3D Printed Tetrakis(triphenylphosphine)palladium (0) Impregnated Stirrer Devices for Suzuki-Miyaura Cross-Coupling Reactions

Abstract

3D printed materials can be readily modified to create bespoke structures that incorporate a range of catalysts at the point of printing. In this present study we report on the design and 3D printing of tetrakis (triphenylphosphine) palladium (0) impregnated 3D printed stirrer devices that were used to catalyze a Suzuki-Miyaura reaction between biaryl compounds in a batch-based approach. It was shown that the devices themselves are reusable, easy to use, air-stable, give access to an array of biaryl compounds in excellent yields and lead to low levels of palladium loss into the reaction. Simple modification of the device’s design by size reduction, meant that they could also be used to reduce the time of the Suzuki-Miyaura reaction by microwave enhanced heating. At the end of the reaction, devices can simply be removed from the flask, washed and reused, analogous to stirrer bead workflows. This makes the overall process of setting up multiple reactions simpler by obviating the need to weigh out catalysts for reactions and the device, once used, can be simply removed from the reaction media at the end of the reaction.

3D Printed Reactors and Kessil Lamp Holders for Flow Photochemistry: Design and System Standardization

“…As a result of the challenges in standardizing and reporting on photochemical setup and reactions in flow chemistry, combined with our research into rapid prototyping and equipment development using 3D printing, we sought to develop a standardized housing for readily available LED lamps that could be used in combination with 3D printed flow photochemistry cells [25][26][27][28][29]. The aim of this was to introduce a low cost, small footprint system that could be combined with existing laboratory equipment to allow researchers to investigate photochemical reactions in flow.…”

3D Printed Reactors and Kessil Lamp Holders for Flow Photochemistry: Design and System Standardization

“…As a result of the challenges in standardizing and reporting on photochemical setup and reactions in flow chemistry, combined with our research into rapid prototyping and equipment development using 3D printing, we sought to develop a standardized housing for readily available LED lamps that could be used in combination with 3D printed flow photochemistry cells [25][26][27][28][29]. The aim of this was to introduce a low cost, small footprint system that could be combined with existing laboratory equipment to allow researchers to investigate photochemical reactions in flow.…”

Rapid Lewis Acid Screening and Reaction Optimization using 3D Printed Catalyst Impregnated Stirrer Devices in the Synthesis of Heterocycles

“…11j However, recent research by our group into catalyst embedded stirrer devices for chemical synthesis has led to the discovery of a resin formulation that is stable to a range of organic solvents and that can be 3D printed with embedded Pd catalysts and that was shown to efficiently catalyze Suzuki-Miyaura reactions with low catalyst loss. 12 As a result of our research into 3D printing and 3D printed catalyst embedded stirrers, we were intrigued by the possibility of extending our research into the area of Lewis Acids (LA), where LA catalysts could be incorporated into SLA 3D printed stirrer devices. Solid supported Lewis Acids have previously been used in the synthesis of heterocycles and active pharmaceutical ingredients (APIs), 13 but whilst they have been used in this approach, they typically require weighing out before use, in much the same way as the use of traditional solution-based catalysts.…”

“…Solid supported Lewis Acids have previously been used in the synthesis of heterocycles and active pharmaceutical ingredients (APIs), 13 but whilst they have been used in this approach, they typically require weighing out before use, in much the same way as the use of traditional solution-based catalysts. 13 Our new paradigm approach therefore provides a much more simplified workflow, 12 where a range of Lewis Acid impregnated stirrers can be readily added to a reaction followed by the reagents. Once the reaction is complete, they can then be removed at the end of the reaction in much the same way as a stirrer bar, making the entire process much simpler to follow, (Figure 1).…”

“…However, the catalyst itself is distributed evenly throughout the device, meaning that only the catalyst near the surface is available for reaction. 12 As such, we estimate that only 10% of the actual catalyst is available for reaction for the carousel stirrer devices. The Sc(OTf)3 impregnated stirrer device has approximately 20 mg of Sc(OTf)3 where as in the reaction 49 mg has been used as a powdered catalyst.…”