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Article

Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde

by
Ioannis Metaxas
,
Eleni Vasilikogiannaki
and
Manolis Stratakis
*
Department of Chemistry, University of Crete, Voutes, 71003 Iraklion, Greece
*
Author to whom correspondence should be addressed.
Nanomaterials 2017, 7(12), 440; https://doi.org/10.3390/nano7120440
Submission received: 18 September 2017 / Revised: 20 November 2017 / Accepted: 6 December 2017 / Published: 12 December 2017
(This article belongs to the Special Issue Noble Metal Nanoparticles in Catalysis)
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Abstract

:
A simple method for the synthesis of formate esters and formamides is presented based on the Au/TiO2-catalyzed aerobic oxidative coupling between alcohols or amines and formaldehyde. The suitable form of formaldehyde is paraformaldehyde, as cyclic trimeric 1,3,5-trioxane is inactive. The reaction proceeds via the formation of an intermediate hemiacetal or hemiaminal, respectively, followed by the Au nanoparticle-catalyzed aerobic oxidation of the intermediate. Typically, the oxidative coupling between formaldehyde (2 equiv) and amines occurs quantitatively at room temperature within 4 h, and there is no need to add a base as in analogous coupling reactions. The oxidative coupling between formaldehyde (typically 3 equiv) and alcohols is unprecedented and occurs more slowly, yet in good to excellent yields and selectivity. Minor side-products (2–12%) from the acetalization of formaldehyde by the alcohol are also formed. The catalyst is recyclable and can be reused after a simple filtration in five consecutive runs with a small loss of activity.

Graphical Abstract

1. Introduction

Supported Au nanoparticles (Au NPs) have emerged during the past two decades as potent catalysts in several organic transformations. The surprising initial observation by Haruta’s group, that Au NPs are capable of oxidizing CO into CO2 even at −70 °C by atmospheric air [1,2], a reaction with great environmental significance, was the starting point of the extended growth of the applications of Au NPs in catalysis. This first breakthrough observation established a metal (Au) that no one could foresee having any major catalytic activity, into the first row of exploration by many research groups worldwide.
The reason for this catalytic activity is that the small clusters of Au deposited on several supports, such as metal oxides or polymeric materials, in contrast to bulk gold, which is formally inactive, exhibit unexpected properties. The key role of the support is not only to stabilize and protect Au clusters from leaking, aggregation, or against oxidation, which deactivates them in certain cases, but, in many reports, it is proposed that there is a synergy in the catalytic activity among metal oxide and Au NPs.
Following the Au NPs-catalyzed aerobic oxidation of CO, the first major step towards their recognition as powerful catalysts was triggered by their application in the aerobic oxidation of organic compounds, such as alcohols, aldehydes, amines, alkenes, etc. [3,4,5,6,7,8]. Such transformations gained significant attention within the organic community, due to their green nature, as the oxidant is simply the atmospheric air. The second major step in the field of catalysis using Au NPs, which essentially expanded during the first decade of this century, was rather unexpected, as nanogold catalysts found catalytic applications in organic transformations beyond aerobic oxidations. Such transformations are typically catalyzed either by ionic Au substances or by Pd(0) and other noble metals, mostly under homogeneous conditions [9,10,11,12,13].
The results that will be presented and analyzed below were triggered during our recent studies on the difunctionalization of oxetanes with a silylborane catalyzed by supported Au nanoparticles [14]. It was found that activated α,α-disubstituted oxetanes do not undergo silaboration and, in the absence of the silylborane, two competing Au-nanoparticle-catalyzed pathways take place in 1,2-dichloroethane (DCE) as a solvent: isomerization into homoallylic alcohols or a retro [2+2] decomposition forming an alkene and formaldehyde. Generally, the first path is prevailing. A typical example is shown in Scheme 1, regarding the case of 2-methyl-2-phenyloxetane (1).
Surprisingly, though, one of the minor side-products was the formate of the homoallylic alcohol (1b), and we reasonably considered its formation as arising from the reaction of homoallylic alcohol 1a (isomerization product of the main path a) with formaldehyde, which is formed via the retro [2+2] decomposition path of the oxetane (path b). The isomerization mechanism of activated oxetanes into homoallylic alcohols catalyzed by Au/TiO2 (path b) is obviously identical to the concerted process for the isomerization of activated epoxides into allylic alcohols, previously established by our group [15] and requires the synergy among electrophilic Au nanoparticles and the basic oxygen atoms of the support. Additional experiments established that, under the reaction conditions, alkene 1c does not arise via a retro carbonyl-ene reaction of homoallylic alcohol 1a, but also, 1a is not formed via a direct carbonyl-ene reaction among alkene 1c and formaldehyde.
We, therefore, focused on a possible methodology for the synthesis of formate esters, based on the reaction between an alcohol and formaldehyde in the presence of Au/TiO2 under aerobic conditions. In this concept, essentially the in situ catalytic oxidation of the produced labile hemiacetal is anticipated. As a second task, we extended this concept to the mild and facile synthesis of formamides from the corresponding amines without using an external base as in previous reported analogous oxidative coupling protocols.

