Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

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Catalytic Enantioselective Primary C–H Borylation for Acyclic All-Carbon Quaternary Stereocenters

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1635 - 1643

Published: Jan. 5, 2024

Creating a perfect catalyst to operate enzyme-like chiral recognition has been long-sought aim. A challenging example in this context is constructing acyclic all-carbon quaternary stereogenic centers by transition metal-catalyzed enantioselective C–H activation. We now report highly iridium-catalyzed primary borylation of α-all-carbon substituted 2,2-dimethyl amides enabled tailor-made bidentate boryl ligand (CBL). The success the current transformation attributed CBL/iridium catalyst, which confined pocket. This protocol provides diverse array stereocenters with excellent enantiocontrol and distinct structural features. Computational study reveals that steric hindrance CBL could regulate type dominant orbital interaction between substrate, crucial conferring high induction.

Language: Английский

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Dual Catalytic C(sp²)–H Activation of Azaheterocycles toward C–N Atropisomers

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710

Published: Feb. 14, 2025

Language: Английский

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Enantioselective C−H Bond Functionalization Involving Arene Ruthenium(II) Catalysis

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 29(7)

Published: Oct. 27, 2022

The p-Cymene ruthenium(II) complex is one of the most widely used catalysts in C-H activation. However, enantioselective activation promoted by arene complexes has not been realized until recently. revealed strategies include intramolecular nitrene insertion, use chiral transient directing groups, carboxylic acid, relay catalysis, and ligands. In this minireview, these advances are summarized discussed hope spurring further developments.

Language: Английский

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Site‐ and Stereoselective C(sp³)−H Borylation of Strained (Hetero)Cycloalkanols Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 30, 2022

Transition metal-catalyzed site- and stereoselective C-H activation of strained (hetero)cycloalkanes remains a formidable challenge. We herein report carbamate-directed iridium-catalyzed asymmetric β-C(sp3 )-H borylation cyclopropanol derivatives. A variety densely functionalized cyclopropanols were obtained in good enantioselectivities via desymmetrization kinetic resolution. In addition, site-selective C(sp3 methine groups furnished α-borylated (hetero)cycloalkanols moderate to yields. The synthetic utility the method was further shown gram-scale synthesis diverse downstream transformations borylated products.

Language: Английский

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Synthesis of Chiral Sulfoximines via Iridium‐Catalyzed Regio‐ and Enantioselective C−H Borylation: A Remarkable Sidearm Effect of Ligand

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(6)

Published: Dec. 13, 2022

Transition metal-catalyzed enantioselective C-H activation of prochiral sulfoximines for non-annulated products remains a formidable challenge. We herein report iridium-catalyzed borylation N-silyl diaryl using well-designed chiral bidentate boryl ligand with bulky side arm. This method is capable accommodating broad range substrates under mild reaction conditions, affording vast array high enantioselectivities. also demonstrated the synthetic utility on preparative-scale diverse downstream transformations, including synthesis version bioactive molecules. Computational studies showed that arm confers regio- and enantioselectivity through steric effect.

Language: Английский

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Synthesis of P- and S-Stereogenic Compounds via Enantioselective C–H Functionalization

Synthesis, Journal Year: 2022, Volume and Issue: 54(21), P. 4784 - 4794

Published: March 18, 2022

Abstract Transition metal-catalyzed enantioselective C–H functionalization has emerged as an efficient and powerful strategy to access various chiral molecules. Recently, this also provided a complementary pathway the construction of P- S-stereogenic compounds. In short review, we summarize development applications catalytic systems: Pd(II)/mono-N-protected amino acids (MPAA), Pd(0)/trivalent phosphorus ligands, cyclopentadienyl-ligated metal catalysts [CpxM(III)] (M = Rh, Ir), half-sandwich d6 Ir(III) Ru(II) with carboxylic acid (CCA) ligand, Ir(I)/chiral bidentate boryl cation, for accessing these compounds via functionalization. 1 Introduction 2 Pd(II)/Mono-N-protected Amino Acids 3 Pd(0)/Trivalent Phosphorus Chiral Ligands 4 Cyclopentadienyl-Ligated Metal Catalysts Ir) 5 Half-sandwich Carboxylic Acid Ligand 6 Ir(I)/Chiral Bidentate Boryl 7 Cation 8 Conclusion Outlook

Language: Английский

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Palladium‐Catalyzed Atroposelective Kinetic C−H Olefination and Allylation for the Synthesis of C−B Axial Chirality

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 16, 2023

Abstract The direct C−H functionalization of 1,2‐benzazaborines, especially asymmetric version, remains a great challenge. Here we report palladium‐catalyzed enantioselective olefination and allylation reactions 1,2‐benzazaborines. This approach is kinetic resolution (KR), providing various C−B axially chiral 2‐aryl‐1,2‐benzazaborines 3‐substituted in generally high yields with excellent enantioselectivities (selectivity (S) factor up to 354). synthetic potential this reaction showcased by late‐stage modification complex molecules, scale‐up reaction, applications.

Language: Английский

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Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(6)

Published: Dec. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Language: Английский

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Advances in Exploring Cyclopentadienyl (Cp) Rhodium Catalysts Featuring Diastereotopic or Enantiotopic Cp Faces for Asymmetric C–H Activation

Synthesis, Journal Year: 2023, Volume and Issue: 55(09), P. 1309 - 1321

Published: Jan. 2, 2023

Abstract Chiral cyclopentadienyl rhodium (CpRh) complexes have emerged as a class of powerful catalysts for enantioselective C–H activation reactions. In terms Cp ligand development, the mainstream is to design chiral ligands with C 2 symmetry in order avoid problem face selectivity during their metalation rhodium. recent years, CpRh diastereotopic or enantiotopic faces were also revealed and successfully applied asymmetric activation. These advances are summarized this short review together perspectives future development. 1 Introduction Ligands Diastereotopic Faces 3 Enantiotopic 4 Conclusion Outlook

Language: Английский

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