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

Insight into structure-property relationship of diazo-based carbene-type dyes towards high fixing performance on synthetic fiber DOI
Hua Jiang,

Xiaokang Xie,

Lulu Shi

et al.

Dyes and Pigments, Journal Year: 2025, Volume and Issue: unknown, P. 112755 - 112755

Published: March 1, 2025

Language: Английский

Citations

0
Metal-Associated Enols as Key Intermediates in Controlling Enantioselectivity in Carbene Insertion Reactions DOI
Garima Jindal,

Dipti K. Dodiya,

Mahesh Singh Harariya

et al.

Synlett, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Abstract Transition-metal-catalysed asymmetric carbene insertion reactions into various X–H bonds typically suffer from poor stereoselectivity. It has been proposed that the presence of metal-free intermediates leads to erosion selectivity. In current account, we discuss our recent efforts understand mechanism and stereochemical model Rh- Fe-catalysed indole phenol. Our detailed DFT calculations show all transformations adopt a common involving an enol intermediate, further tautomerisation which is key stereodetermining step. To account for enantioinduction, propose novel metal-associated species can be solving challenges in reactions. The geometry metal–enol complex interaction between chiral metal prochiral play important roles driving reaction toward particular stereoisomer. 1 Introduction 2 Rh-Catalysed Carbene Insertion Indole 3 Fe-Catalysed C–H Functionalisation 4 O–H 5 Conclusion

Language: Английский

Citations

0
A combined experimental and computational study reveals a crossover between conventional cross-coupling and carbene insertion pathways in a Pd catalyzed C(sp2)–H insertion DOI Creative Commons

Arushi Tyagi,

Kritika Gaur,

Anubhav Goswami

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Computational (DFT and DLPNO-CCSD(T)) calculations along with experimental tools (deuterium labelling, kinetic studies using VTNA, ESI-HRMS UV) are used to probe the mechanism of a Pd(ii)-catalyzed enantioselective carbene insertion into C(sp2)-H indole. Using deuterium labelling studies, we demonstrate intermediacy metal-hydride species, which contrasts mechanistic routes for other transition metals (Rh, Fe, Au, Cu, etc.). Our VTNA study reveals order be one in both diazo indole, microkinetic modelling aligns well computationally predicted mechanism. The is further supported by detection most stable intermediate catalytic cycle ESI-HRMS. An investigation origin stereoselectivity DLPNO-CCSD(T) presents new paradigm, wherein stereocontrol arises during formation Pd itself as opposed proton transfer steps found all metal catalysts.

Language: Английский

Citations

0
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