48 publications

48 publications

Achiral Cyclopentadienone Iron Tricarbonyl Complexes Embedded in Streptavidin: An Access to Artificial Iron Hydrogenases and Application in Asymmetric Hydrogenation

Renaud, J.-L.; Ward, T. R.

Catal. Lett., 2016, 10.1007/s10562-015-1681-6

We report on the synthesis of biotinylated (cyclopentadienone)iron tricarbonyl complexes, the in situ generation of the corresponding streptavidin conjugates and their application in asymmetric hydrogenation of imines and ketones.


Metal: Fe
Ligand type: CO; Cyclopentadienone
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 20
ee: 34
PDB: ---
Notes: ---

A Highly Active Biohybrid Catalyst for Olefin Metathesis in Water: Impact of a Hydrophobic Cavity in a β-Barrel Protein

Okuda, J.

ACS Catal., 2015, 10.1021/acscatal.5b01792

A series of Grubbs–Hoveyda type catalyst precursors for olefin metathesis containing a maleimide moiety in the backbone of the NHC ligand was covalently incorporated in the cavity of the β-barrel protein nitrobindin. By using two protein mutants with different cavity sizes and choosing the suitable spacer length, an artificial metalloenzyme for olefin metathesis reactions in water in the absence of any organic cosolvents was obtained. High efficiencies reaching TON > 9000 in the ROMP of a water-soluble 7-oxanorbornene derivative and TON > 100 in ring-closing metathesis (RCM) of 4,4-bis(hydroxymethyl)-1,6-heptadiene in water under relatively mild conditions (pH 6, T = 25–40 °C) were observed.


Metal: Ru
Ligand type: Carbene
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 9900
ee: ---
PDB: ---
Notes: ROMP (cis/trans: 48/52)

Metal: Ru
Ligand type: Carbene
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 100
ee: ---
PDB: ---
Notes: RCM

A Hybrid Ring- Opening Metathesis Polymerization Catalyst Based on an Engineered Variant of the Beta-Barrel Protein FhuA

Okuda, J.; Schwaneberg, U.

Chem. - Eur. J., 2013, 10.1002/chem.201301515

A β‐barrel protein hybrid catalyst was prepared by covalently anchoring a Grubbs–Hoveyda type olefin metathesis catalyst at a single accessible cysteine amino acid in the barrel interior of a variant of β‐barrel transmembrane protein ferric hydroxamate uptake protein component A (FhuA). Activity of this hybrid catalyst type was demonstrated by ring‐opening metathesis polymerization of a 7‐oxanorbornene derivative in aqueous solution.


Metal: Ru
Ligand type: Carbene
Host protein: FhuA ΔCVFtev
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 955
ee: ---
PDB: ---
Notes: ROMP

An Artificial Oxygenase Built from Scratch: Substrate Binding Site Identified Using a Docking Approach

Cavazza, C.; Ménage, S.

Angew. Chem., Int. Ed., 2014, 10.1002/anie.201209021

The substrate for an artificial iron monooxygenase was selected by using docking calculations. The high catalytic efficiency of the reported enzyme for sulfide oxidation was directly correlated to the predicted substrate binding mode in the protein cavity, thus illustrating the synergetic effect of the substrate binding site, protein scaffold, and catalytic site.


Metal: Fe
Ligand type: BPMCN; BPMEN
Host protein: NikA
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Sulfoxidation
Max TON: 199
ee: ≤5
PDB: ---
Notes: ---

Antibody-Metalloporphyrin Catalytic Assembly Mimics Natural Oxidation Enzymes

Keinan, E.

J. Am. Chem. Soc., 1999, 10.1021/ja990314q


Metal: Ru
Ligand type: Porphyrin
Host protein: Antibody SN37.4
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Sulfoxidation
Max TON: 750
ee: 43
PDB: ---
Notes: ---

Aqueous Phase Transfer Hydrogenation of Aryl Ketones Catalysed by Achiral Ruthenium(II) and Rhodium(III) Complexes and their Papain Conjugates

Salmain, M.

