Rh-Catalyzed α-Arylation of Cyclic 1,3-Dicarbonyls with Benzocyclobutenols Enabled by a Cyclic Iodonium Ylide Strategy

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4383 - 4387

Published: May 14, 2024

To date, the general and catalytic α-arylation of cyclic 1,3-dicarbonyls remains elusive. We now report first Rh-catalyzed with benzocyclobutenols through a iodonium ylide strategy. Our strategy represents good solution for previously challenging sterically demanding aryl partners, which is especially appropriate structurally unique heteroaromatic 1,3-dicarbonyls. approach features mild conditions, readily available starting materials, high yields, excellent functional group-tolerance, simple operation, providing expedient access toward medically important 2-aryl (hetero)cyclic The practicality this demonstrated by gram-scale synthesis, one-pot numerous downstream transformations.

Language: Английский

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Mechanism and Origin of Nickel-Catalyzed Decarbonylative Construction of C(sp²)–C(sp³) Bonds from Carboxylic Acids and Their Derivatives

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

Published: March 31, 2025

Nickel-catalyzed arylation of carboxylic acids provides a ligand-controlled chemoselectivity-switchable method for the construction C(sp2)-C(sp3) bonds. Here, we employed density functional theory to provide detailed understanding mechanism and origin nickel-catalyzed carbonyl transformation. This reaction generates decarbonylation products through oxidative addition, activation C-C bonds, decarbonylation, binding alkyl radicals with Ni(III) complexes, final reduction elimination step. The bonds in aromatic carboxylate esters is more favorable than C-O bond because interaction between nickel catalyst π orbitals substrate's moiety during activation. induction effect ligand group together determines transfer tendency group.

Language: Английский

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Computational Exploration of 1,2-Carboamine Carbonylation Catalyzed by Nickel

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 4484 - 4495

Published: March 12, 2024

Nickel-catalyzed carbonylation of alkenes is a stereoselective and regioselective method for the synthesis amide compounds. Theoretical predictions with density functional theory calculations revealed mechanism origin stereoselectivity regioselectivity nickel-catalyzed norbornene. The reaction proceeds through oxidative addition, migration insertion alkenes, subsequent reduction elimination to afford cis-carbonylation product. C–N bond activation amides unfavorable because addition ability C–C stronger than that bond. determining step migratory strained olefin. structural analysis shows steroselectivity controlled by steric hindrance methyl groups olefins substituents IMes in ligands.

Language: Английский

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Co(III)-Catalyzed C6-Selective C–H Activation/Pyridine Migration of 2-Pyridones with Propiolates

Organic Letters, Journal Year: 2023, Volume and Issue: unknown

Published: Dec. 21, 2023

A versatile Co(III)-catalyzed C6-selective C–H activation/pyridine migration of 2-pyridones with available propiolates as coupling partners was demonstrated. This method features high atom economy, excellent regioselectivity, and good functional group tolerance by employing an inexpensive Co(III) catalyst under mild reaction conditions. Moreover, gram-scale synthesis late-stage modifications pharmaceuticals were performed to prove the effectiveness these synthetic approaches.

Language: Английский

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Five-membered ring systems: Pyrroles and benzo analogs

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 123 - 173

Published: Jan. 1, 2024

Language: Английский

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