Synlett 2017; 28(18): 2465-2467
DOI: 10.1055/s-0036-1588504
cluster
© Georg Thieme Verlag Stuttgart · New York

Tetrabutylammonium Bifluoride as an Efficient Activating Agent for Copper-Catalyzed Vinylsilane Cross-Coupling Reactions

Loïc Cornelissen
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST) – Université Catholique de Louvain, Place Louis Pasteur 1, bte L4.01.02, 1348 Louvain-la-Neuve, Belgium   Email: olivier.riant@uclouvain.be
,
Audric Nagy
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST) – Université Catholique de Louvain, Place Louis Pasteur 1, bte L4.01.02, 1348 Louvain-la-Neuve, Belgium   Email: olivier.riant@uclouvain.be
,
Tom Leyssens
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST) – Université Catholique de Louvain, Place Louis Pasteur 1, bte L4.01.02, 1348 Louvain-la-Neuve, Belgium   Email: olivier.riant@uclouvain.be
,
Institute of Condensed Matter and Nanosciences, Molecules, Solids and Reactivity (IMCN/MOST) – Université Catholique de Louvain, Place Louis Pasteur 1, bte L4.01.02, 1348 Louvain-la-Neuve, Belgium   Email: olivier.riant@uclouvain.be
› Author Affiliations
Further Information

Publication History

Received: 08 May 2017

Accepted after revision: 22 June 2017

Publication Date:
25 August 2017 (online)


Published as part of the Cluster Silicon in Synthesis and Catalysis

Abstract

Vinylsilanes are versatile and efficient nucleophiles in cross-coupling reactions. Herein is described the use of tetrabutylammonium bifluoride as a mild, cheap and scalable activating agent in several copper-catalyzed vinylsilane cross-couplings.

Supporting Information

 
  • References and Notes

  • 5 Cornelissen L. Vercruysse S. Sanhadji A. Riant O. Eur. J. Org. Chem. 2014; 35
  • 6 Cornelissen L. Cirriez V. Vercruysse S. Riant O. Chem. Commun. 2014; 50: 8018
  • 7 Cornelissen L. Lefrancq M. Riant O. Org. Lett. 2014; 16: 3024
  • 8 TBAHF2 was easily synthesized in large scale from TBA(HSO4) and KHF2 according to: Landini D. Molinari H. Pensa M. Rampoldi A. Synthesis 1988; 953 ; TBAHF2was used as a 25 wt% solution in MeCN and could be stored in the fridge for extended periods
  • 9 Vinylsilane Cross-Couplings: Typical Procedure To a mixture of (E)-2-[4-(triethoxysilyl)but-3-enyl]isoindoline-1,3-dione (1a, 0.20 mmol, 1.0 equiv) and (bromoethynyl)benzene (0.30 mmol, 1.5 equiv) in an oven-dried vial was added TBAHF2 (0.5 mmol, 2.5 equiv, 25 wt% solution in MeCN). Cu[MeCN]4PF6 (0.01 mmol, 0.05 equiv) was added, and the resulting mixture was stirred at 40 °C in an oil bath for 16 h. The solution was diluted with Et2O (5 mL), filtered through a short pad of silica and eluted with Et2O (25 mL). The solution was evaporated under reduced pressure to afford the crude product. The crude product (94% NMR yield using CHBr3 as an internal standard) could be purified by flash chromatography using 20% EtOAc in PE to afford 2a as a pale orange solid. Rf = 0.68 (95% CH2Cl2 in PE). IR (thin film): 1771, 1497, 1394, 1364, 1340, 1219, 1055, 959, 870, 754, 719, 689 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.85 (dd, J = 5.4, 3.1 Hz, 2 H), 7.71 (dd, J = 5.4, 3.1 Hz, 2 H), 7.45–7.35 (m, 2 H), 7.34–7.22 (m, 3 H), 6.19 (dt, J = 15.4, 7.2 Hz, 1 H), 5.77 (d, J = 15.8 Hz, 1 H), 3.80 (t, J = 7.1 Hz, 2 H), 2.68–2.49 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 168.16, 139.56, 133.94, 131.96, 131.42, 128.20 (br), 128.01, 123.25, 112.51, 88.85, 87.56, 36.95, 32.21. ESI-HRMS: m/z calcd for C20H16O2N1[MH+] 302.1176; found: 302.1174.
  • 10 See Supporting Information for a more detailed survey of activating agents.
  • 11 For a review about higher-coordinated molecular silicon compounds, see: Wagler J. Böhme U. Kroke E. Struct Bond. 2014; 155: 29
  • 12 Trost BM. Ball ZT. Jöge T. J. Am. Chem. Soc. 2002; 124: 7922
  • 15 Synthesis of α-vinylalkoxysilanes: Trost BM. Ball ZT. J. Am. Chem. Soc. 2005; 127: 17644
  • 16 Synthesis of β-(Z)-vinylalkoxysilanes: Faller JW. D’Alliessi DG. Organometallics 2002; 21: 1743