Enantio‐ and Diastereoselective Synthesis of Chiral Tetrasubstituted α‐Amino Allenoates Bearing a Vicinal All‐Carbon Quaternary Stereocenter with Dual‐Copper‐Catalysis

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 1, 2023

The skeletons of chiral tetrasubstituted allenes bearing a vicinal all-carbon quaternary stereocenter are importance but still challenging to synthesize. Herein, we report enantio- and diastereoselective γ-additions 1-alkynyl ketimines with dual-copper-catalysis under mild conditions, affording α-amino allenoates in high yields (up 99 % yield) excellent enantioselectivities ee) diastereoselectivities >20 : 1 dr). Importantly, the stereodivergent synthesis products was realized by asymmetric γ-addition reaction Grignard reagent promoted epimerization. Moreover, dual-copper-catalyzed reactions were smoothly applied gram-scale adopted introduce allenyl moieties into bioactive molecules. Mechanistic experiments density functional theory (DFT) calculations demonstrated that catalyzed double copper catalysts.

Language: Английский

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Chiral Aldehyde Catalysis-Enabled Asymmetric α-Functionalization of Activated Primary Amines

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(5), P. 776 - 794

Published: Feb. 21, 2024

ConspectusThe development of catalytic activation modes provides a reliable and effective platform for designing new enantioselective reactions preparing chiral molecules with diverse structures. Chiral aldehyde catalysis is an attractive concept in asymmetric catalysis, which utilizes catalyst to promote the hydroamination allylic amines, α-functionalization primary or transamination α-keto esters. Typically, aldehyde-catalyzed amines efficient straightforward method synthesis α-functionalized does not require any additional protection deprotection manipulations amine group. However, achieving stereoselective transformations high efficiency enantioselectivity by this strategy has remained intractable challenge.This Account summarizes our endeavors application catalysis. Using as catalyst, we reported α-C alkylation 2-aminomalonate 3-indolylmethanol 2014, represents first activated amine. Subsequently, several axially catalysts were continuously prepared using BINOL starting material, their applications explored. On one hand, they used organocatalysts realize various α-amino acid esters, such 1,4-addition toward conjugated enones/α,β-unsaturated diesters cyclic 1-azadienes well α-arylation/allylation benzylation corresponding halohydrocarbons. Notably, taking advantage difference distribution sites between two catalysts, disclosed diastereodivergent 1,6-conjugated addition Mannich reactions. other potential cooperative transition metal also been demonstrated. Enabled combination aldehyde, palladium complex, Lewis acid, α-allylation amino esters allyl alcohol was established. Moreover, ternary system successfully 1,3-dienes, allenes, allenylic 1,3-disubstituted arylmethanol cascade Heck-alkylation reaction. The nickel complex allows α-propargylation propargylic excellent enantioselectivities. These provide large library optically active acids. With those key building blocks, formal multiple natural products biologically significant unnatural accomplished. This includes stereodivergent pyrrolizidine alkaloid NP25302 product (

Language: Английский

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Palladium-catalysed aryl/monofluoroalkylation of allenamides: access to fluoroalkyl indoles and isoquinolones

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(28), P. 3794 - 3797

Published: Jan. 1, 2024

Efficient access to fluoroalkyl indoles and isoquinolones through palladium-catalysed aryl/monofluoroalkylation of allenamides has been developed.

Language: Английский

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Asymmetric three-component Tsuji–Trost allylation reaction enabled by chiral aldehyde/palladium combined catalysis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(26), P. 10232 - 10236

Published: Jan. 1, 2024

An asymmetric three-component allylation reaction is achieved under the promotion of chiral aldehyde/palladium combined catalysis via mixed Heck/allylation cascades.

Language: Английский

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Asymmetric bifunctionalization of allenes with aryl iodides and amino acids enabled by chiral aldehyde/palladium combined catalysis

Chemical Science, Journal Year: 2024, Volume and Issue: 15(32), P. 12983 - 12988

Published: Jan. 1, 2024

An asymmetric bifunctionalization of allenes with aryl/alkenyl iodides and amino acid esters is achieved under the promotion chiral aldehyde/palladium combined catalysis.

Language: Английский

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Research Progress on Transition Metal Catalyzed Hydrocarbonation Reactions of N-Allenamines

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 151 - 151

Published: Jan. 1, 2025

Language: Английский

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Asymmetric α-Allylation of N-Unprotected Amino Acid Esters with 1,3-Disubstituted Allyl Acetates Enabled by Chiral-Aldehyde/Palladium Catalysis

Organic Letters, Journal Year: 2023, Volume and Issue: 25(31), P. 5790 - 5794

Published: July 31, 2023

A chiral aldehyde/palladium catalysis-enabled asymmetric α-allylation of NH2-unprotected amino acid esters with 1,3-disubstituted allyl acetates is described in this work. With the utilization different phosphine ligands, both anti- and syn-selective allylation reactions are achieved enantioselectively. series α,α-disubstituted bearing two adjacent centers produced moderate-to-excellent yields, diastereoselectivities, enantioselectivities.

Language: Английский

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Access to Axially Chiral Aryl Aldehydes via Carbene-Catalyzed Nitrile Formation and Desymmetrization Reaction

Research, Journal Year: 2023, Volume and Issue: 7

Published: Dec. 12, 2023

An approach utilizing N-heterocyclic carbene for nitrile formation and desymmetrization reaction is developed. The process involves kinetic resolution, with the axially chiral aryl monoaldehydes obtained in moderate yields excellent optical purities. These can be conveniently transformed into functionalized molecules, showing great potential as catalysts organic chemistry.

Language: Английский

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Enantio‐ and Diastereoselective Synthesis of Chiral Tetrasubstituted α‐Amino Allenoates Bearing a Vicinal All‐Carbon Quaternary Stereocenter with Dual‐Copper‐Catalysis

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(31)

Published: June 1, 2023

Abstract The skeletons of chiral tetrasubstituted allenes bearing a vicinal all‐carbon quaternary stereocenter are importance but still challenging to synthesize. Herein, we report enantio‐ and diastereoselective γ‐additions 1‐alkynyl ketimines with dual‐copper‐catalysis under mild conditions, affording α‐amino allenoates in high yields (up 99 % yield) excellent enantioselectivities ee ) diastereoselectivities >20 : 1 dr ). Importantly, the stereodivergent synthesis products was realized by asymmetric γ‐addition reaction Grignard reagent promoted epimerization. Moreover, dual‐copper‐catalyzed reactions were smoothly applied gram‐scale adopted introduce allenyl moieties into bioactive molecules. Mechanistic experiments density functional theory (DFT) calculations demonstrated that catalyzed double copper catalysts.

Language: Английский

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Palladium-catalyzed regio- and stereoselective allylic alkylation of 5-vinyloxazolidine-2,4-diones with azlactones: synthesis of chiral (Z)-trisubstituted allylic amino acid derivatives

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(21), P. 5463 - 5469

Published: Jan. 1, 2023

Palladium-catalyzed regio- and stereoselective allylic alkylation of 5-vinyloxazolidine-2,4-diones with azlactones worked well to give the Z configuration various trisubstituted amino acid derivatives.

Language: Английский

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