Synergistic Pd/Cu-Catalyzed 1,5-Double Chiral Inductions

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9241 - 9251

Published: March 19, 2024

Much attention has been focused on the catalytic asymmetric creation of single chiral centers or two adjacent stereocenters. However, construction nonadjacent stereocenters is significant importance but challenging because lack remote induction models. Herein, based a C═C bond relay strategy, we report synergistic Pd/Cu-catalyzed 1,5-double model. All four stereoisomers target products bearing 1,5-nonadjacent involving both allenyl axial and central chirality could be obtained divergently by simply changing combination catalysts with different configurations. Control experiments DFT calculations reveal novel mechanism 1,5-oxidative addition, contra-thermodynamic η3-allyl palladium shift, conjugate nucleophilic substitution, which play crucial roles in control reactivity, regio-, enantio-, diastereoselectivity. It expected that this strategy may provide general protocol for synthesis structural motifs distant

Language: Английский

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Mechanism of Asymmetric Homologation of Alkenylboronic Acids with CF₃-Diazomethane via Borotropic Rearrangement

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 4538 - 4548

Published: March 25, 2024

Density functional theory calculations have been performed to investigate the mechanism for BINOL-catalyzed asymmetric homologation of alkenylboronic acids with CF3-diazomethane. The reaction proceeds via a chiral BINOL ester acid substrate. reveal complex scenario formation BINOL-alkenylboronate species, which is key intermediate in catalytic process. aliphatic alcohol additive plays an important role reaction. This study provides rationalization stereoinduction step reaction, and enantioselectivity mainly attributed steric repulsion between CF3 group diazomethane reagent γ-substituent catalyst. potential energy surface obtained by analyzed means microkinetic simulations.

Language: Английский

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Asymmetric synthesis of atropisomers featuring cyclobutane boronic esters facilitated by ring-strained B-ate complexes

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

Published: Dec. 30, 2024

The strain-release-driven reactions of bicyclo[1.1.0]butanes (BCBs) have received significant attention from chemists. Notably, 1,2-migratory enabled by BCB-derived B-ate complexes effectively complement the initiated common BCBs. desired products are particularly valuable for late-stage transformations due to presence C-B bond. However, asymmetric mediated boronate progressed slowly. In this study, we develop an synthesis atropisomers featuring cis-cyclobutane boronic esters facilitated 1,2-carbon or boron migration ring-strained complexes, achieving high enantioselectivity. reaction is compatible with various aryl, alkenyl, alkyl and B

Language: Английский

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Theoretical investigation on the reaction mechanism and origin of stereoselectivity of a three-component coupling reaction under organocatalysis

Molecular Catalysis, Journal Year: 2025, Volume and Issue: 573, P. 114819 - 114819

Published: Jan. 6, 2025

Language: Английский

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Propargyl and Allenyl Organometallics

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

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Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications

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

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

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Asymmetric Synthesis of Propargylic and Allenic Silanes, Germanes, and Stannanes

Chemistry - An Asian Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 20, 2025

Abstract Enantioenriched propargylic and allenic derivatives of silicon, germanium, tin are versatile building blocks for stereoselective synthesis. Consequently, considerable efforts toward their efficient selective synthesis have been made, both through classical approaches chirality transfer catalytic enantioselective strategies that employ the latest developments in transition metal catalysis, organocatalysis, photoredox catalysis. In this review, we survey broadly applicable synthetic discuss scope mechanistic details specific protocols afford these compounds a regio‐ manner.

Language: Английский

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Transition-Metal-Free Insertion of Diazo Compounds, N-Arylsulfonylhydrazones or Ylides into Organoboronic Acids or Their Derivatives

Synlett, Journal Year: 2023, Volume and Issue: 34(18), P. 2071 - 2084

Published: June 5, 2023

Abstract Insertion reactions of carbenes or ylides with organoboronic acids their derivatives have emerged as valuable methods for coupling homologation organoboron compounds under metal-free conditions. The crucial steps these are coordination the electron-rich carbon centers carbene precursors to electron-poor boron center, followed by 1,2-migration corresponding tetracoordinated intermediates. This type unique transformation provides an efficient method construction C–C C–X (X = H, B) bonds. Moreover, C–B bonds generated such transformations can be utilized a handle further derivatization iterative homologations. In this Account, we summarize developments in arena according reactive diazo compound, N-arylsulfonylhydrazone ylide species involved. 1 Introduction 2 Reactions Diazo Compounds 3 N-Arylsulfonylhydrazones 4 Ylides 5 Conclusion

Language: Английский

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Chiral gem-difluoroalkyl reagents: gem-difluoroalkyl propargylic borons and gem-difluoroalkyl α-allenols

Chemical Science, Journal Year: 2023, Volume and Issue: 14(34), P. 9186 - 9190

Published: Jan. 1, 2023

Chiral fluorinated reagents provide new opportunities for the discovery of drugs and functional materials because introduction a group significantly alters molecule's physicochemical properties. gem-difluoroalkyl fragments (R-CF2-C*) are key motifs in many drugs. However, scarcity synthetic methods types chiral limits applications these compounds. Herein, we report two propargylic borons α-allenols their synthesis by means involving rhodium-catalyzed enantioselective B-H bond insertion reactions carbenes Lewis acid-promoted allenylation reactions. The mild, operationally simple method features broad substrate scope good tolerance. These contain easily transformable boron alkynyl or allenyl moieties thus might facilitate rapid modular construction molecules containing other molecules.

Language: Английский

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Creation of a Chiral All-Carbon Quaternary Center Induced by CF₃ and CH₃ Substituents via Cu-Catalyzed Asymmetric Conjugate Addition

Organic Letters, Journal Year: 2024, Volume and Issue: 26(25), P. 5312 - 5317

Published: June 13, 2024

Cu-catalyzed asymmetric construction of a chiral quaternary center bearing CH3 and CF3 groups was achieved with high to excellent enantioselectivity using our originally developed ligands. The conjugate addition Me3Al β-CF3-substituted enones unsaturated ketoesters proceeded efficiently. use gives optically active furanones in yields enantioselectivities. perfluoroalkyl-substituted enone does not seem be favorable the present reaction.

Language: Английский

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