One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives DOI

Zefeng Jin,

LI Cui-ying,

Guodong Shen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(24), P. 5151 - 5159

Published: Aug. 29, 2024

Abstract A copper or silver‐catalyzed cascade addition/5‐ exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis a variety ( Z )‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives diverse substitutions in single vessel. The method is featured pot‐economy as well regio‐ and ‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, relevant indole‐fused indole‐substituted thiophenone were also assembled one pot by merging other bond formation methods. Based on experiments related reports, pathway triggered addition ynone‐derived radical towards C( sp )‐atom was proposed to elucidate probable process transformation.

Language: Английский

Synergistic Photoenzymatic Catalysis Enables Synthesis of a-Tertiary Amino Acids Using Threonine Aldolases DOI

Yao Ouyang,

Claire G. Page,

Catherine Bilodeau

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 13754 - 13759

Published: May 13, 2024

a-Tertiary amino acids are essential components of drugs and agrochemicals, yet traditional syntheses step-intensive provide access to a limited range structures with varying levels enantioselectivity. Here, we report the α-alkylation unprotected alanine glycine by pyridinium salts using pyridoxal (PLP)-dependent threonine aldolases Rose Bengal photoredox catalyst. The strategy efficiently prepares various a-tertiary in single chemical step as enantiomer. UV–vis spectroscopy studies reveal ternary interaction between salt, protein, photocatalyst, which hypothesize is responsible for localizing radical formation active site. This method highlights opportunity combining catalysts enzymes new catalytic functions known enzymes.

Language: Английский

Citations

23
Desymmetrization–Addition Reaction of Cyclopropenes to Imines via Synergistic Photoredox and Cobalt Catalysis DOI

Xiang‐Kui He,

Liang‐Qiu Lu,

Bao-Ru Yuan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18892 - 18898

Published: July 5, 2024

Herein, we designed a reaction for the desymmetrization-addition of cyclopropenes to imines by leveraging synergy between photoredox and asymmetric cobalt catalysis. This protocol facilitated synthesis series chiral functionalized cyclopropanes with high yield, enantioselectivity, diastereoselectivity (44 examples, up 93% yield >99% ee). A possible mechanism involving cyclopropene desymmetrization Co-H species imine addition Co-alkyl was proposed. study provides novel route important extends frontier metallaphotoredox

Language: Английский

Citations

17
CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8888 - 8895

Published: Jan. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Language: Английский

Citations

4
Research Progress in the Synthesis of α-Tertiary Amines via Radical Strategies DOI

Jia‐Heng Fang,

Run Tian,

Ji‐Jun Chen

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(1), P. 22 - 22

Published: Jan. 1, 2025

Language: Английский

Citations

0
Photo‐Promoted Nitrogen‐Centered Radical Mediated Intermolecular Aminative Carbonylation of Tertiary Allyl Alcohols to Access β‐Amino Ketones through (Hetero)Aryl Migration DOI Creative Commons

Ming Hou,

Yuanrui Wang,

Hefei Yang

et al.

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

Published: March 12, 2025

Abstract Carbon monoxide, as a crucial C1 synthon, has been widely used in the difunctionalization of alkenes. Additionally, nitrogen‐centered radicals (NCRs) are also effective intermediates for constructing C−N bonds. Herein, radical‐mediated aminative carbonylation strategy producing β ‐amino ketones from tertiary allyl alcohols disclosed. Good yields with different functional groups were generated effectively under light irradiation.

Language: Английский

Citations

0
Photoredox/Palladium-Catalyzed Reduction Alkylation of Imines and Ammonium Salts via Dual C–N Bond Cleavage DOI
Tao Ju, Zhi‐Hao Wang,

Ai-Ling Lu

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 16, 2025

Here, we report a photoredox/palladium-catalyzed reduction alkylation of imines and ammonium salts via dual C-N cleavage. This reaction proceeds under mild, green, operationally simple conditions, offering broad scope secondary amine compounds with alpha quaternary carbon. Mechanistic studies indicate that the α-amino carbanion, generated by successive single-electron transfer process, is key intermediate in photoredox/palladium catalysis.

