Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Nov. 2, 2023

With the rapid development of asymmetric catalysis, demand for enantioselective synthesis complex and diverse molecules with different chiral elements is increasing. Owing to unique features atropisomerism, catalytic atropisomers has attracted a considerable interest from chemical science community. In particular, introducing additional elements, such as carbon centered chirality, heteroatomic planar helical into provides an opportunity incorporate new properties axially compounds, thus expanding potential applications atropisomers. Thus, it important perform transformations synthesize bearing multiple elements. spite challenges in transformations, recent years, chemists have devised powerful strategies under organocatalysis or metal synthesizing wide range enantioenriched Therefore, become emerging field. This review summarizes progress this field indicates challenges, thereby promoting horizon.

Language: Английский

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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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Trifluoromethyl Rhodium‐Carbynoid in [2+1+2] Cycloadditions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 18, 2024

Abstract Trifluoromethyl cationic carbyne (CF 3 C + :) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid =M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared used in Rh‐catalyzed three‐component [2+1+2] cycloadditions for the first time with commercially available N ‐fused heteroarenes nitriles, yielding series of imidazo[1,5‐ ] ‐heterocycles that interest medicinal chemistry, which insertion Rh‐carbynoid =Rh) into C=N bonds involved. This strategy demonstrates synthetic applications late‐stage modification pharmaceuticals, construction CD ‐containing ‐heterocycles, gram‐scale experiments, synthesis phosphodiesterase 10A inhibitor analog. These highly valuable modifiable exhibit good antitumor activity vitro, thus demonstrating their potential chemistry.

Language: Английский

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Catalytic Enantioselective α-Allylation of Deconjugated Butenolides with Aza-π-allylpalladium 1,4-Dipoles: Access to Optically Pure 2-Piperidones Bearing an All-Carbon Quaternary Stereocenter

Organic Letters, Journal Year: 2022, Volume and Issue: 24(45), P. 8348 - 8353

Published: Nov. 10, 2022

A palladium-catalyzed enantioselective α-allylation of deconjugated butenolides with aza-π-allylpalladium 1,4-diploes, in situ generated from palladium-mediated decarboxylation cyclic carbamates and amide-substituted acyclic carbonates, has been successfully developed. An array enantioenriched 2-piperidones bearing an all-carbon quaternary stereocenter were obtained high yields excellent enantioselectivities (up to 99% yield ee). The utility this method was also showcased by a large-scale reaction synthetic transformations the product.

Language: Английский

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Palladium-Catalyzed Ligand-Directed Divergent Decarboxylative Cycloadditions of Vinyloxazolidine-2,4-diones with 1,3,5-Triazinanes

Organic Letters, Journal Year: 2024, Volume and Issue: 26(8), P. 1589 - 1594

Published: Feb. 22, 2024

This study demonstrates a highly efficient regiodivergent ligand-controlled palladium-catalyzed cycloaddition reaction of vinyloxazolidine-2,4-diones with 1,3,5-triazinanes. In the presence diphosphine ligand, proceeds via (5+2) pathway to afford 1,3-diazepin-4-ones in excellent yields, while using monophosphine smoothly (3+2) give imidazolidin-4-ones good yields.

Language: Английский

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Phosphine-Catalyzed Stereospecific and Enantioselective Desymmetrizative [3+2] Cycloaddition of MBH Carbonates and N-(2-tert-Butylphenyl)maleimides

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(12), P. 9068 - 9077

Published: June 1, 2024

Herein, we report an l-valine-derived amide phosphine-catalyzed [3+2] cyclization of MBH carbonates and N-(2-tert-butylphenyl)maleimides via asymmetric desymmetrization. Bicyclic N-aryl succinimide derivatives bearing three continuous chiral centers with a remote C–N atropisomeric chirality were constructed stereospecifically enantioselectively. A wide variety could be employed in this process to deliver highly optically pure moderate excellent yields.

Language: Английский

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Formal oxygen atom insertion as a skeletal-editing step: rapid access natural-product-inspired bispiro[oxindole-oxazinane] hybrids

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(13), P. 3307 - 3312

Published: Jan. 1, 2023

An unprecedented example of skeletal editing pyrrolidines to 1,2-oxazinanes expands the applicability scope “single-atom” skeletal-editing technologies.

Language: Английский

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Palladium-catalyzed asymmetric (4 + 3) cycloaddition of N-2,2,2-trifluoroethylisatin ketimines: access to optically active spirooxindoles

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(11), P. 2648 - 2652

Published: Jan. 1, 2023

Herein, we disclose the first Pd-catalyzed enantioselective (4 + 3) cycloaddition of N -2,2,2-trifluoroethylisatin ketimines with 2-methylidenetrimethylene carbonate.

Language: Английский

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Recent Advances in Catalytic Desymmetrization for the Synthesis of Axially Chiral Biaryls

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 7, 2024

Abstract Atropisomeric compounds have been discovered in pharmaceuticals and materials science, their enantioselective syntheses gained tremendous attention. Among strategies for catalytic atroposelective synthesis, desymmetrization provides robust straightforward approaches to axially chiral biaryls. Due the relative ease of substrate design compared other strategies, has emerged as a pivotal stage converting fascinating chemistry into its counterpart, despite challenges such formation achiral products by subsequent reactions long distance between reaction site stereogenic axis. This review offers comprehensive overview recent advancements using organo‐ metal catalysts, addressing solutions, aims provide insights future developments this field.

Language: Английский

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Phosphine-Catalyzed Atroposelective Formal [3 + 2] Cycloaddition Desymmetrization of N-Arylmaleimides

Organic Letters, Journal Year: 2022, Volume and Issue: 24(36), P. 6494 - 6498

Published: Sept. 7, 2022

Herein, a new strategy for the enantioselective synthesis of axially chiral N-aryl succinimides was devised by [3 + 2] annulation MBH carbonates and maleimides under phosphine. This desymmetrization process allows quick construction both two stereogenic carbon centers remote CAr-N atropisomeric chirality. A series structurally diverse were obtained with good to excellent yields, diastereoselectivities, enantioselectivities. The is mild, efficient, scalable features broad substrate scope.

Language: Английский

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