO460
5CsOH·H2O9110CsF39
1 Reaction conditions: 1a (0.20 mmol), AuPd–Fe3O4 (1.4 mol%), base (3.0 equiv), O2 (1.0 atm), methanol (1.0 mL), r. t., 18 h. 2 Determined from 1H NMR spectral analysis through the use of mesitylene as an internal standard.
Table
Table 3. Comparison on the Effect of Alloy Bimetallic Catalyst and Combination of Two Metal Catalysts 1.
Table 3. Comparison on the Effect of Alloy Bimetallic Catalyst and Combination of Two Metal Catalysts 1.
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EntryCatalyst 3Product Yield with Various R Group (%) 2
H4-Me4-OMe3-NO23-CN
1 4Au5161272523
2 5Pd57281885
3 6Au + Pd9062342632
4 7AuPd9169837359
1 Reaction conditions: 1 (0.20 mmol), catalyst, CsOH·H2O (3.0 equiv), O2 (1.0 atm), methanol (1.0 mL), r. t., 18 h. 2 Yields were determined from 1H NMR spectral analysis through the use of mesitylene as an internal standard. 3 Catalyst composition: Au–Fe3O4 (5.47 wt% Au), Pd–Fe3O4 (8.20 wt% Pd), AuPd–Fe3O4 (11.7 wt% Au, 6.23 wt% Pd, Au:Pd = 1:0.99). 4 Au–Fe3O4 (2.8 mol%) used. 5 Pd–Fe3O4 (2.8 mol%) used. 6 Au–Fe3O4 (1.4 mol%), Pd–Fe3O4 (1.4 mol%) used. 7 AuPd–Fe3O4 (1.4 mol%) used.
Table
Table 4. Reactivity comparison of various AuPd catalysts 1.
Table 4. Reactivity comparison of various AuPd catalysts 1.
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EntryCatalystYield 2
1Au1Pd0.23–Fe3O476
2Au1Pd0.39–Fe3O476
3Au1Pd1.08–Fe3O491
4Au0.65Pd1–Fe3O479
5Au0.39Pd1–Fe3O469
1 Reaction conditions: 1a (0.20 mmol), catalyst (2.0 mol%), CsOH·H2O (3.0 equiv), O2 (1.0 atm), methanol (1.0 mL), r. t., 18 h. 2 Determined from 1H NMR spectral analysis through the use of mesitylene as an internal standard.
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Yang, S.; Cho, A.; Cho, J.H.; Kim, B.M. Oxidative N-Formylation of Secondary Amines Catalyzed by Reusable Bimetallic AuPd–Fe3O4 Nanoparticles. Nanomaterials 2021, 11, 2101. https://doi.org/10.3390/nano11082101

AMA Style

Yang S, Cho A, Cho JH, Kim BM. Oxidative N-Formylation of Secondary Amines Catalyzed by Reusable Bimetallic AuPd–Fe3O4 Nanoparticles. Nanomaterials. 2021; 11(8):2101. https://doi.org/10.3390/nano11082101

Chicago/Turabian Style

Yang, Sabyuk, Ahra Cho, Jin Hee Cho, and Byeong Moon Kim. 2021. "Oxidative N-Formylation of Secondary Amines Catalyzed by Reusable Bimetallic AuPd–Fe3O4 Nanoparticles" Nanomaterials 11, no. 8: 2101. https://doi.org/10.3390/nano11082101

APA Style

Yang, S., Cho, A., Cho, J. H., & Kim, B. M. (2021). Oxidative N-Formylation of Secondary Amines Catalyzed by Reusable Bimetallic AuPd–Fe3O4 Nanoparticles. Nanomaterials, 11(8), 2101. https://doi.org/10.3390/nano11082101

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