Synlett 2017; 28(19): 2594-2598
DOI: 10.1055/s-0036-1591495
cluster
© Georg Thieme Verlag Stuttgart · New York

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

Shao-Chi Lee
a  Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany   Email: Magnus.Rueping@rwth-aachen.de
,
Lin Guo
a  Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany   Email: Magnus.Rueping@rwth-aachen.de
,
Huifeng Yue
a  Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany   Email: Magnus.Rueping@rwth-aachen.de
,
Hsuan-Hung Liao
a  Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany   Email: Magnus.Rueping@rwth-aachen.de
,
a  Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany   Email: Magnus.Rueping@rwth-aachen.de
b  King Abdullah University of Science and Technology (KAUST), KAUST Catalysis Center (KCC), Thuwal, 23955-6900, Saudi Arabia   Email: magnus.rueping@kaust.edu.sa
› Author Affiliations
Further Information

Publication History

Received: 11 July 2017

Accepted after revision: 25 September 2017

Publication Date:
23 October 2017 (online)


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.

Supporting Information

 
  • References and Notes

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  • 24 Recently, a protocol for the decarbonylative borylation of amides was established by Shi and co-workers, see ref. 12c. With a catalytic system consisting of nickel and an N-hetero­cyclic carbene ligand, the N-Boc,N-Me-derived amides were converted into the corresponding borylation products in moderate to high yields. Interestingly, distorted cyclic imides were completely unsuccessful.
  • 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).