- Cross-Linked Artificial Enzyme Crystals as Heterogeneous Catalysts for Oxidation Reactions
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Designing systems that merge the advantages of heterogeneous catalysis, enzymology, and molecular catalysis represents the next major goal for sustainable chemistry. Cross-linked enzyme crystals display most of these essential assets (well-designed mesoporous support, protein selectivity, and molecular recognition of substrates). Nevertheless, a lack of reaction diversity, particularly in the field of oxidation, remains a constraint for their increased use in the field. Here, thanks to the design of cross-linked artificial nonheme iron oxygenase crystals, we filled this gap by developing biobased heterogeneous catalysts capable of oxidizing carbon-carbon double bonds. First, reductive O2 activation induces selective oxidative cleavage, revealing the indestructible character of the solid catalyst (at least 30 000 turnover numbers without any loss of activity). Second, the use of 2-electron oxidants allows selective and high-efficiency hydroxychlorination with thousands of turnover numbers. This new technology by far outperforms catalysis using the inorganic complexes alone, or even the artificial enzymes in solution. The combination of easy catalyst synthesis, the improvement of "omic" technologies, and automation of protein crystallization makes this strategy a real opportunity for the future of (bio)catalysis.
- Lopez, Sarah,Rondot, Laurianne,Leprêtre, Chloé,Marchi-Delapierre, Caroline,Ménage, Stéphane,Cavazza, Christine
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supporting information
p. 17994 - 18002
(2017/12/26)
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- Enantioselective synthesis of vicinal halohydrins via dynamic kinetic resolution
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(Chemical Equation Presented) Expanding the scope of enantioselective catalysis via DKR, transfer hydrogenation of a variety of cyclic α-halo ketones was accomplished using the Noyori/Ikariya (R,R)- or (S,S)-I catalysts and either HCO2H/Et3N or HCO2Na/n-Bu 4NBr in H2O/CH2Cl2 as the hydrogen sources. Good yields of vicinal bromo-, chloro-, and fluorohydrins with excellent de and ee levels were achieved in most cases after a simple tuning of reaction conditions.
- Ros, Abel,Magriz, Antonio,Dietrich, Hansjoerg,Fernandez, Rosario,Alvarez, Eleuterio,Lassaletta, Jose M.
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p. 127 - 130
(2007/10/03)
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