2. Results

2.1. Synthesis of Formate Esters

To test this concept, we initially examined the reaction of a simple alcohol (1-octanol, 2) with formaldehyde in the presence of Au/TiO2 (2 mol %). There are two stable solid sources of formaldehyde: paraformaldehyde, which is a linear polymeric form and delivers formaldehyde upon heating, and 1,3,5-trioxane, which is the cyclic trimeric acetal form. Treatment of 1-octanol with 3 molar equivalents of paraformaldehyde in 1,2-dichloroethane (DCE) and heating to 65 °C for 10 h, led to the quantitative consumption of the alcohol and to a mixture of formate ester 2a and acetal 2b in a relative ratio 2a/2b = 95/5 (Scheme 2). The mixture was chromatographed and 2a was isolated in 80% yield. Contrary to paraformaldehyde, we could not achieve any reaction with 1,3,5-trioxane.
Acetal 2b [16] is not a precursor of formate 2a, as it was separately treated with paraformaldehyde under conditions identical to the reaction, but no reaction was seen. Apparently, from the reaction between 1-octanol and formaldehyde, the labile hemiacetal 2c is reversibly formed, which then undergoes aerobic oxidation catalyzed by Au/TiO2, leading to formate 2a. The aldehyde functionality of formate ester is deactivated toward further nucleophilic attack by an alcohol molecule, as the corresponding dioctyl carbonate ester was not detected by GC-MS.
For the optimization of the reaction, a series of solvents and Au nanoparticle catalysts [17] was tested. Au/TiO2 is more efficient compared to Au/Al2O3 or Au/ZnO. These commercially available catalysts have similar wt % content in Au and average nanoparticle size. As per the solvents, although in toluene the reaction is taking place slightly slowly, the product selectivity (2a/2b) is better than in DCE. All other solvents gave inferior results in terms of conversion rates or selectivity (Table 1). The catalyst is easily recyclable and reusable after filtration and drying in the oven at 90 °C for 2 h, in five consecutive runs (see footnote of Table 1). A small decline in activity was observed, apparently due to some loss of material during the recycling process.
Subsequently, we tested a series of alcohols to examine the scope and limitations of their formylation, using Au/TiO2 (2 mol %) as the catalyst, 3 equiv of paraformaldehyde, toluene as the solvent, and heating to 80 °C for 10 h (Figure 1). Primary alcohols are, in general, good substrates and provide the corresponding formate esters in selectivity 92–99%. Primary benzylic alcohols are competitively oxidized into the corresponding benzaldehydes in a relative ratio of ~15–20%, while the formation of other minor side products drops the yield of formates to around 50–55%. Secondary alcohols are less prone to react due to steric reasons and require 5 equiv of paraformaldehyde and ~20 h to reach completion. Phenols are rather unreactive even using a large excess of paraformaldehyde (10 equiv) and extended reaction times; under these conditions <5% of formate ester was seen by GC-MS.
The Au-NP-catalyzed aerobic oxidation of hemiacetals has been well documented in the literature, as a protocol to prepare esters or lactones [18,19,20,21,22]. Yet for acyclic esters, one of the reactants has to be used in large excess (e.g., the reaction of benzaldehyde in methanol as a solvent to form methyl benzoate). Our approach is essentially the first example for the synthesis of formate esters employing a formaldehyde-alcohol oxidative coupling. Generally, formate esters can be prepared by the acid-catalyzed [23] or N-heterocyclic carbene-promoted [24] transesterification of alcohols with ethyl formate, and in the presence of PPh3/CBr4 [25], by the direct esterification of alcohols with formic acid catalyzed by I2 [26], and via the Pd-catalyzed carbonylation of alcohols with CO [27]. The only example for the synthesis of formate esters using Au nanoparticle catalysis, was recently reported by the groups of Hammond and Xu [28] employing a tandem Au/TiO2-catalyzed reduction/formylation of aromatic aldehydes with HCOOH.

