Catalytic Enantioselective [3+2] Cycloaddition of N‐Metalated Azomethine Ylides

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(28)

Published: March 7, 2023

Abstract Asymmetric [3+2] cycloaddition reactions are fascinating and powerful methods for the synthesis of enantioenriched pyrrolidines up to four stereocentres. Pyrrolidines important compounds both biology organocatalytic applications. This review summarizes most recent advances in enantioselective by cycloadditions azomethine ylides using metal catalysis. It has been organized type catalysis used further arranged complexity nature dipolarophile. The presentation each reaction highlights their advantages limitations.

Language: Английский

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Transition-metal-catalyzed asymmetric defluorinative reactions

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(15), P. 3909 - 3928

Published: Jan. 1, 2023

The latest achievements in transition-metal-catalyzed enantioselective defluorinative coupling reactions have been comprehensively summarized on the basis of classification transition-metal catalysts.

Language: Английский

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Fe-Catalyzed Alkylazidation of α-Trifluoromethylalkenes: An Access to Quaternary Stereocenters Containing CF₃ and N₃ Groups

Organic Letters, Journal Year: 2023, Volume and Issue: 25(8), P. 1336 - 1341

Published: Feb. 23, 2023

A concise Fe-catalyzed alkylazidation of α-trifluoromethylalkenes via a C–C bond cleavage/radical addition/azidation cascade is described. This protocol features broad substrate scope, excellent functional group compatibility, and the ability to be performed on gram scale, thus offering practical step-economic approach synthetically useful tertiary α-trifluoromethyl azides.

Language: Английский

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Asymmetric synthesis of difluorinated α-quaternary amino acids (DFAAs) via Cu-catalyzed difluorobenzylation of aldimine esters

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 35(12), P. 109665 - 109665

Published: Feb. 23, 2024

Language: Английский

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La(OTf)₃-Catalyzed [3+2] Cycloaddition Reactions for the Synthesis of Benzo[d]oxazoles/Benzofurans

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 3809 - 3820

Published: Feb. 23, 2024

The La(OTf)3-catalyzed [3+2] cycloaddition reactions for the synthesis of benzo[d]oxazoles/benzofurans via quinones and 1,2-di-tert-butyl-3-(cyanimino)diaziridine (1,3-di-tert-butyl-2-cyanoguanidine)/vinyl azides have been explored. A series 5-hydroxybenzofuran-4-carboxylic acid derivatives 5-hydroxybenzo[d]oxazole-4-carboxylic were conveniently obtained with high yields good stereoselectivities, which could be used further transformations to valuable compounds.

Language: Английский

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Enantioselective Pd- and Cu-Catalyzed Hydrofunctionalization of Methylenecyclopropanes via a Distal C–C Bond Cleavage

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

Published: Jan. 28, 2025

The enantioselective ring-opening reactions of methylenecyclopropanes (MCPs) involving C–C bond activation via oxidative addition transition metals have been rarely reported. Here, we disclose a Pd/Cu-catalyzed enantio- and regioselective coupling between cyclic imino esters MCPs to produce α-allylated 2H-pyrrole derivatives. In this reaction, azomethine ylide formed by chiral copper catalyst with ketimine ester would serve as nucleophile react activated palladium catalysis. This bimetallic system exhibited broad substrate scope high regio- enantioselectivities.

Language: Английский

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α,α-Difluorinated Allylsulfones: gem-Difluoroethylenyl Reagents for Synthesis of Fluorinated Chiral α-Quaternary Amino Acids

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

Published: March 25, 2025

Among numerous fluorine-containing molecules, chiral gem-difluoroethylenes (C═CF2) exhibited unique properties in agrochemicals, pharmaceuticals, and materials science. However, the general synthetic methods were limited to functionalization/defluorination of trifluoromethylalkenes. Here, we disclose a new type difluoroethylenyl reagent, α,α-difluoro allylsulfones, which allows highly enantioselective Cu-catalyzed desulfonylative SN2′ substitution with benzylideneamino esters. This protocol presents novel strategy for construction diversified α-quaternary amino acid derivatives containing gem-difluoroethylene moiety excellent results (up 86% yield, generally 90–98% ee). The ease synthesis applications this protocol, transformations products revealed potential utility chemistry.

Language: Английский

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Enhancing the Efficacy of Chiral Ligands and Catalysts: Siloxane-Substituted Oxazoline Ferrocenes as Next-Generation Candidates

Molecules, Journal Year: 2024, Volume and Issue: 29(5), P. 968 - 968

Published: Feb. 22, 2024

Since the discovery of classical chiral oxazoline ferrocene ligands in 1995, they have become pivotal transition metal-catalyzed asymmetric transformations. Over past decade, a notable evolution has been observed with emergence siloxane-substituted ferrocenes, demonstrating significant potential as and catalysts. These compounds consistently delivered exceptional results diverse mechanistically distinct transformations, surpassing capabilities ligands. This review meticulously delineates research progress on compounds. It encompasses synthesis crucial precursors desired products, highlights their achievements catalysis reactions, delves into exploration derivatization these compounds, emphasizing introduction ionophilic groups impact recovery metal In addition to presenting current state knowledge, this propels future directions by identifying topics for further investigation concerning siloxane-tagged derivatives. derivatives are poised be promising candidates next generation highly efficient

Language: Английский

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Sustainable Manufacturing of trans-4-Trifluoromethyl-l-proline via Stereochemical Editing: A Combined In Silico and Experimental Approach

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(10), P. 3827 - 3836

Published: July 31, 2024

Ibuzatrelvir (1) is a second-generation, orally bioavailable, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) main protease inhibitor clinical candidate. Herein, we report the implementation of an in silico and high-throughput experimentation strategy leading to identification rapid, efficient, sustainable route trans-4-trifluoromethyl-l-proline (2), key building block for ibuzatrelvir. This novel synthetic features stereochemical editing step enable efficient scalable protocol that operates under mild conditions with high stereoselectivity, providing effective access more than 235 kg five-step sequence from readily available starting materials.

Language: Английский

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Diverse Synthesis of Fused Polyheterocyclic Compounds via [3 + 2] Cycloaddition of In Situ-Generated Heteroaromatic N-Ylides and Electron-Deficient Olefins

Molecules, Journal Year: 2023, Volume and Issue: 28(11), P. 4410 - 4410

Published: May 29, 2023

[3 + 2] Cycloaddition reactions of heteroaromatic N-ylides with electron-deficient olefins have been developed. The N-ylides, in situ generated from N-phenacylbenzothiazolium bromides, can smoothly react maleimides under very mild conditions, affording fused polycyclic octahydropyrrolo[3,4-c]pyrroles good-to-excellent isolated yields. This reaction concept could also be extended to 3-trifluoroethylidene oxindoles and benzylidenemalononitriles as for accessing highly functionalized polyheterocyclic compounds. A gram-scale experiment was carried out verify the practicability methodology.

Language: Английский

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