Appl. Organomet. Chem., 2013, 10.1002/aoc.2929


Metal: Rh
Ligand type: Cp*; Poly-pyridine
Host protein: Papain (PAP)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 96
ee: 15
PDB: ---
Notes: ---

Artificial Diels–Alderase based on the Transmembrane Protein FhuA

Okuda, J.

Beilstein J. Org. Chem., 2016, 10.3762/bjoc.12.124


Metal: Cu
Ligand type: Terpyridine
Host protein: FhuA
Anchoring strategy: Cystein-maleimide
Optimization: Chemical
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Artificial Metalloenzymes Derived from Bovine β-Lactoglobulin for the Asymmetric Transfer Hydrogenation of an Aryl Ketone – Synthesis, Characterization and Catalytic Activity

Salmain, M.

Dalton Trans., 2014, 10.1039/c3dt53253d


Metal: Rh
Ligand type: Cp*; Poly-pyridine
Host protein: ß-lactoglobulin
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 14
ee: 32
PDB: ---
Notes: ---

Artificial Metalloenzymes for Enantioselective Catalysis: The Phenomenon of Protein Accelerated Catalysis

Ward, T. R.

J. Organomet. Chem., 2004, 10.1016/j.jorganchem.2004.09.032


Metal: Rh
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: ---
ee: 94
PDB: ---
Notes: Reduction of acetamidoacrylic acid. 3.0-fold protein acceleration.

Metal: Rh
Host protein: Avidin (Av)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: ---
ee: 39
PDB: ---
Notes: Reduction of acetamidoacrylic acid. 12.0-fold protein acceleration.

Artificial Metalloenzymes for Olefin Metathesis Based on the Biotin-(Strept)Avidin Technology

Ward, T. R.

Chem. Commun., 2011, 10.1039/c1cc15004a


Metal: Ru
Ligand type: Carbene
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 14
ee: ---
PDB: ---
Notes: RCM

Metal: Ru
Ligand type: Carbene
Host protein: Avidin (Av)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 19
ee: ---
PDB: ---
Notes: RCM

A Structural View of Synthetic Cofactor Integration into [FeFe]-Hydrogenases

Apfel, U.-P.; Happe, T.; Kurisu, G.

Chem. Sci., 2016, 10.1039/C5SC03397G


Metal: Fe
Ligand type: CN; CO; Dithiolate
Anchoring strategy: Dative
Optimization: Chemical
Reaction: H2 evolution
Max TON: ---
ee: ---
PDB: 4XDC
Notes: H2 evolution activity of the ArM: 2874 (mmol H2)*min-1*(mg protein)-1.

Asymmetric Catalytic Sulfoxidation by a Novel VIV8 Cluster Catalyst in the Presence of Serum Albumin: A Simple and Green Oxidation System

Bian, H.-D.; Huang, F.-P.

RSC Adv., 2016, 10.1039/C6RA08153C


Metal: V
Anchoring strategy: Undefined
Optimization: Chemical
Reaction: Sulfoxidation
Max TON: 140
ee: 77
PDB: ---
Notes: Screening with different serum albumins.

Bovine Serum Albumin-Cobalt(II) Schiff Base Complex Hybrid: An Efficient Artificial Metalloenzyme for Enantioselective Sulfoxidation using Hydrogen Peroxide

Bian, H.-D.; Liang, H.

Dalton Trans., 2016, 10.1039/C5DT04507J


Metal: Co
Ligand type: Amine; Phenolate
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Sulfoxidation
Max TON: 98
ee: 87
PDB: ---
Notes: ---

Catalytic Water Oxidation by Iridium-Modified Carbonic Anhydrase

Lee, S.-Y.

Chem. - Asian J., 2017, 10.1002/asia.201701543


Metal: Ir
Ligand type: Amino acid
Anchoring strategy: Metal substitution
Optimization: Chemical
Reaction: Water oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Sodium periodate as sacrificial oxidant. TOF at pH 7 and 30°C is 39.8 min-1.

Chalcogenide Substitution in the [2Fe] Cluster of [FeFe]-Hydrogenases Conserves High Enzymatic Activity

Apfel, U.-P.; Happe, T.