2.2. Synthesis of Formamides

Given the ability of alcohols to oxidatively couple with paraformaldehyde yielding formate esters, we decided to examine the analogous coupling reaction using amines. To our delight, a series of secondary amines couple in the presence of Au/TiO2 (2 mol %) quantitatively with paraformaldehyde (2.0 equiv) in DCE as a solvent to form cleanly the corresponding formamides within 4 h at room temperature (Figure 2). The resulting products are pure and there is no need for chromatographic purification. An exception was the bulky 2,2,6,6-tetramethylpiperidine (22) which did not provide any product. The reaction was performed on 1.0 gr scale of piperidine, and reached completion after 32 h in ambient conditions, yielding formamide 15a in 86% isolated yield. The extended reaction time is due to the fact that both small- and large-scale reactions are run into the same flask and the limiting factor is the amount of molecular oxygen at the liquid-air interface. From the mechanistic point of view, amine attacks formaldehyde, forming the corresponding hemiaminal, which is fast and cleanly oxidized by O2 into the corresponding formamides, a process catalyzed by Au nanoparticles.
There are a few recent analogous Au-catalyzed reports on the synthesis of formamides utilizing the formaldehyde/amine oxidative coupling concept. Shi and colleagues [29] have used a homemade Au/Al2O3 catalyst, which operates at room temperature and 1 atm O2 pressure and requires a base, such as NaOH in H2O as a solvent. Doris and Namboothiri [30] used a carbon nanotube-Au nanohybrid as a catalyst, and aqueous toluene as a solvent, while NaOH is also required. Prior to these reports, Sakurai’s group had shown an analogous NaOH-promoted coupling using Au nanoclusters stabilized by poly(N-vinyl-2-pyrrolidone) as a catalyst [31]. The characteristics of our catalytic system are that it is commercially available, provides quantitative reactions within a relatively short period of time (as all previous protocols more or less do), it simply operates under an open-air flask, while there is no need of a base, as in all analogous oxidative coupling protocols reported to date.
It is possible that the support of Au nanoparticles (titania) itself plays the role of a base in our process. We had previously invoked the crucial role of oxygen atoms of TiO2 as the required basic site in the synergistic isomerization of epoxides into allylic alcohols catalyzed by Au/TiO2 [15]. Note that formamides can also be prepared via nano Au-catalyzed coupling reactions between amines and methanol [32,33]. In those protocols which require rather harsh conditions and excess of reagents, methanol is oxidized into formaldehyde, which then undergoes oxidative coupling with the amine. Surprisingly, in one of these reports [33], where Au-nanopore was used as a catalyst, the direct oxidative coupling between formaldehyde and an amine was unsuccessful. The concept of coupling alcohols other than methanol, and amines for the synthesis of amides under Au nanoparticle-catalysis, has also been shown to be synthetically useful [34,35]. Finally, Au nanoparticle catalysis has also been used in the synthesis of formamides by other approaches, such as in the reaction of amines with CO2 or ammonium formate under reductive conditions [36,37].
Apart from nano Au-catalysis, the synthesis of formamides is feasible in the literature based on the catalytic transamidation of amines with HCONH2 [38], treatment of amines with CO2 and a hydrosilane or with H2 under various catalytic conditions [39,40,41], Ru-catalyzed dehydrogenative coupling between amines [42] or nitriles [43] and methanol, and the base-catalyzed carbonylation of amines with carbon monoxide [44].

3. Experimental Section

3.1. Catalysts

The supported Au nanoparticles on TiO2, Al2O3, or ZnO having a gold content ~1 wt %, which were used in our studies, are commercially available from Strem Chemicals Inc. The average crystallite size of Au nanoparticles is ~2–3 nm. Prior to use, they were ground in a mortar, and the resulting purple dust was kept in a dark-colored bottle.

3.2. Catalytic Reactions

Typical reaction of alcohol or amine formylation: In a vial are placed 0.4 mmol of the alcohol, 1.2 mmol of paraformaldehyde, and 160 mg of Au/TiO2 (~1.0 mol % in Au, 2 mol %) in 2 mL of toluene. The heterogeneous mixture is heated to 80 °C until the alcohol is consumed. The slurry is then filtered with the aid of 2 mL of dichloromethane under a low pressure through a short pad of silica gel or celite, and the filtrate is evaporated. Chromatographic purification is accompanied, if required. Regarding the formylation of amines, the amount of paraformaldehyde used is 2.0 equivalents relative to the amine and the reaction takes place at room temperature. After filtration and evaporation of the solvents, the resulting formamides are pure and generally do not require any chromatographic purification.

