Nickel-Catalyzed Decarbonylative Silylation, Borylation, and Amination of Arylamides via a Deamidative Reaction Pathway

Published as part of the Cluster C–O Activation

Abstract

A nickel-catalyzed decarbonylative silylation, borylation, and amination of amides has been developed. This new methodology allows the direct interconversion of amides to arylsilanes, arylboronates, and arylamines and enables a facile route for carbon–heteroatom bond formations in a straightforward and mild fashion.

Key words

nickel catalysis - decarbonylation - amination - silylation - borylation

• References and Notes

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• 25 General Procedure for the Nickel-Catalyzed Decarbonylative Silylation of Arylamides via a Deamidative Reaction Pathway In a nitrogen-filled glovebox, a 10 mL oven-dried sealed tube containing a stirring bar was charged with the corresponding amide (0.20 mmol, 1.0 equiv), yellow Ni(COD)₂ (5.5 mg, 10 mol%), copper fluoride(II) (6.1 mg, 30 mol%), and potassium fluoride (34.9 mg, 0.60 mmol, 3.0 equiv). Subsequently, freshly distilled toluene (1.0 mL) was added, and then triethylsilylborane (96.9 mg, 0.40 mmol, 2.0 equiv) and tri-n-butylphosphine ligand (20 μL, 40 mol%) were added, respectively, via microsyringe. The tube with the mixture was sealed and removed from the glovebox. After stirring at 160 °C for 36 h, the mixture was allowed to cool to room temperature, diluted with EtOAc (5 mL), and filtered through a Celite plug, eluting with additional EtOAc (10 mL). The filtrate was concentrated and purified by column chromatography on silica gel to yield the product. Synthesis of 8i Following the general procedure, starting from 1-(4-fluorobenzoyl)piperidine-2,6-dione (47.0 mg, 0.20 mmol), the title product was isolated as colorless oil after flash chromatography on silica gel, 18.5 mg (44%). ¹H NMR (600 MHz, CDCl₃): δ = 7.48–7.43 (m, 2 H), 7.08–7.01 (m, 2 H), 0.95 (t, J = 7.8 Hz, 9 H), 0.8–0.76 (m, 6 H). ¹³C NMR (150 MHz, CDCl₃): δ = 164.3, 162.7, 136.0, 135.9, 132.7, 132.7, 114.9, 114.7, 7.3, 3.4. ¹⁹F NMR (564 MHz, CDCl₃): δ = –112.69; IR (ATR): ν = 3031, 2951, 2882, 2327, 2102, 1898, 1586, 1498, 1459, 1231, 1161, 1100, 1007, 818, 721 cm^–1. ESI-MS: m/z (%) = 210.0 (38) [M⁺], 182.1 (28), 181.0 (47), 153.0 (20).