Dalton Trans., 2017, 10.1039/C7DT03785F


Metal: Fe
Ligand type: CN; CO; Diselenolate
Anchoring strategy: Dative
Optimization: Chemical
Reaction: H2 evolution
Max TON: ---
ee: ---
PDB: 5OEF
Notes: ---

Chemically Engineered Papain as Artificial Formate Dehydrogenase for NAD(P)H Regeneration

Salmain, M.

Org. Biomol. Chem., 2011, 10.1039/c1ob05482a


Metal: Rh
Ligand type: Cp*; Poly-pyridine
Host protein: Papain (PAP)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Hydrogenation
Max TON: ---
ee: ---
PDB: ---
Notes: TOF = 52.1 h-1 for NAD+

Chemical Optimization of Artificial Metalloenzymes Based on the Biotin-Avidin Technology: (S)-Selective and Solvent-Tolerant Hydrogenation Catalysts via the Introduction of Chiral Amino Acid Spacers

Ward, T. R.

Chem. Commun., 2005, 10.1039/b509015f


Metal: Rh
Ligand type: Phosphine
Host protein: Streptavidin (Sav)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: ---
ee: ---
PDB: ---
Notes: ---

Cobaloxime-Based Artificial Hydrogenase

Artero, V.

Inorg. Chem., 2014, 10.1021/ic501014c


Metal: Co
Ligand type: Oxime
Host protein: Myoglobin (Mb)
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: H2 evolution
Max TON: 5
ee: ---
PDB: ---
Notes: Sperm whale myoglobin

Copper–Phthalocyanine Conjugates of Serum Albumins as Enantioselective Catalysts in Diels–Alder Reactions

Reetz, M. T.

Angew. Chem., Int. Ed., 2005, 10.1002/anie.200504561


Metal: Cu
Ligand type: Phthalocyanine
Anchoring strategy: Supramolecular
Optimization: Chemical
Max TON: 45.5
ee: 98
PDB: ---
Notes: ---

Covalent Anchoring of a Racemization Catalyst to CALB-Beads: Towards Dual Immobilization of DKR Catalysts

Klein Gebbink, R. J. M.; van Koten, G.

Tetrahedron Lett., 2011, 10.1016/j.tetlet.2011.01.106


Metal: Ru
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Acylation
Max TON: ---
ee: >99%
PDB: ---
Notes: Lipase CALB is immobilized on a solid support (Novozym®435). Dynamic kinetic resolution (DKR) of 1-phenylethanol to the acylated product.

Cross-Linked Artificial Enzyme Crystals as Heterogeneous Catalysts for Oxidation Reactions

Cavazza, C.; Ménage, S.

J. Am. Chem. Soc., 2017, 10.1021/jacs.7b09343


Metal: Fe
Ligand type: ---
Host protein: NikA
Anchoring strategy: Supramolecular
Optimization: Chemical
Max TON: 28000
ee: ---
PDB: 5ON0
Notes: Cross-Linked Enzyme Crystals (CLEC) as catalysts.

Metal: Fe
Ligand type: ---
Host protein: NikA
Anchoring strategy: Supramolecular
Optimization: Chemical
Max TON: 5900
ee: ---
PDB: 5ON0
Notes: Cross-Linked Enzyme Crystals (CLEC) as catalysts.

Design of Metal Cofactors Activated by a Protein–Protein Electron Transfer System

Ueno, T.

Proc. Natl. Acad. Sci. U. S. A., 2006, 10.1073/pnas.0510968103


Metal: Fe
Ligand type: Salophen
Host protein: Heme oxygenase (HO)
Anchoring strategy: Reconstitution
Optimization: Chemical
Reaction: O2 reduction
Max TON: ---
ee: ---
PDB: 1WZD
Notes: ---

Diruthenium Diacetate-Catalyzed Aerobic Oxidation of Hydroxylamines and Improved Chemoselectivity by Immobilization to Lysozyme

Cardona, F.; Goti, A.; Messori, L.

ChemCatChem, 2017, 10.1002/cctc.201701083


Metal: Ru
Ligand type: Amino acid; OAc
Host protein: Lysozyme
Anchoring strategy: Dative
Optimization: Chemical
Max TON: 1000
ee: ---
PDB: ---
Notes: ---

Enantioselective Transfer Hydrogenation of Ketone Catalysed by Artificial Metalloenzymes Derived from Bovine β-Lactoglobulin

Salmain, M.