3.3. Characterization of Products

Octyl formate (2a): 1H NMR (500 MHz, CDCl3): 8.06 (br s, 1H), 4.16 (td, J1 = 7.0 Hz, J2 = 0.5 Hz, 2H), 1.69–1.63 (m, 2H), 1.40–1.22 (m, 10H), 0.88 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): 161.2, 64.1, 31.7, 29.1, 28.5, 25.8, 22.6, 14.1.
Dec-9-en-1-yl formate (3a): 1H NMR (500 MHz, CDCl3): 8.05 (br s, 1H), 5.80 (ddq, J1 = 16.0 Hz, J2 = 10.0 Hz, J2 = 7.0 Hz, 1H), 4.99 (br d, J = 16.0 Hz, 1H), 4.94 (br d, J = 10.0 Hz, 1H), 4.15 (td, J1 = 7.0 Hz, J2 = 0.5 Hz, 2H), 2.06–2.02 (m, 2H), 1.67–1.63 (m, 2H), 1.38–1.24 (m, 12H); 13C NMR (125 MHz, CDCl3): 161.2, 139.1, 114.1, 64.1, 33.8, 29.4, 29.3, 29.1, 29.0, 28.9, 28.5, 25.8.
Dec-5-yn-1-yl formate (4a): 1H NMR (500 MHz, CDCl3): 8.06 (br s, 1H), 4.18 (t, J = 7.0 Hz, 2H), 2.21–2.12 (m, 4H), 1.81–1.76 (m, 2H), 1.58–1.38 (m, 6H), 0.90 (t, J = 7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3): 161.1, 80.9, 79.1, 63.6, 31.2, 27.6, 25.4, 21.9, 18.4, 18.3, 13.6.
5-Phenylpentyl formate (5a): 1H NMR (300 MHz, CDCl3): 8.06 (br s, 1H), 7.30–7.15 (m, 5H), 4.16 (t, J = 7.0 Hz, 2H), 2.61 (t, J = 7.5 Hz, 2H), 1.70–1.36 (m, 8H); 13C NMR (75 MHz, CDCl3): 161.2, 142.6, 128.4, 128.2, 125.6, 64.0, 35.8, 31.3, 28.8, 28.4, 25.7.
Phenethyl formate (6a): 1H NMR (300 MHz, CDCl3): 8.05 (br s, 1H), 7.36–7.23 (m, 5H), 4.40 (t, J = 7.0 Hz, 2H), 2.99 (t, J = 7.5 Hz, 2H); 13C NMR (75 MHz, CDCl3): 161.0, 137.4, 128.9, 128.6, 126.7, 64.4, 34.9.
2-Cyclohexylethyl formate (7a): 1H NMR (300 MHz, CDCl3): 8.06 (br s, 1H), 4.20 (t, J = 7.0 Hz, 2H), 1.75–0.88 (m, 13H); 13C NMR (75 MHz, CDCl3): 161.2, 62.2, 35.8, 34.4, 33.1, 26.4, 26.2.
3,7-Dimethyloct-6-en-1-yl formate (8a): 1H NMR (300 MHz, CDCl3): 8.06 (br s, 1H), 5.08 (t, J = 7.0 Hz, 2H), 4.23–4.16 (m, 2H), 2.05–1.93 (m, 2H), 1.72–1.15 (m, 7H), 1.71 (s, 3H), 1.65 (s, 3H), 0.92 (d, J = 7.0 Hz, 3H); 13C NMR (75 MHz, CDCl3): 161.2, 131.4, 124.4, 62.5, 36.9, 35.3, 29.3, 25.7, 25.3, 19.3, 17.6.
3-Methoxybenzyl formate (12a): 1H NMR (500 MHz, CDCl3): 8.15 (br s, 1H), 7.31–7.28 (m, 1H), 6.96–6.87 (m, 2H), 5.18 (s, 2H), 3.82 (s, 3H); 13C NMR (125 MHz, CDCl3): 160.7, 159.7, 136.6, 129.7, 120.4, 114.0, 113.6, 65.5, 55.2.
