Synlett 2014; 25(09): 1241-1245
DOI: 10.1055/s-0033-1341200
letter
© Georg Thieme Verlag Stuttgart · New York

Palladium-Catalyzed Carbonylation of Aryl Bromides with N-Substituted Cyanamides

Zhong Lian
a  Center for Insoluble Protein Structures, Interdisciplinary Nanoscience Center, Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C, Denmark
,
Stig D. Friis
a  Center for Insoluble Protein Structures, Interdisciplinary Nanoscience Center, Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C, Denmark
,
Anders T. Lindhardt*
b  Department of Engineering, Aarhus University, Finlandsgade 22, 8200 Aarhus N, Denmark   Fax: +4541893001   Email: lindhardt@eng.au.dk   Email: ts@chem.au.dk
,
Troels Skrydstrup*
a  Center for Insoluble Protein Structures, Interdisciplinary Nanoscience Center, Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C, Denmark
› Author Affiliations
Further Information

Publication History

Received: 20 February 2014

Accepted after revision: 19 March 2014

Publication Date:
11 April 2014 (eFirst)

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Abstract

The palladium(0)-catalyzed three-component coupling reaction of aryl bromides, carbon monoxide, and N-alkyl cyan­amides has been developed employing a two-chamber system with ex situ generation of carbon monoxide from a silacarboxylic acid. The reactions proceeded well and were complete with a reaction time of only five hours leading to the corresponding N-alkyl cyanamides in good yields. The methodology was further extended to 13C isotope labeling of the carbonyl group through the use of a 13CO produced from the corresponding 13C-labeled version of the sila­carboxylic acid.

Key words

N-alkyl cyanamides - transition-metal catalysis - isotope labeling - aminocarbonylation - multicomponent reaction - palladium

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett. Included are general methods, an experimental section and copies of 1H and 13C NMR spectra for all products.
  • Supporting Information
 

  • References and Notes

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  • 16 General Procedure for the Synthesis of N-Benzyl-N-cyano-2-naphthamide (3a) In an argon-filled glovebox to chamber 1 of the two-chamber system was added 2-bromonaphthalene (42 mg, 0.20 mmol), [Pd(cinnamyl)Cl]2 (5.0 mg, 0.01 mmol), CataCXium A (8.0 mg, 0.02 mmol), K3PO4 (65 mg, 0.3 mmol), and butyronitrile (1.0 mL) in that order. The chamber was closed with a screwcap fitted with a Teflon seal. To chamber 2 of the two-chamber system was added methyldiphenylsila-carboxylic acid (122 mg, 0.50 mmol) and KF (30 mg, 0.50 mmol). The chamber was closed with a screwcap fitted with a Teflon seal. The loaded two-chamber system was removed from the glovebox and heated to 30 °C for 15 min. Then N-benzyl cyanamide (31 mg, 0.24 mmol) in butyronitrile (1.0 mL) was added to chamber 1. Lastly butyronitrile (2.0 mL) was added to chamber 2. This reaction was stirred at 90 °C for 5 h and was then cooled to r.t. The solids were filtrated off, and the reaction was concentrated under vacuum. The crude residue was subjected to flash chromatography using pentane–EtOAc (10:1) as eluent. This resulted in 46 mg (81%) of 3a as white solid. 1H NMR (400 MHz, CDCl3): δ = 8.43 (s, 1 H), 7.94–7.98 (m, 2 H), 7.91 (d, J = 8.4 Hz, 1 H), 7.85 (d, J = 8.4 Hz, 1 H), 7.44–7.84 (m, 7 H), 4.98 (s, 2 H). 13C NMR (100 MHz, CDCl3): δ = 168.1, 135.3, 133.8, 131.9, 130.0, 129.2, 129.1 (2 C), 129.0 (2 C), 128.8, 128.7, 128.6, 127.9, 127.8, 127.2, 124.3, 111.1, 51.4. HRMS: m/z calcd for C19H15N2O [M + H]+: 287.1184; found: 287.1178. 13C-Labeled N-Benzyl-N-cyano-2-naphthamide (13C-3a) According to the general procedure. Flash chromatography using pentane–EtOAc (10:1) as eluent resulted in 46 mg (80% yield) as a white solid. 1H NMR (400 MHz, CDCl3): δ = 8.40 (d, J = 4.4 Hz, 1 H), 7.81–7.96 (m, 4 H), 7.41–7.64 (m, 7 H), 4.96 (d, J = 2.8 Hz, 2 H). 13C NMR (0100 MHz, CDCl3): δ = 168.1 (13C-enriched), 135.4, 133.9, 132.0 (d, J = 5.1 Hz), 130.1 (d, J = 2.2 Hz), 129.3 (2 C), 129.1 (d, J = 2.9 Hz, 2 C), 128.8, 128.7, 128.6, 128.4, 127.9, 127.7, 127.3, 124.3 (d, J = 2.2 Hz), 111.1 (d, J = 3.6 Hz), 51.5. HRMS: m/z calcd for C18 13CH15N2O [M + H]+: 288.1218; found: 288.1213.