Chem. Commun., 2012, 10.1039/c2cc36980j


Metal: Rh
Ligand type: Cp*; Poly-pyridine
Host protein: ß-lactoglobulin
Anchoring strategy: Supramolecular
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 34
ee: 26
PDB: ---
Notes: ---

Hybrid [FeFe]-Hydrogenases with Modified Active Sites Show Remarkable Residual Enzymatic Activity

Lubitz, W.; Reijerse, E.

Biochemistry, 2015, 10.1021/bi501391d


Metal: Fe
Ligand type: CN; CO; Dithiolate
Anchoring strategy: Dative
Optimization: Chemical
Max TON: ---
ee: ---
PDB: ---
Notes: H2 evolution: TOF = 450 s-1. H2 oxidation: TOF = 150 s-1.

Hybrid Ruthenium ROMP Catalysts Based on an Engineered Variant of β-Barrel Protein FhuA ΔCVFtev: Effect of Spacer Length

Okuda, J.

Chem. - Asian J., 2015, 10.1002/asia.201403005


Metal: Ru
Ligand type: Carbene
Host protein: FhuA ΔCVFtev
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Olefin metathesis
Max TON: 555
ee: ---
PDB: ---
Notes: ROMP; cis/trans = 58/42

Immobilization of Two Organometallic Complexes into a Single Cage to Construct Protein-Based Microcompartment

Ueno, T.

Chem. Commun., 2016, 10.1039/C6CC00679E


Metal: Ir
Ligand type: Amino acid; Cp*
Host protein: Apo-ferritin
Anchoring strategy: Dative
Optimization: Chemical
Reaction: Hydrogenation
Max TON: ~2
ee: 15
PDB: 5E2D
Notes: Tandem reaction (Hydrogenation and Suzuki-Miyaura coupling) to form biphenylethanol from 4-iodoacetophenone and phenylboronic acid. TON and ee are given for the tandem reaction product.

Metal: Pd
Ligand type: Allyl; Amino acid
Host protein: Apo-ferritin
Anchoring strategy: Dative
Optimization: Chemical
Max TON: ~1
ee: 15
PDB: 5E2D
Notes: Tandem reaction (Hydrogenation and Suzuki-Miyaura coupling) to form biphenylethanol from 4-iodoacetophenone and phenylboronic acid.

Manganese Terpyridine Artificial Metalloenzymes for Benzylic Oxygenation and Olefin Epoxidation

Lewis, J. C.

Tetrahedron, 2014, 10.1016/j.tet.2014.03.008


Metal: Mn
Ligand type: Poly-pyridine
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Max TON: 19.2
ee: ---
PDB: 3EMM
Notes: ---

Metal: Mn
Ligand type: Poly-pyridine
Host protein: Nitrobindin (Nb)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Epoxidation
Max TON: 19.8
ee: ---
PDB: 3EMM
Notes: ---

Metal-Conjugated Affinity Labels: A New Concept to Create Enantioselective Artificial Metalloenzymes

Eppinger, J.

ChemistryOpen, 2013, 10.1002/open.201200044


Metal: Rh
Ligand type: Cp*; Phosphine
Host protein: Papain (PAP)
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 89
ee: 64
PDB: ---
Notes: ---

Metal: Ru
Ligand type: Benzene; Phosphine
Host protein: Bromelain
Anchoring strategy: Covalent
Optimization: Chemical
Reaction: Hydrogenation
Max TON: 44
ee: 20
PDB: ---
Notes: ---

Metal Incorporated Horseradish Peroxidase (HRP) Catalyzed Oxidation of Resveratrol: Selective Dimerization or Decomposition

Pan, Y.

RSC Adv., 2013, 10.1039/c3ra43784a


Metal: Ca; Co; Mn; Ni; Zn
Ligand type: Undefined
Anchoring strategy: Undefined
Optimization: Chemical
Reaction: Oxidation
Max TON: ---
ee: ---
PDB: ---
Notes: Oxidation of resveratrol. Dimerisation product obtained.