Benzyl formate (13a): 1H NMR (300 MHz, CDCl3): 8.15 (br s, 1H), 7.40–7.36 (m, 5H), 5.22 (br s, 2H); 13C NMR (75 MHz, CDCl3): 160.7, 135.2, 128.6, 128.5, 128.3, 65.7.
Piperidine-1-carbaldehyde (15a): 1H NMR (500 MHz, CDCl3): 7.99 (br s, 1H), 3.47 (t, J = 6.0 Hz, 2H), 3.29 (t, J = 6.0 Hz, 2H), 1.69–1.52 (m, 6H); 13C NMR (125 MHz, CDCl3): 160.8, 46.8, 40.6, 26.5, 25.0, 24.7.
N,N-Diethylformamide (16a): 1H NMR (500 MHz, CDCl3): 8.04 (br s, 1H), 3.36 (q, J = 7.5 Hz, 2H), 3.27 (q, J = 7.5 Hz, 2H), 1.18 (t, J = 7.5 Hz, 3H), 1.12 (t, J = 7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3): 162.2, 41.8, 36.5, 14.8, 12.7.
N-Butyl-N-methylformamide (17a): 1H NMR (300 MHz, CDCl3); two rotamers in a relative ratio ~2/1: 8.04 (br s, 1H from the two rotamers), 3.29 (t, J = 7.0 Hz, 2H of the minor rotamer), 3.19 (t, J = 7.0 Hz, 2H of the major rotamer), 2.92 (s, 3H of the minor rotamer), 2.85 (s, 3H of the major rotamer), 1.70–1.52 (m, 2H from the two rotamers), 0.90 (t, J = 7.5 Hz, 3H of the minor rotamer), 0.89 (t, J = 7.5 Hz, 3H of the major rotamer); 13C NMR (75 MHz, CDCl3): 162.7 (major rotamer), 162.5 (minor rotamer), 51.2 (major rotamer), 45.7 (minor rotamer), 34.5 (minor rotamer), 29.3 (major rotamer), 21.1 (major rotamer), 19.9 (minor rotamer), 11.1 (minor rotamer), 10.7 (major rotamer).
Morpholine-4-carbaldehyde (18a): 1H NMR (500 MHz, CDCl3): 8.06 (br s, 1H), 3.70 (t, J = 5.0 Hz, 2H), 3.67 (t, J = 5.0 Hz, 2H), 3.58 (t, J = 5.0 Hz, 2H), 3.40 (t, J = 5.0 Hz, 2H); 13C NMR (125 MHz, CDCl3): 160.8, 67.2, 66.4, 45.8, 40.6.
Pyrrolidine-1-carbaldehyde (19a): 1H NMR (300 MHz, CDCl3): 8.30 (br s, 1H), 3.53 (t, J = 5.0 Hz, 2H), 3.44 (t, J = 5.0 Hz, 2H), 1.95–1.89 (m, 4H); 13C NMR (75 MHz, CDCl3): 161.0, 46.2, 43.3, 24.9, 24.2.
N,N-Dibutylformamide (20a): 1H NMR (500 MHz, CDCl3): 8.03 (br s, 1H), 3.27 (t, J = 7.5 Hz, 2H), 3.18 (q, J = 7.5 Hz, 2H), 1.54–1.46 (m, 4H), 1.34–1.26 (m, 4H), 0.92 (t, J = 7.5 Hz, 6H); 13C NMR (125 MHz, CDCl3): 162.7, 47.2, 41.8, 30.7, 29.6, 20.1, 19.6, 13.8, 13.6.
4-Methylpiperidine-1-carbaldehyde (21a): 1H NMR (300 MHz, CDCl3): 8.00 (br s, 1H), 4.38–4.32 (m, 1H), 3.60–3.54 (m, 1H), 3.09–2.99 (m, 1H), 2.65–2.55 (m, 1H), 1.77–1.52 (m, 3H), 1.18–1.02 (m, 2H), 0.95 (d, J = 6.5 Hz, 3H); 13C NMR (75 MHz, CDCl3): 160.8, 46.2, 39.9, 34.7, 33.2, 31.3, 21.7.

