Chiral dinitrogen ligand enabled asymmetric Pd/norbornene cooperative catalysis toward the assembly of C–N axially chiral scaffolds

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

Published: June 8, 2024

Abstract C − N axially chiral compounds have recently attracted significant interest among synthetic chemistry community due to their widespread application in pharmaceuticals, advanced materials and organic synthesis. Although the emerging asymmetric Catellani reaction offers great opportunity for modular efficient preparation, only operative NBE strategy date requires using half stoichiometric amount of 2,6-disubstituted bromoarenes as electrophiles. We herein report an assembly C–N scaffolds through a distinct ligand strategy. The crucial source, biimidazoline (BiIM) dinitrogen ligand, is used relatively low loading permits use less bulky bromoarenes. method also features feedstock plain NBE, high reactivity, good enantioselectivity, ease operation scale-up. Applications preparation optoelectronic material candidates featuring two axes C–H activation been demonstrated.

Language: Английский

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Catalytic ortho C–H methylation and trideuteromethylation of arylthianthrenium salts via the Catellani strategy

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3333 - 3340

Published: Jan. 1, 2024

We report a Pd/NBE cooperative catalyzed ortho C–H methylation and trideuteromethylation of arylthianthrenium salts, enabling the efficient synthesis wide variety (trideutero)methylated arenes in moderate to good yields.

Language: Английский

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Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(41)

Published: July 9, 2024

In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)-stereogenic molecules by utilizing the catalytic atroposelective Catellani-type C-H arylation/desymmetric intramolecular N-arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent-dictated inversion compounds.

Language: Английский

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Modular Synthesis of Polysubstituted α-Phosphorylated Arenes via the Catellani Strategy

Organic Letters, Journal Year: 2024, Volume and Issue: 26(27), P. 5770 - 5775

Published: June 28, 2024

In this paper, we described a palladium/norbornene-catalyzed

Language: Английский

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Catalytic Ortho C-H Methylation and Trideuteromethylation of Ar-ylthianthrenium Salts via the Catellani Strategy

Published: Feb. 26, 2024

We reported a Pd/NBE cooperative catalyzed ortho C−H methylation and trideuteromethylation of arylthianthrenium salts, enabling the efficient synthesis wide variety (trideutero)methylated arenes in moderate to good yields. The method demonstrates excel-lent tolerance towards functional groups, scalability, potential extension late-stage functionalization biorelevant mole-cules. In combined with thianthrenation arenes, this approach provides an effective for site-selective (trideutero)methylation arenes. Additionally, reaction represents first example Catellani involving aryl sul-fonium salts.

Language: Английский

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Solvent‐Controlled Enantiodivergent Construction of P(V)‐Stereogenic Molecules via Palladium‐Catalyzed Annulation of Prochiral N‐Aryl Phosphonamides with Aromatic Iodides

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(41)

Published: July 9, 2024

Abstract In this work, we describe an efficient and modular method for enantiodivergent accessing P(V)‐stereogenic molecules by utilizing the catalytic atroposelective Catellani‐type C−H arylation/desymmetric intramolecular N ‐arylation cascade reaction. The enantioselectivity of protocol was proved to be tuned polarity solvent, thus providing a wide range both chiral enantiomers in moderate good yields with excellent enantiomeric excesses. Noteworthy is that strategy developed herein represents unprecedented example solvent‐dictated inversion compounds.

Language: Английский

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Palladium-Catalyzed Enantioselective Synthesis of P(V)-Stereogenic Compounds via Desymmetric Annulation of Prochiral Phosphinamides and Aryl Iodides

Organic Letters, Journal Year: 2024, Volume and Issue: 27(1), P. 121 - 128

Published: Dec. 30, 2024

The enantioselective synthesis of P(V)-stereogenic compounds has emerged as an interesting research topic primarily due to their significant biological activity and broad application prospects. Herein, we disclose a method for the construction from prochiral phosphinamides aryl iodides via palladium- chiral norbornene-catalyzed desymmetric annulation. were formed with scope excellent enantiomeric excesses. It is noteworthy that synthetic value this procedure was proven by variety transition metal-catalyzed cross-coupling reactions using C–Br bond on product versatile linchpin electrophile.

Language: Английский

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