Hybrid Metal Catalysts as Valuable Tools in Organic Synthesis: An Overview of the Recent Advances in Asymmetric C─C Bond Formation Reactions DOI Creative Commons
Isabella Rimoldi, Giulia Coffetti, Raffaella Gandolfi

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(21), P. 5090 - 5090

Published: Oct. 28, 2024

Carbon–carbon bond formation represents a key reaction in organic synthesis, resulting paramount importance for constructing the carbon backbone of molecules. However, traditional metal-based catalysis, despite its advantages, often struggles with issues related to efficiency, selectivity, and sustainability. On other hand, while biocatalysis offers superior selectivity due an extraordinary recognition process substrate, scope applicable reactions remains somewhat limited. In this context, Artificial Metalloenzymes (ArMs) Metallo Peptides (MPs) offer promising not fully explored solution, merging two fields transition metal catalysis biotransformations, by inserting catalytically active cofactor into customizable protein scaffold or coordinating ion directly short tunable amino acid (Aa) sequence, respectively. As result, these hybrid catalysts have gained attention as valuable tools challenging catalytic transformations, providing systems new-to-nature properties synthesis. This review overview recent advances development ArMs MPs, focusing on their application asymmetric carbon–carbon bond-forming reactions, such carbene insertion, Michael additions, Friedel–Crafts cross-coupling cyclopropanation, underscoring versatility synthesizing biologically relevant compounds.

Language: Английский

Automated Flow Synthesis of Artificial Heme Enzymes for Enantiodivergent Biocatalysis DOI
Giulio Fittolani, Dennis A. Kutateladze, Andrei Loas

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

The remarkable efficiency with which enzymes catalyze small-molecule reactions has driven their widespread application in organic chemistry. Here, we employ automated fast-flow solid-phase synthesis to access catalytically active full-length without restrictions on the number and structure of noncanonical amino acids incorporated. We demonstrate total syntheses iron-dependent Bacillus subtilis myoglobin (BsMb) sperm whale (SwMb). synthetic displayed excellent enantioselectivity yield carbene transfer reactions. Absolute control over styrene cyclopropanation was achieved using L- D-BsMb mutants, delivered each enantiomer cyclopropane product identical opposite enantiomeric enrichment. BsMb mutants outfitted were used facilitate detailed structure-activity relationship studies, revealing a previously unrecognized hydrogen-bonding interaction as primary driver cyclopropanation. anticipate that our approach will advance biocatalysis by providing reliable rapid fully possessing acids.

Language: Английский

Citations

0
Nickel-Catalyzed Reductive Arylation of gem-Bromofluorocyclopropanes To Construct Monofluorinated Cyclopropane Derivatives DOI
Wen Zhang, Yuheng Huang,

Tian-Rui Wu

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 19, 2025

A nickel-catalyzed reductive cross-coupling of gem-bromofluorocyclopropanes with aryl bromides for the synthesis monofluorinated cyclopropane derivatives is reported. Different from cleavage route ring reported by previous works, this catalytic system shows excellent regioselectivity control cyclic selectivity, giving as major product. This transformation demonstrates mild conditions, high efficiency, a broad substrate scope, and good functional group compatibility, providing facile method diversified cyclopropane-containing drugs bioactive molecules.

Language: Английский

Citations

0
Diastereoselective synthesis of 5,5-Difluoroisoxazolidine via [3 + 2] cycloaddition between Nitrones and Difluoroacrylates DOI
Miaomiao Zhang, Lingyu Kong, Shengqiang Li

et al.

Tetrahedron Letters, Journal Year: 2025, Volume and Issue: unknown, P. 155647 - 155647

Published: May 1, 2025

Language: Английский

Citations

0
Engineering metalloenzymes for new-to-nature carbene and nitrene transfer biocatalysis DOI
Weitao Pan, Xinlong Fan, Wei Jiang

et al.

CHINESE JOURNAL OF CATALYSIS (CHINESE VERSION), Journal Year: 2025, Volume and Issue: 72, P. 4 - 23

Published: May 1, 2025

Language: Английский

Citations

0
Asymmetric Transfer Hydrogenation of gem-Difluorocyclopropenyl Ketones: The Synthesis and Functionalization of Enantioenriched cis gem-Difluorocyclopropyl Ketones DOI

Olivier Charron,

Marharyta Kosiuha,

Phannarath Phansavath

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(19), P. 14073 - 14080

Published: Sept. 16, 2024

The asymmetric transfer hydrogenation of

Language: Английский

Citations

1
Hybrid Metal Catalysts as Valuable Tools in Organic Synthesis: An Overview of the Recent Advances in Asymmetric C─C Bond Formation Reactions DOI Creative Commons
Isabella Rimoldi, Giulia Coffetti, Raffaella Gandolfi

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(21), P. 5090 - 5090

Published: Oct. 28, 2024

Carbon–carbon bond formation represents a key reaction in organic synthesis, resulting paramount importance for constructing the carbon backbone of molecules. However, traditional metal-based catalysis, despite its advantages, often struggles with issues related to efficiency, selectivity, and sustainability. On other hand, while biocatalysis offers superior selectivity due an extraordinary recognition process substrate, scope applicable reactions remains somewhat limited. In this context, Artificial Metalloenzymes (ArMs) Metallo Peptides (MPs) offer promising not fully explored solution, merging two fields transition metal catalysis biotransformations, by inserting catalytically active cofactor into customizable protein scaffold or coordinating ion directly short tunable amino acid (Aa) sequence, respectively. As result, these hybrid catalysts have gained attention as valuable tools challenging catalytic transformations, providing systems new-to-nature properties synthesis. This review overview recent advances development ArMs MPs, focusing on their application asymmetric carbon–carbon bond-forming reactions, such carbene insertion, Michael additions, Friedel–Crafts cross-coupling cyclopropanation, underscoring versatility synthesizing biologically relevant compounds.

Language: Английский

Citations

0