4. Conclusions

In conclusion, we present herein a novel method for the synthesis of formate esters through an aerobic oxidative coupling between alcohols and paraformaldehyde catalyzed by commercially available Au nanoparticles supported on TiO2. The coupling occurs through the Au nanoparticle-catalyzed oxidation of the labile hemiacetal by air. This concept was also applied to the synthesis of formamides. The formaldehyde-amine oxidative coupling occurs more readily than in the case of alcohols, and there is no need to use a base additive, as is the case in the currently known analogous coupling methodologies.

Supplementary Materials

The 1H and 13C NMR copies of products are available online at https://www.mdpi.com/2079-4991/7/12/440/s1.

Acknowledgments

This work was supported by the Special Account for Research Funds of the University of Crete.

Author Contributions

E.V. did the initial experiments regarding the Au-catalyzed transformations of oxetane 1, and tested the Au/TiO2-catalyzed formylation of 1-octanol with paraformaldehyde, that triggered the development of the current methodologies. I.M. performed all the experiments and interpretation of results. M.S. supervised this work, prepared and reviewed the manuscript.

Conflicts of Interest

The authors declare no conflict of interest.

References and Note

  1. Haruta, M.; Yamada, N.; Kobayashi, T.; Iijima, S. Gold catalysts prepared by coprecipitation for low-temperature oxidation of hydrogen and of carbon monoxide. J. Catal. 1989, 115, 301–309. [Google Scholar] [CrossRef]
  2. Ishida, T.; Koga, H.; Okumura, M.; Haruta, M. Advances in gold catalysis and understanding the catalytic mechanism. Chem. Rec. 2016, 16, 2278–2293. [Google Scholar] [CrossRef] [PubMed]
  3. Min, B.K.; Friend, C.M. Heterogeneous gold-based catalysis for green chemistry:  Low-temperature CO oxidation and propene oxidation. Chem. Rev. 2007, 107, 2709–2724. [Google Scholar] [CrossRef] [PubMed]
  4. Della Pina, C.; Falletta, E.; Rossik, M. Update on selective oxidation using gold. Chem. Soc. Rev. 2012, 41, 350–369. [Google Scholar] [CrossRef] [PubMed]
  5. Corma, A.; Garcia, H. Supported gold nanoparticles as catalysts for organic reactions. Chem. Soc. Rev. 2008, 37, 2096–2126. [Google Scholar] [CrossRef] [PubMed]
  6. Della Pina, C.; Falletta, E. Gold-catalyzed oxidation in organic synthesis: A promise kept. Catal. Sci. Technol. 2011, 1, 1564–1571. [Google Scholar] [CrossRef]
  7. Zhang, Y.; Cui, X.; Shi, F.; Deng, Y. Nano-gold catalysis in fine chemical synthesis. Chem. Rev. 2012, 112, 2467–2505. [Google Scholar] [CrossRef] [PubMed]
  8. Sharma, A.S.; Kaur, H.; Shah, D. Selective oxidation of alcohols by supported gold nanoparticles: Recent advances. RSC Adv. 2016, 6, 28688–28727. [Google Scholar] [CrossRef]
  9. Stratakis, M.; Garcia, H. Catalysis by supported gold nanoparticles: Beyond aerobic oxidative processes. Chem. Rev. 2012, 112, 4469–4506. [Google Scholar] [CrossRef] [PubMed]
  10. Pan, M.; Brush, A.J.; Pozun, Z.D.; Ham, H.C.; Yu, W.-Y.; Henkelman, G.; Hwang, G.S.; Mullins, C.B. Model studies of heterogeneous catalytic hydrogenation reactions with gold. Chem. Soc. Rev. 2013, 42, 5002–5013. [Google Scholar] [CrossRef] [PubMed]
  11. Mitsudome, T.; Kaneda, K. Gold nanoparticle catalysts for selective hydrogenations. Green Chem. 2013, 15, 2636–2654. [Google Scholar] [CrossRef]
  12. Takale, B.S.; Bao, M.; Yamamoto, Y. Gold nanoparticle (AuNPs) and gold nanopore (AuNPore) catalysts in organic synthesis. Org. Biomol. Chem. 2014, 12, 2005–2027. [Google Scholar] [CrossRef] [PubMed]
  13. Liu, X.; He, L.; Liu, Y.-M.; Cao, Y. Supported gold catalysis: From small molecule activation to green chemical synthesis. Acc. Chem. Res. 2014, 47, 793–804. [Google Scholar] [CrossRef] [PubMed]
  14. Vasilikogiannaki, E.; Louka, A.; Stratakis, M. Gold-nanoparticle-catalyzed silaboration of oxetanes and unactivated epoxides. Organometallics 2016, 35, 3895–3902. [Google Scholar] [CrossRef]
  15. Raptis, C.; Garcia, H.; Stratakis, M. Selective isomerization of epoxides to allylic alcohols catalyzed by TiO2-supported gold nanoparticles. Angew. Chem. Int. 2009, 48, 3133–3136. [Google Scholar] [CrossRef] [PubMed]
  16. Loksha, Y.M.; Pedersen, E.B.; Loddo, R.; Sanna, G.; Collu, G.; Giliberti, G.; La Colla, P. Synthesis of novel fluoro analogues of MKC442 as microbicides. J. Med. Chem. 2014, 57, 5169–5178. [Google Scholar] [CrossRef] [PubMed]
  17. The screened catalysts Au/TiO2, Au/Al2O3, and Au/ZnO (~1 wt % in Au) are commercially available by Strem Chemicals, and have an average gold crystallite size of ~2–3 nm.
