Gold-amine cooperative catalysis for reductions and reductive aminations using formic acid as hydrogen source

doi:10.1016/j.apcatb.2020.118728

Applied Catalysis B: Environmental

Volume 267, 15 June 2020, 118728

https://doi.org/10.1016/j.apcatb.2020.118728 Get rights and content

Highlights

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A gold catalyst assisted by amine was applied in transfer hydrogenation reactions.
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High reaction rate was obtained when using an appropriate amine.
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Decomposition of Au-formate species is involved in the rate-determining step of the reaction.
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The catalyst could be reused up to five times without any significant loss of activity.
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Efficient and selective method to catalyze the semihydrogenation of alkynes and synthesis of valuables amines.

Abstract

Selective hydrogenation of alkynes to alkenes and reductive amination are industrially important reactions to synthesize a variety of fine and bulk chemicals. We report herein on a green and convenient approach for Z-alkenes and secondary amines using gold catalyst and formic acid (FA) as a green reductant. Furthermore, we highlight that the key to successfully obtain high reaction rates is to use an appropriate amine, which acts cooperatively with the gold surface, to activate formic acid. Studies with deuterium-labeled hydrogen donors gave insights that the decomposition of Au-formate species is involved in the rate-determining step. Moreover, various valuable secondary amines could be synthetized from readily available nitro and carbonyl compounds. This new strategy provides a cleaner, safer, more efficient and selective way to catalyze the synthesis of Z-alkenes and valuable amines.

Graphical abstract

Transfer hydrogenation via amine-assisted formate decomposition at the Au NPs interface is a cleaner, safer, more efficient and selective manner to access Z-alkynes and valuables amines.

Introduction

Catalytic hydrogenation constitutes one of the most fundamental methodologies in organic synthesis and in chemical industry, contributing to the production of numerous fine and bulk products [1]. In general, hydrogenation reactions are carried out by using molecular hydrogen as reductant. However, these reactions typically require high H₂ pressure, which can lead to substrate over-reduction. Moreover, elaborate experimental setups are often required [2]. In this sense, an attractive alternative to the common use of molecular hydrogen is the utilization of inexpensive and readily available hydrogen donors, a strategy known as transfer hydrogenation (TH) [[3], [4], [5]].

Among the various hydrogen donors used in TH, formic acid (FA, HCOOH) has emerged as a green and bio-renewable hydrogen carrier which the additional advantage of utilizing CO₂ [3,6]. In fact, a significant number of protocols using FA as hydride source has emerged, employing either homogeneous or heterogeneous catalysts [2]. Recently, heterogeneous catalysts based on gold nanoparticles (Au NPs) in the presence of FA have shown promising catalytic properties in chemoselective reduction reactions [[7], [8], [9]]. Gold-based catalysts used in the TH reaction rely on Au NPs supported on titania [9,10] or Au-NPore [11]. Furthermore, Vilhanova et al. [8] described Au NPs supported on silica as an active catalyst in transfer hydrogenations of N-heterocyclic compounds using FA/triethylamine as a hydrogen-donor mixture. The activity of the previously related system is attributed to the exceptionally small sub-nanometer gold particles. Despite these important achievements, little is known about how the addition of base (or amines) affects the hydrogenation reactions using FA as H-source. Recently, we have shown that the adsorption of amines on a gold surface decreases the energy barrier for the dissociation of H₂ as well as the transfer of the H⁻/H⁺ pair to the organic moiety [12].

In an effort to shed light on the catalytic activity of gold catalysts in TH reactions, we herein report a general study on the influence of different amines. The preparation and catalytic activity of well-controlled Au NPs supported on silica were monitored by adding different amines to Au NPs and by using FA as the H-source. The catalyst systems were first explored towards the selective hydrogenation of alkynes and then to the synthesis of secondary amines via reductive amination of readily available nitro and carbonyl compounds. Au NPs in combination with amines were found to be an efficient and highly selective catalytic system for TH reactions with FA. Both the desired alkenes and secondary amines were obtained under mild conditions in moderate to excellent yields.

