Infrared irradiation or microwave assisted cross-coupling reactions using sulfur-containing ferrocenyl-palladacycles

doi:10.1016/j.jorganchem.2016.05.017

Journal of Organometallic Chemistry

Volume 818, 1 September 2016, Pages 7-14

https://doi.org/10.1016/j.jorganchem.2016.05.017 Get rights and content

Highlights

•
New palladacycles were successfully obtained from a ferrocenyl thionoester precursor.
•
Palladacycle 4a shows excellent catalytic properties in Heck and Suzuki reactions.
•
Microwave and infrared are compared as energy sources to promote CC reactions.
•
IR is an efficient and accessible alternative energy source to assist CC reactions.

Abstract

The synthesis of four new sulfur-containing palladacycles 3a-d [FcC(S)OEtPdClZR₃, where: 3a, ZR₃: PPh₃; 3b, ZR₃: P(o-Tol)₃; 3c, ZR₃: PMe₃; 3d, ZR₃: SbPh₃] from ferrocenyl thionoester 1 [FcC(S)OEt] in good yields is reported. The catalytic applications of these cyclopalladated complexes in Heck and Suzuki cross-coupling reactions were also evaluated, in combination with infrared or microwave as energy sources. The coupled products of these reactions were obtained in good to excellent yields, short reaction times and low catalyst loading.

Graphical abstract

The catalytic applications of four new sulfur-containing cyclopalladated complexes in Heck and Suzuki cross-coupling reactions, in combination with different energy sources are reported. We found that infrared irradiation (IR) is an efficient, economical and accessible alternative source of energy to assist both coupling reaction.

Introduction

Since the first report in 1995, on the synthesis and applications of Herrmann-Beller’s palladacycle in catalytic C single bond C coupling reactions [1], palladacycles with a widespread range of structural arrangements and synthetic accessibility have attracted great interest as catalytic precursors [2], [3]. Currently, diverse examples of palladacycles synthesized from ferrocenyl compounds like ferrocenyl imines [4], ferrocenyl oximes [5], (dimethylaminomethyl) ferrocene [6], and 2-pyridylferrocene and their analogues [7], ferrocenyl imidazoline [8], and ferrocenyl oxazoline [9] have been reported.

Likewise, organosulfur ligands are very common precursors used in the synthesis of very stable palladacycles [2], and include different frameworks such as pincer type ligands, thioethers, thiourea based ligands, sulfur substituted NHCs, thiosemicarbazones and sulfated Schiff bases [10]. However, only some palladacycles using ferrocenyl thiocarbonyl compounds are known [11], maybe due to the difficulty of extending routine synthetic methodologies to ferrocenyl compounds. An approach for obtaining these kinds of palladacycles is using ferrocenyl thioamides as ligands [12]. Thiocarbonyl precursors can be prepared via a Willgerodt-Kindler reaction [13] or using a sulfurative demetalation reaction of Fischer ferrocenyl carbene complexes [14].

On the other hand, infrared irradiation is an energy source scarcely used as non-conventional heating in comparison to microwaves [15]. Some applications in organic synthesis show that infrared irradiation efficiently promotes condensation reactions [16], oxidation reactions [17], heterocyclic compound syntheses [18], and Diels-Alder reactions [19], among others [20]. As a research program focused on the use of infrared irradiation in C single bond C coupling reactions, we have started to explore the use of IR to assist the Heck coupling reaction with very good results [21]. In this context and, with regards to further applications of ferrocenyl thiocarbonyls, we hereby report the synthesis of four new monomeric cyclopalladated complexes, using as a precursor a O-ethyl ferrocenyl thionoester and three different trialkylphosphines and triphenylstibine. We also describe the catalytic applications of these new cyclopalladated complexes in Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions promoted by different heating sources, such as microwave and infrared.

Section snippets

Synthesis and characterization of palladacycles 3a-d

At first, O-ethyl ferrocenyl thionoester 1 was prepared by a sulfurative demetalation reaction in good yields, from a ferrocenyl ethoxycarbene chromium complex [22], in accordance with a protocol developed earlier by our group [14]. Palladacycles 3a-d were prepared by direct cyclopalladation of 1 with [Na₂PdCl₄] generated in situ in methanol at room temperature, obtaining a deep purple solid, insoluble in chlorinated solvents. FAB⁺ mass spectrometry showed a molecular ion at 830 m/z assigned to

Conclusions

We have developed the synthesis of four new palladacycles complexes 3(a–d) in good yields via C single bond H bond activation on a ferrocenyl thionoester precursor. As we have shown, these new palladium (II) complexes are promising as catalytic precursors for Heck and Suzuki coupling reactions. Their stability to air and moisture, avoids the use of inert conditions and facilitates all the manipulation in open atmosphere. The coupled products of these reactions were obtained in good to excellent yields,

General considerations

The synthesis of precursor 1 was carried out in an inert atmosphere of nitrogen gas using standard Schlenk techniques. Anhydrous THF was obtained by distillation under an inert atmosphere over sodium benzophenone. Column chromatography was performed using 70–230 mesh silica gel. All reagents and solvents were obtained from commercial suppliers and used without further purification. All compounds were characterized by IR spectra, recorded on a Perkin-Elmer 283B or 1420 spectrophotometer, by

Acknowledgements

The authors would like to acknowledge the technical assistance provided by Martin Cruz Villafañe, Rocio Patiño, Nayeli López, Luis Velasco, and Javier Perez. We would also like to thank DGAPA IN205014 and CONACYT for the Ph.D. grant extended to J. A. B.-V., reference number 240047.

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Infrared irradiation or microwave assisted cross-coupling reactions using sulfur-containing ferrocenyl-palladacycles

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Synthesis and characterization of palladacycles 3a-d

Conclusions

General considerations

Acknowledgements

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