  18. Abad, A.; Corma, A.; Garcia, H. Catalyst parameters determining activity and selectivity of supported gold nanoparticles for the aerobic oxidation of alcohols: The molecular reaction mechanism. Chem. Eur. J. 2008, 14, 212–222. [Google Scholar] [CrossRef] [PubMed]
  19. Huang, J.; Dai, W.-L.; Li, H.; Fan, K. Au/TiO2 as high efficient catalyst for the selective oxidative cyclization of 1,4-butanediol to γ-butyrolactone. J. Catal. 2007, 252, 69–76. [Google Scholar] [CrossRef]
  20. Fristrup, P.; Johansen, L.B.; Christensen, C.H. Mechanistic investigation of the gold-catalyzed aerobic oxidation of aldehydes: Added insight from Hammett studies and isotopic labelling experiments. Chem. Commun. 2008, 2750–2752. [Google Scholar] [CrossRef] [PubMed]
  21. Oliveira, R.L.; Kiyohara, P.K.; Rossi, L.N. Clean preparation of methyl esters in one-step oxidative esterification of primary alcohols catalyzed by supported gold nanoparticles. Green Chem. 2009, 11, 1366–1370. [Google Scholar] [CrossRef]
  22. Li, G.; Enache, D.I.; Edwards, J.; Carley, A.F.; Knight, D.W.; Hutchings, G.J. Solvent-free oxidation of benzyl alcohol with oxygen using zeolite-supported Au and Au–Pd catalysts. Catal. Lett. 2006, 110, 7–13. [Google Scholar] [CrossRef]
  23. Niknam, K.; Saberi, D. Preparation of sulfuric acid ([3-(3-silicapropyl)sulfanyl]propyl)ester: A new and recyclable catalyst for the formylation and acetylation of alcohols under heterogeneous conditions. Appl. Catal. A Gen. 2009, 366, 220–225. [Google Scholar] [CrossRef]
  24. Fernando, J.E.M.; Levens, A.; Moock, D.; Lupton, D.W. N-Heterocyclic carbene catalyzed transformylation. Synthesis 2017, 49, 3505–3510. [Google Scholar]
  25. Hagiwara, H.; Morohashi, K.; Sakai, H.; Suzuki, T.; Ando, M. Acetylation and formylation of alcohols with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl formate. Tetrahedron 1998, 54, 5845–5852. [Google Scholar] [CrossRef]
  26. Amin, R.; Ardeshir, K.; Heidar Ali, A.-N.; Zahra, T.-R. Formylation of alcohol with formic acid under solvent-free and neutral conditions catalyzed by free I2 or I2 generated in situ from Fe(NO3)3·9H2O/NaI. Chin. J. Catal. 2011, 32, 60–64. [Google Scholar] [CrossRef]
  27. Jiang, L.-B.; Li, R.; Li, H.-P.; Qi, X.; Wu, X.-F. Palladium-catalyzed carbonylative synthesis of aryl formates under mild conditions. ChemCatChem 2016, 8, 1788–1791. [Google Scholar] [CrossRef]
  28. Liang, S.; Monsen, P.; Hammond, G.B.; Xu, B. Au/TiO2 catalyzed reductive amination of aldehydes and ketones using formic acid as reductant. Org. Chem. Front. 2016, 3, 505–509. [Google Scholar] [CrossRef]
  29. 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]
  30. Shah, N.; Gravel, E.; Jawale, D.V.; Doris, E.; Namboothiri, I.N.N. Carbon nanotube-gold nanohybrid catalyzed N-formylation of amines by using aqueous formaldehyde. ChemCatChem 2014, 6, 2201–2205. [Google Scholar] [CrossRef]
  31. 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]
  32. 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] [PubMed]
  33. 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] [PubMed]
  34. Soule, J.-F.; Miyamura, H.; Kobayashi, S. Powerful amide synthesis from alcohols and amines under aerobic conditions catalyzed by gold or gold/iron, -nickel or -cobalt nanoparticles. J. Am. Chem. Soc. 2011, 133, 18550–18553. [Google Scholar] [CrossRef] [PubMed]
  35. Wang, Y.; Zhu, D.; Tang, L.; Wang, S.; Wang, Z. Highly efficient amide synthesis from alcohols and amines by virtue of a water-soluble gold/DNA catalyst. Angew. Chem. Int. Ed. 2011, 50, 8917–8921. [Google Scholar] [CrossRef] [PubMed]
  36. Lou, X.B.; He, L.; Qian, Y.; Liu, Y.M.; Cao, Y.; Fan, K.N. Highly Chemo- and Regioselective Transfer Reduction of Aromatic Nitro Compounds using Ammonium Formate Catalyzed by Supported Gold Nanoparticles. Adv. Synth. Catal. 2011, 353, 281–286. [Google Scholar] [CrossRef]
  37. Mitsudome, T.; Urayama, T.; Fujita, S.; Maeno, Z.; Mizugaki, T.; Jitsukawa, K.; Kaneda, K. A titanium dioxide-supported gold nanoparticle catalyst for the selective N-formylation of functionalized amines with CO2 and H2. ChemCatChem 2017, 9, 3632–3636. [Google Scholar] [CrossRef]
  38. El Dine, T.M.; Evans, D.; Rouden, J.; Blanchet, J. Formamide synthesis through borinic acid-catalysed transamidation under mild conditions. Chem. Eur. J. 2016, 22, 5894–5898. [Google Scholar] [CrossRef] [PubMed]
  39. Hulla, M.; Bobbink, F.D.; Das, S.; Dyson, P.J. CO2-based N-formylation of amines catalyzed by fluoride and hydroxide anions. ChemCatChem 2016, 8, 3338–3342. [Google Scholar] [CrossRef]