Section snippets

Materials

HAuCl₄·3H₂O (hydrogen tetrachloroaurate trihydrate, 48 % in gold, Sigma–Aldrich), Na₃C₆H₅O₇ (Sodium citrate tribasic dehydrate, ≥99,0 %, Sigma–Aldrich), C₇₆H₅₂O₄₆ (Tannic acid, ≥99,9 %, Sigma-Aldrich), TEOS (Tetraethyl orthosilicate, 98 %, Sigma-Aldrich), APTES ((3-Aminopropyl)triethoxysilane, 99 %, Sigma-Aldrich), NH₄OH (Ammonium hydroxide, 28 %, Mallinckrodt), Toluene (Mallinckrodt, 99,9 %), K₂CO₃ (Potassium Carbonate, 99 %, Synth Brazil), Ethanol (99 %, Synth Brazil). Unless otherwise

Catalyst preparation and characterization

We started our studies with the preparation of Au/SiO₂-NH₂ catalyst with Stöber silica as the support followed by the immobilization of pre-synthesized Au NPs at its surface (sol-immobilization method). SiO₂ microspheres were prepared according to a previously reported method [10] and functionalized with amino-propyl groups [11]. A scanning electron microscopy image (Fig. S1A, Supporting information) shows that the support possesses controlled spherical morphology and a very uniform particle

Conclusions

In summary, we have successfully applied gold catalysis for the selective transfer hydrogenation of alkynes and reductive coupling of nitro and carbonyl compounds. By combining renewable formic acid as hydrogen source with the appropriate amine and the supported gold nanoparticles, a benign and sustainable method for the chemical synthesis of a range of alkenes and secondary amines was developed. The gold catalyst could be reused up to five times without any significant loss of activity.

CRediT authorship contribution statement

Jhonatan L. Fiorio: Conceptualization, Methodology, Investigation, Validation, Writing - original draft. Thaylan P. Araújo: Methodology, Investigation, Validation, Writing - review & editing. Eduardo C.M. Barbosa: Methodology, Investigation, Validation, Writing - review & editing. Jhon Quiroz: . Pedro H.C. Camargo: Conceptualization, Resources, Validation, Supervision, Funding acquisition, Writing - review & editing. Matthias Rudolph: Methodology, Validation, Writing - review & editing. A.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors are grateful to the Brazilian government agencies FAPESP (grant numbers 2016/16738-7, 2015/21366-9 and 2015/26308-7), Serrapilheira Institute (grant number Serra-1709-16900), CNPq, and CAPES for financial support. L. M. R. and P.H.C.C. thank CNPq for the research fellowships. J. Q., T.P.A., and E.C.M.B. thank FAPESP for the fellowships (grant numbers 2016/17866-9, 2017/07564-8, and 2015/11452-5, respectively). J.L.F also thanks CAPES-DAAD-CNPQ for his scholarship (Grant

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View full text

Gold-amine cooperative catalysis for reductions and reductive aminations using formic acid as hydrogen source

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Catalyst preparation and characterization

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

Chin. J. Catal.

Adv. Synth. Catal.

Adv. Synth. Catal.

Adv. Synth. Catal.

Appl. Catal. A Gen.

J. Catal.

Org. Chem. Front.

Catalytic transfer hydrogenation

Chem. Rev.

The golden age of transfer hydrogenation

Chem. Rev.

Supported gold catalysis: from small molecule activation to green chemical synthesis

Acc. Chem. Res.

Supported gold nanoparticles catalyzed cis-selective semihydrogenation of alkynes using ammonium formate as the reductant

Chem. Commun.

Cis-semihydrogenation of alkynes with amine borane complexes catalyzed by gold nanoparticles under mild conditions

Chem. Commun.

Catalysis by supported gold nanoparticles: beyond aerobic oxidative processes

Chem. Rev.

Selective transfer semihydrogenation of alkynes with nanoporous gold catalysts

J. Org. Chem.

Gold–ligand-catalyzed selective hydrogenation of alkynes into cis -alkenes via H2 heterolytic activation by frustrated lewis pairs

ACS Catal.

Stöber synthesis of monodispersed luminescent silica nanoparticles for bioanalytical assays

Langmuir