Language: Английский

Citations

0
Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis DOI Creative Commons

Mengyang Shen,

C. NIU,

Xuchao Wang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(6), P. 2312 - 2322

Published: June 11, 2024

Enantioenriched 3-methylpyrrolidine, with its unique chiral nitrogen-containing core skeleton, exists widely in various functional molecules, including natural products, bioactive compounds, and pharmaceuticals. Traditional methods for synthesizing these valuable methyl-substituted heterocycles often involve enzymatic processes or complex procedures auxiliaries, limiting the substrate scope efficiency. Efficient catalytic methylation, especially an enantioselective manner, has been a long-standing challenge chemical synthesis. Herein, we present novel approach remote stereoselective installation of methyl group onto N-heterocycles, leveraging CoH-catalyzed asymmetric hydromethylation strategy. By effectively combining commercial cobalt precursor modified bisoxazoline (BOX) ligand, variety easily accessible 3-pyrrolines can be converted to enantiopure 3-(isotopic labeling)methylpyrrolidine compounds outstanding enantioselectivity. This efficient protocol streamlines two-step synthesis enantioenriched which previously required up five six steps under harsh conditions expensive starting materials.

Language: Английский

Citations

3
A General Enantioselective α-Alkyl Amino Acid Derivatives Synthesis Enabled by Cobalt-Catalyzed Reductive Addition DOI

Chengxi Zhang,

Xianqing Wu, Jingping Qü

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Enantioenriched unnatural amino acids represent a prevalent motif in organic chemistry, with profound applications biochemistry, medicinal and materials science. Herein, we report cobalt-catalyzed aza-Barbier reaction of dehydroglycines unactivated alkyl halides to afford α-amino esters high enantioselectivity. This catalytic reductive alkylative addition protocol circumvents the use moisture-, air-sensitive organometallic reagents, stoichiometric chiral auxiliaries, enabling conversion variety primary, secondary, even tertiary α-alkyl-amino under mild conditions, thus leading broad functional group tolerance. The expedient access biologically active motifs demonstrates practicality this by reducing number synthetic steps enhancing efficiency.

Language: Английский

Citations

3
Harnessing the potential of acyl triazoles in bifunctional cobalt-catalyzed radical cross-coupling reactions DOI Creative Commons
Chang‐Yin Tan, Sungwoo Hong

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

Published: Aug. 13, 2024

Persistent radicals facilitate numerous selective radical coupling reactions. Here, we have identified acyl triazole as a new and versatile moiety for generating persistent intermediates through single-electron transfer processes. The efficient generation of these is facilitated by the formation substrate-coordinated cobalt complexes, which subsequently engage in cross-coupling Remarkably, triazole-coordinated complexes exhibit metal-hydride hydrogen atom (MHAT) capabilities with alkenes, enabling synthesis diverse ketone products without need external ligands. By leveraging effect, this catalytic approach also allows development other reactions two representative precursors. discovery triazoles effective substrates ligands catalysis, combined bifunctional nature system, opens up avenues design sustainable organic transformations. radical-mediated has emerged powerful tool forging C–C bonds. authors identify processes, context cobalt-catalysed carbon-carbon couplings under photoirradiation.

Language: Английский

Citations

2
Advances in Transition Metal Catalysis and Organocatalysis Approaches towards Asymmetric Synthesis of β-Amino Acid Derivatives DOI

Farrukh Sajjad,

Shuyue Zhang, Ming‐Hua Xu

et al.

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

Published: Aug. 16, 2024

Abstract The stereoselective synthesis of β-amino acids has attracted major attention among the synthetic community in recent years. This review provides an overview important advances chiral acid over past decade. It covers development enantioselective methods using transition-metal complexes or organocatalysts, mainly including catalytic asymmetric hydrogenation, Mannich reaction, multicomponent reactions diazo compounds, and conjugate addition. Additionally, optically active by other approaches are also summarized. 1 Introduction 2 Strategies towards Asymmetric Synthesis β-Amino Acids 2.1 Hydrogenation 2.2 Reaction 2.3 Conjugate Addition 2.4 Multicomponent Reactions 2.5 Miscellaneous 2.5.1 from Chiral Amines 2.5.2 Isoxazolidinones 2.5.3 Other Methodologies 3 Summary Outlook

Language: Английский

Citations

2