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

Double strain-release enables formal C–O/C–F and C–N/C–F ring-opening metathesis DOI Creative Commons

Yulei Zhu,

Jie Jia,

Xiangyu Song

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13800 - 13806

Published: Jan. 1, 2024

Metathesis reactions have been established as a powerful tool in organic synthesis. While great advances were achieved double-bond metathesis, like olefin metathesis and carbonyl single-bond has received less attention the past decade. Herein, we describe first C(sp

Language: Английский

Citations

5
Catalytic prenyl conjugate additions for synthesis of enantiomerically enriched PPAPs DOI
Shawn Voon Hwee Ng, Casey Howshall,

T. Ho

et al.

Science, Journal Year: 2024, Volume and Issue: 386(6718), P. 167 - 175

Published: Oct. 10, 2024

Polycyclic polyprenylated acylphloroglucinols (PPAPs) are a class of >400 natural products with broad spectrum bioactivity, ranging from antidepressant and antimicrobial to anti-obesity anticancer activity. Here, we present scalable, regio-, site-, enantioselective catalytic method for synthesis cyclic β-prenyl ketones, compounds that can be used efficient syntheses many PPAPs in high enantiomeric purity. The transformation is prenyl conjugate addition β-ketoesters promoted by readily accessible chiral copper catalyst involving an easy-to-prepare isolable organoborate reagent. Reactions reach completion just few minutes at room temperature. importance this advance highlighted the preparation intermediates previously generate racemic PPAPs. We also nemorosonol (14 steps, 20% yield) its one-step conversion another PPAP, garcibracteatone (52% yield).

Language: Английский

Citations

3
(1R)-2,3,4,6-Tetra-O-benzyl-1-C-allyl-1-deoxy-1-C-(2-thiazolyl)-D-galactopyranose DOI Creative Commons
Clark Ferrari,

Alessandro Dondoni,

Alberto Marra

et al.

Molbank, Journal Year: 2025, Volume and Issue: 2025(1), P. M1949 - M1949

Published: Jan. 8, 2025

We have previously reported that thiazolylketol acetates, synthesized by the addition of 2-lithiothiazole to sugar lactones followed acetylation, are efficient glycosyl donors affording O-, N-, P-, and C-glycosides. After first example C-glycosidation recently described us, we report here on unexpected outcome reaction a acetate with allyltrimethylsilane in presence trimethylsilyl triflate. The obtained intermediate, an intramolecular N-thiazolium salt, could be stereoselectively converted into desired allyl C-thiazolylketoside.

Language: Английский

Citations

0
Three-component synthesis of β-sulfonyl enamines and dienamines enabled by silver(i) acetate DOI Creative Commons
Jakub Koudelka, Tomáš Tobrman

RSC Advances, Journal Year: 2025, Volume and Issue: 15(5), P. 3602 - 3606

Published: Jan. 1, 2025

The three-component synthesis of β-sulfonyl enamines and δ-sulfonyl dienamines is achieved by silver acetate-mediated condensation secondary tertiary amines with sodium sulfinates.

Language: Английский

Citations

0
Preserving precise choreography of bonds in Z-stereoretentive olefin metathesis by using quinoxaline-2,3-dithiolate ligand DOI Creative Commons
Łukasz Grzesiński, Maryana А. Nadirova, Jannick Guschlbauer

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 17, 2024

The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, Ru Z-selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits synthetic applications. To address this issue, we develop a catalyst capable of providing Z-alkenes with under harsh conditions. Our research reveals dithiolate ligand that, stabilised by resonance, delivers up to 150 °C concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing catalysts. Notably, trait does not compromise new catalyst's usability classical conditions, matching activity known stereoretentive Density Functional Theory calculations were employed understand reaction mechanism selectivity, investigate poisoning that may undergo how it competes catalytic activity. Furthermore, quinoxaline-based enables valorisation bio-sourced alkene feedstocks production agricultural sex pheromones pest control.

Language: Английский

Citations

3
Molybdenum Catalyzed Acceptorless Dehydrogenation of Alcohols for the Synthesis of Quinolines DOI Creative Commons
Beatriz García, Beatriz Royo

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: Feb. 23, 2024

Abstract The first molybdenum triazolylidene complexes catalyzing the atom‐economical synthesis of quinolines through acceptorless dehydrogenative coupling alcohols is reported. A new family Mo(0) bearing chelating bis‐1,2,3‐triazolylidene, pyridyl‐1,2,3‐triazolylidene, and bis‐triazole ligands have been prepared applied as catalysts for quinolines. Interestingly, Mo bis‐1,2,3‐triazolylidene with alkyl groups (Et, n ‐Bu) displayed superior catalytic activities than those containing aryl substituents on rings. Control experiments corroborated that reaction involves dehydrogenation pathway.

Language: Английский

Citations

2
Preserving Precise Choreography of Bonds in Stereoretentive Olefin Metathesis: New Type of Ligand Allows High Z-Selectivity Even at Elevated Temperature DOI Creative Commons
Łukasz Grzesiński,

Maryana Nadirova,

Jannick Guschlbauer

et al.

Published: May 17, 2024

The Z-alkene geometry is prevalent in various chemical compounds, including numerous building blocks, fine chemicals, and natural products. Unfortunately, established Mo, W, Ru Z‑selective catalysts lose their selectivity at high temperatures required for industrial processes like reactive distillation, which limits synthetic applications. To address this issue, we developed a catalyst capable of providing Z-alkenes with under harsh conditions. Our research revealed novel dithiolate ligand that, stabilised by resonance, delivers up to 150 °C concentrated mixtures. This distinguishes the dithioquinoxaline complex from existing Z-selective catalysts. Notably, unique trait does not compromise new catalyst’s usability classical conditions, matching activity known stereoretentive Density Functional Theory (DFT) calculations were employed understand reaction mechanism selectivity, investigate poisoning that may undergo how it competes catalytic activity. Furthermore, quinoxaline-based enables valorisation bio-sourced alkene feedstocks production agricultural sex pheromones pest control.

Language: Английский

Citations

2
Cobalt-Catalyzed Chemo- and Stereoselective Transfer Semihydrogenation of 1,3-Dienes with Water as a Hydrogen Source DOI
Heng Wang,

Xiaofeng Jie,

Ting Su

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23476 - 23486

Published: Aug. 7, 2024

(

Citations

1
Transition-metal-free isofunctional reaction of α,β-unsaturated ketones/nitriles DOI

Runyou Ye,

Jialin Ming,

Qinyue Tao

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 29, 2024

Language: Английский

Citations

1
Synthesis of Z-gem-Cl,CF3-Substituted Alkenes by Stereoselective Cross-Metathesis and the Role of Disubstituted Mo Alkylidenes DOI
Qinghe Liu, Can Qin, Jing Wan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22485 - 22497

Published: July 30, 2024

Stereochemically defined organofluorine compounds are central to drug discovery and development. Here, we present a catalytic cross-metathesis method for the synthesis of

Language: Английский

Citations

1