  40. Fang, C.; Lu, C.; Liu, M.; Zhu, Y.; Fu, Y.; Lin, B.-L. Selective formylation and methylation of amines using carbon dioxide and hydrosilane catalyzed by alkaline metal carbonates. ACS Catal. 2016, 6, 7876–7881. [Google Scholar] [CrossRef]
  41. Liu, H.; Mei, Q.; Xu, Q.; Song, J.; Liu, H.; Han, B. Synthesis of formamides containing unsaturated groups by N-formylation of amines using CO2 with H2. Green Chem. 2017, 19, 196–201. [Google Scholar] [CrossRef]
  42. Ortega, N.; Richter, C.; Glorius, F. N-Formylation of amines by methanol activation. Org. Lett. 2013, 15, 1776–1779. [Google Scholar] [CrossRef] [PubMed]
  43. 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]
  44. Li, W.; Wu, X.-F. A practical and general base-catalyzed carbonylation of amines for the synthesis of N-formamides. Chem. Eur. J. 2015, 21, 14943–14948. [Google Scholar] [CrossRef] [PubMed]
Nanomaterials 07 00440 sch001 550
Scheme 1. The transformations of an oxetane (1) in the presence of Au/TiO2 and a proposed mechanism, which triggered the current study of a methodology for the formation of formate esters and formamides via the aerobic oxidative coupling between alcohols/amines and paraformaldehyde.
Scheme 1. The transformations of an oxetane (1) in the presence of Au/TiO2 and a proposed mechanism, which triggered the current study of a methodology for the formation of formate esters and formamides via the aerobic oxidative coupling between alcohols/amines and paraformaldehyde.
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Nanomaterials 07 00440 sch002 550
Scheme 2. Aerobic oxidative coupling between 1-octanol and paraformaldehyde forming 1-octyl formate (2b) catalyzed by Au/TiO2 and the proposed mechanism.
Scheme 2. Aerobic oxidative coupling between 1-octanol and paraformaldehyde forming 1-octyl formate (2b) catalyzed by Au/TiO2 and the proposed mechanism.
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Figure 1. Formylation of alcohols via their aerobic oxidative coupling with paraformaldehyde catalyzed by Au/TiO2. a Isolated yields after column chromatography, except if referred as yields by GC. b Reaction time 18–22 h, 5 equiv of paraformaldehyde. c Side products from the partial oxidation of benzylic alcohols (~15%), acetalization of formaldehyde (~5–10%), and the formation of minor amounts of dibenzyl ethers (~10%) drops the yield of formates.
Figure 1. Formylation of alcohols via their aerobic oxidative coupling with paraformaldehyde catalyzed by Au/TiO2. a Isolated yields after column chromatography, except if referred as yields by GC. b Reaction time 18–22 h, 5 equiv of paraformaldehyde. c Side products from the partial oxidation of benzylic alcohols (~15%), acetalization of formaldehyde (~5–10%), and the formation of minor amounts of dibenzyl ethers (~10%) drops the yield of formates.
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Figure 2. N-Formylation of secondary amines via oxidative coupling with paraformaldehyde catalyzed by Au/TiO2.
Figure 2. N-Formylation of secondary amines via oxidative coupling with paraformaldehyde catalyzed by Au/TiO2.
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Table
Table 1. Optimization of conditions regarding the Au nanoparticle-catalyzed formylation of 1-octanol (2) with paraformaldehyde.
Table 1. Optimization of conditions regarding the Au nanoparticle-catalyzed formylation of 1-octanol (2) with paraformaldehyde.
Nanomaterials 07 00440 i001
EntryCatalystSolventConversion (%)Selectivity (2a/2b)
1Au/TiO21,2-Dichloroethane10095/5
2Au/TiO2Ethyl acetate4592/8
3Au/TiO2Tetrahydrofuran3479/21
4Au/TiO2Toluene89 a,b98/2
5Au/TiO2Hexane3497/3
6Au/Al2O31,2-Dichloroethane3596/4
7Au/ZnO1,2-Dichloroethane5098/2
8Au/Al2O3Toluene5Not Determined
9Au/ZnOToluene6199/1
a Conversion 100% after 12–13 h, or after 10 h at 80 °C. b Regarding recycling studies, in the 2nd run: 100% conversion after 13 h; 3rd run: 100% conversion after 15 h; 4th run: 100% conversion after 15 h; 5th run: 100% conversion after 16 h.

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MDPI and ACS Style

Metaxas, I.; Vasilikogiannaki, E.; Stratakis, M. Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde. Nanomaterials 2017, 7, 440. https://doi.org/10.3390/nano7120440

AMA Style

Metaxas I, Vasilikogiannaki E, Stratakis M. Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde. Nanomaterials. 2017; 7(12):440. https://doi.org/10.3390/nano7120440

Chicago/Turabian Style

Metaxas, Ioannis, Eleni Vasilikogiannaki, and Manolis Stratakis. 2017. "Synthesis of Formate Esters and Formamides Using an Au/TiO2-Catalyzed Aerobic Oxidative Coupling of Paraformaldehyde" Nanomaterials 7, no. 12: 440. https://doi.org/10.3390/nano7120440

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