Designing artificial metalloenzymes by tuning of the environment beyond the primary coordination sphere

C Van Stappen, Y Deng, Y Liu, H Heidari… - Chemical …, 2022 - ACS Publications
Metalloenzymes catalyze a variety of reactions using a limited number of natural amino
acids and metallocofactors. Therefore, the environment beyond the primary coordination …

Engineering new catalytic activities in enzymes

K Chen, FH Arnold - Nature Catalysis, 2020 - nature.com
The efficiency, selectivity and sustainability benefits offered by enzymes are enticing
chemists to consider biocatalytic transformations to complement or even supplant more …

Navigating the unnatural reaction space: directed evolution of heme proteins for selective carbene and nitrene transfer

Y Yang, FH Arnold - Accounts of Chemical Research, 2021 - ACS Publications
Conspectus Despite the astonishing diversity of naturally occurring biocatalytic processes,
enzymes do not catalyze many of the transformations favored by synthetic chemists. Either …

Nature's machinery, repurposed: expanding the repertoire of iron-dependent oxygenases

NP Dunham, FH Arnold - ACS catalysis, 2020 - ACS Publications
Iron is an especially important redox-active cofactor in biology because of its ability to
mediate reactions with atmospheric O2. Iron-dependent oxygenases exploit this earth …

Dual-function enzyme catalysis for enantioselective carbon–nitrogen bond formation

Z Liu, C Calvó-Tusell, AZ Zhou, K Chen… - Nature Chemistry, 2021 - nature.com
Chiral amines can be made by insertion of a carbene into an N–H bond using two-catalyst
systems that combine a transition metal-based carbene-transfer catalyst and a chiral proton …

Iron catalysts with N-ligands for carbene transfer of diazo reagents

C Damiano, P Sonzini, E Gallo - Chemical Society Reviews, 2020 - pubs.rsc.org
Transition-metal-catalyzed carbene transfer reactions, involving diazo compounds and their
precursors, are powerful tools for creating new C–C bonds. Depending on the involved …

Iron: A worthy contender in metal carbene chemistry

VF Batista, DC GA Pinto, AMS Silva - ACS Catalysis, 2020 - ACS Publications
Carbene transfer reactions hold a pivotal role in organic synthesis, allowing the prompt
construction of complex molecules from accessible reagents. Iron complexes emerged as …

Origin and Control of Chemoselectivity in Cytochrome c Catalyzed Carbene Transfer into Si–H and N–H bonds

M Garcia-Borràs, SBJ Kan, RD Lewis… - Journal of the …, 2021 - ACS Publications
A cytochrome c heme protein was recently engineered to catalyze the formation of carbon–
silicon bonds via carbene insertion into Si–H bonds, a reaction that was not previously …

Synthesis of Rhodium Complexes with Chiral Diene Ligands via Diastereoselective Coordination and Their Application in the Asymmetric Insertion of Diazo …

NM Ankudinov, DA Chusov, YV Nelyubina… - Angewandte …, 2021 - Wiley Online Library
A new method for the synthesis of chiral diene rhodium catalysts is introduced. The readily
available racemic tetrafluorobenzobarrelene complexes [(R2‐TFB) RhCl] 2 were separated …

Enzymatic lactone-carbene C–H insertion to build contiguous chiral centers

AZ Zhou, K Chen, FH Arnold - ACS Catalysis, 2020 - ACS Publications
We report a biocatalytic platform of engineered cytochrome P411 enzymes (P450s with axial
serine ligation) to carry out efficient lactone-carbene insertion into primary and secondary α …