An efficient catalyst for the synthesis of ortho-substituted biaryls by the Suzuki cross-coupling: Triphenylphosphine adduct of cyclopalladated ferrocenylimine

doi:10.1016/j.jorganchem.2006.09.023

Journal of Organometallic Chemistry

Volume 691, Issue 26, 15 December 2006, Pages 5688-5696

https://doi.org/10.1016/j.jorganchem.2006.09.023 Get rights and content

Abstract

The air and moisture stable triphenylphosphine adduct of cyclopalladated ferrocenylimine 2 has been successfully used in palladium-catalyzed Suzuki cross-coupling for the synthesis of ortho-substituted biaryls in air. In the presence of 0.05 mol% of 2 as catalyst and 3 equivalent of CsF as base in dioxane at 100 °C, ortho-substituted biaryls were synthesized with moderate to high yields in the reactions of 2-methoxy-1-naphthylboronic acid with aryl halides, and 14 new ortho-substituted biaryls were obtained and characterized.

Graphical abstract

Introduction

ortho-Substituted biaryls are important structure moieties of biologically active compounds and organic functional materials [1]. However, the linking of sterically hindered carbon centers is very difficult and the formation of ortho-substituted biaryls under mild conditions has remained elusive [2]. Thus, a general method for the synthesis of hindered biaryls has yet to be realized [3]. The Suzuki cross-coupling is among the most powerful tools for the construction of biaryl bonds due to its efficiency and wide functional-group tolerance [4]. There is currently considerable interest in the development of efficient catalysts that can catalyze the Suzuki-coupling reaction to form ortho-substituted biaryls [5], [6]. Advances have been made with efficacious supporting ligands, such as phosphines [5] and N-heterocyclic carbenes [6] to increase the activity of catalysts. Moreover, palladacyclic catalysts are among the most active catalysts for carbon–carbon and carbon-heteroatom bond formation and have attracted much attention owning to their availability, facile modification, insensitivity to air or moisture and easy handling as compared with the most other catalysts [7]. However, only in rare cases Suzuki couplings of sterically hindered substrates have been investigated with palladacycles. Bedford et al. reported recently that phosphinito-based palladacycles in the presence of PCy₃ were efficient catalysts for the Suzuki coupling of sterically hindered substrates [8].

Although many palladacycles have been reported for Suzuki coupling, there are no large difference in catalyst activity because they generate a ligand-free nanoparticles as active species for oxidative addition of haloarenes[9]. Our laboratory has been focusing on the studies of cyclometallation of ferrocenylimines and their applications [10]. We found that cyclopalladated ferrocenylimines, such as 1, were efficient catalysts for the Heck reaction [11], the dimerization of arylmercurials [12], and the Suzuki coupling reaction [13]. As an extension of our studies, we report herein the preparation of ortho-substituted biaryls by the Suzuki cross-coupling using 2 as palladacyclic catalyst and 2-methoxy-1-naphthylboronic acid as a hindered partner.

Section snippets

Results and discussion

Initially, the Suzuki cross-coupling reactions of 4-methoxylphenyl bromide with 2-methoxy-1-naphthylboronic acid were carried out with various catalysts, bases and solvents. The results were shown in Table 1. The performance of catalyst 1 and 2 was first tested (entries 1–3), and 2 exhibited higher activity with a loading as low as 0.1 mol%. The Suzuki cross-coupling reactions were generally carried out under the protection of inert gas [3](h), [14]. We found that the reaction occurred smoothly

General

Reactions were monitored by thin-layer chromatography, which was carried out on silica gel coated glass plates (60 F₂₅₄). Melting points were measured with the use of a WC-1 microscopic apparatus. Elemental analyses were conducted with a Carlo Erba 1160 elemental analyzer. IR spectra were collected on a Bruker VEC-TOR22 spectrophotometer in KBr pellets. ¹H and ¹³C NMR spectra were recorded on a Bruker DPX-400 spectrometer in CDCl₃ with TMS as an internal standard. Mass spectra were recorded

Acknowledgements

We are grateful to the National Natural Science Foundation of China (Project 20472074) and the Innovation Found for Outstanding Scholar of Henan Province (Project 0621001100) for the financial support given to this research. We thank professor Zhu Zhiwu for valuable discussion of this paper.

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An efficient catalyst for the synthesis of ortho-substituted biaryls by the Suzuki cross-coupling: Triphenylphosphine adduct of cyclopalladated ferrocenylimine

Abstract

Graphical abstract

Introduction

Section snippets

Results and discussion

General

Acknowledgements

Eur. J. Inorg. Chem.

Chem. Commun.

J. Organomet. Chem.

J. Organomet. Chem.

Coord. Chem. Rev.

Chem. Rev.

J. Organomet. Chem.

Acta Chim. Sin.

Org. Process Res. Dev.

Angew. Chem., Int. Ed. Engl.

Tetrahedron

Chem. Rev.

Chem. Rev.

Metal-Catalyzed Cross-Coupling Reactions

J. Org. Chem.

Tetrahedron Lett.

Chem. Commun.

J. Am. Chem. Soc.

Tetrahedron: Asymmetry

Org. Lett.

Tetrahedron

Eur. J. Org. Chem.

Org. Lett.

Chem. Rev.

J. Organomet. Chem.

Top. Curr. Chem.

J. Am. Chem. Soc.

Org. Lett.

J. Am. Chem. Soc.