Artificial metalloenzymes as selective catalysts in aqueous media

Steinreiber, Johannes; Ward, Thomas R.

doi:10.1016/j.ccr.2007.09.016

Cited by 179 publications

(100 citation statements)

References 126 publications

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“…In recent years the use of metallic species with suitable ligands has allowed chemists to carry out reactions in biphasic systems so permitting an easy separation of the used catalyst, confined in a phase different from that of reagents and products, and its re-use in recycling experiments; in particular, the use of both water as co-solvent for biphasic reactions and easily recyclable water-soluble catalysts are highly desirable for the realization of green processes [1][2][3][4]. In the last years natural compounds, such as aminoacids, peptides, proteins and sugars have been used as ligands for metallic species active as catalysts [5][6][7][8][9]. In this context, some years ago we reported highly efficient and chemoselective hydroformylation [10][11][12] and hydrogenation [8] reactions using water-soluble complexes derived from the interaction between Rh(CO) 2 (acac) or [Ir(COD)Cl] 2 , respectively, with human serum albumin (HSA).…”

Section: Introductionmentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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a b s t r a c tRh(DHTANa) is a new water-soluble catalyst easily obtained by mixing in water the catalytic precursor [Rh(COD)Cl] 2 and the dihydrothioctic acid sodium salt (DHTANa). This catalyst showed to be very active in the hydrogenation of unsaturated substrates as 2-cyclohexen-1-one, the biomass-derived furfural and acetophenone. In this last case the catalytic system obtained by using as water-soluble ligand (R)-(DHTANa) afforded (R)-1-phenylethanol with very modest enantioselectivity. Rh(DHTANa) was active also in the aqueous biphase hydroformylation of styrene producing exclusively the two corresponding aldehydes with 80-86% selectivity toward the branched aldehyde 2-phenylpropanal. This new catalytic system was easily recycled in both hydrogenation and hydroformylation processes and no leaching phenomenon was observed.

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Section: Introductionmentioning

confidence: 99%

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Paganelli

Piccolo²,

Pontini

et al. 2015

Catalysis Today

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“…All chemicals and DNA oligomers were obtained from commercial sources and used without further purification. Synthesis of Ethyl 4-Chloro-1,10-phenanthroline-3-carboxylate (2). Ethyl 4-oxo-1,4-dihydro-1,10-phenanthroline-3-carboxylate 16 (1, 5.00 g, 18.6 mmol) was dissolved in POCl 3 (25 mL) and the solution was refluxed for 30 min.…”

Section: Methodsmentioning

confidence: 99%

Genetic Incorporation of a Phenanthroline-Containing Amino Acid in Escherichia coli

Jin¹,

Lee²,

Lee³

et al. 2014

Bulletin of the Korean Chemical Society

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A simple and general method that selectively introduces metal binding sites into a protein can greatly increase the ability to design and biosynthesize artificial metalloproteins. Here, we report the incorporation of a phenanthroline-containing amino acid (Phen-Ala) into proteins in Escherichia coli by using the tRNA Tyr CUAand tyrosyl aminoacyl-tRNA synthetase pair (BpyRS) from Methanococcus jannaschii, which was originally developed for a bipyridine-containing amino acid (Bpy-Ala). The incorporation efficiency of BpyRS for PhenAla was comparable to that for Bpy-Ala. Because of its high metal-binding ability and characteristic spectral properties, Phen-Ala can be a useful alternative to the existing metal-chelating amino acids for the design and synthesis of artificial metalloproteins.

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“…One of them is the design of artificial metalloenzymes obtained by the insertion of homogeneous catalysts into protein cavities; an approach with a tremendous potential in biocatalysis [2][3][4]. Numerous systems built on this concept have already been reported that include enzymes able to perform Diels-Alder reactions [5][6], transfer hydrogenation [7,8], sulfoxidation [9][10][11] and hydration [12] among others.…”

Section: Introductionmentioning

confidence: 99%

Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme

Ortega‐Carrasco

Lledós

Maréchal

2014

J. R. Soc. Interface.

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In recent years, the design of artificial metalloenzymes obtained by the insertion of homogeneous catalysts into biological macromolecules has become a major field of research. These hybrids, and the corresponding X-ray structures of several of them, are offering opportunities to better understand the synergy between organometallic and biological subsystems. In this work, we investigate the resting state and activation process of a hybrid inspired by an oxidative haemoenzyme but presenting an unexpected reactivity and structural features. An extensive series of quantum mechanics/molecular mechanics calculations show that the resting state and the activation processes of the novel enzyme differ from naturally occurring haemoenzymes in terms of the electronic state of the metal, participation of the first coordination sphere of the metal and the dynamic process. This study presents novel insights into the sensitivity of the association between organometallic and biological partners and illustrates the molecular challenge that represents the design of efficient enzymes based on this strategy.

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Artificial metalloenzymes as selective catalysts in aqueous media

Cited by 179 publications

References 126 publications

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Aqueous-phase hydrogenation and hydroformylation reactions catalyzed by a new water-soluble [rhodium]–thioligand complex

Genetic Incorporation of a Phenanthroline-Containing Amino Acid in Escherichia coli

Unravelling novel synergies between organometallic and biological partners: a quantum mechanics/molecular mechanics study of an artificial metalloenzyme

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