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Biotage® PS-PPh3-Pd

Highly Effective Supported Palladium Catalyst, Re-usable

PS-PPh3Pd

Biotage® PS-PPh3-Pd resin is a polystyrene-supported equivalent of the small molecule catalyst tetrakis(triphenylphosphine) palladium(0) [Pd(Ph3P)4]. The primary application for the resin is as a catalyst for Suzuki-Miyaura coupling reactions between arylboronic acids and aryl halides. PS-PPh3-Pd may also have applications in other types of palladium-catalyzed processes in which Pd(Ph3P)4 is used. The Suzuki reaction is one of the most widely practiced coupling protocols for the preparation of symmetrical and unsymmetrical biaryl compounds. The resin was developed to perform in a manner similar to that of the well-established catalyst, while facilitating reagent handling and simplifying workup, product isolation, and removal of palladium.

CONSUMABLES

Part No. Description Product type Pack Size Price
PS-PPh3 800473 Biotage® PS-PPh3-Pd, 1 g Consumables 1 Log in for price
PS-PPh3 800474 Biotage® PS-PPh3-Pd, 10 g Consumables 1 Log in for price
PS-PPh3 800475 Biotage® PS-PPh3-Pd, 25 g Consumables 1 Log in for price
PS-PPh3 800476 Biotage® PS-PPh3-Pd, 100 g Consumables 1 Log in for price

Committed to preserving our shared environment – further details available on request.

Can be used in processes in compliance with cGMP standards.

Manufacture of consumables is accredited by the world renowned British Standards Institute.

Flexible supply chains, back up manufacturing and warehousing ensures supply risk reduction

Can be used in processes in compliance with GLP standards.

Products which are scaleable from lab or development to process scale.

Long to indefinite product shelf life, reduced process risk.

Supports pharma guidelines for reducing elemental impurities in APIs.

Further extractable information provided on request.

Raw materials certified free of materials of human or animal origin.

Chemical substances used in our manufacturing process do not require registration.

Able to withstand mechanical stirring and heating under normal reaction conditions.

Download the product note.

 

Application

Pd(Ph3P)4 is preferred to other palladium catalysts for this application because of its mild reaction conditions and broad scope of reactivity. However, despite the widespread use of palladium-mediated catalytic reactions, removal of residual palladium during workup and product isolation remains a major problem. Reducing the palladium content to the parts per million (ppm) level, as is required for active pharmaceutical ingredients, is particularly challenging.

Scope and Usage

PS-PPh3-Pd offers scope and reactivity similar to that of Pd(Ph3P)4 with the additional convenience of a polymer supported reagent for handling and purification. Unlike the small molecule reagent, PS-PPh3-Pd has been found to be stable to air and can be stored at room temperature for extended periods of time without degradation. The resin may be weighed out on the bench using regular weighing tools and requires no special handling techniques. Typical reaction conditions for Suzuki cross-coupling reactions of aryl bromides and iodides with arylboronic acids utilize 0.5 mol% of PS-PPh3-Pd catalyst. The reactions are performed in a mixture of dimethoxyethane (DME) and EtOH (1:1) in the presence of aqueous K2CO3 at 75 °C for 16 h. After the reaction is complete, the reaction mixture is diluted with DCM and water, followed by separation and filtration of the organic layer through a silica gel SPE cartridge. The product is then concentrated. Using this protocol the products are typically obtained in excellent yield and purity, and contain <100 ppm residual palladium.

Suzuki Reaction Reacivity

To evaluate the scope and reactivity of PS-PPh3-Pd resin, a series of Suzuki coupling reactions was performed. Substrates included various aryl bromides and arylboronic acids. Coupling reactions were carried out using 0.5 mol% of the bound catalyst. For comparison purposes, most of the reactions were also conducted with 0.5 mol% of the small molecule catalyst, Pd(Ph3P)4, as a control. In all cases, the standard protocol was followed and the products analysed by GC to determine the % conversion of starting material. The chemical purity was determined by GC and/or 1H-NMR. The range of aryl bromides, including the heterocyclic bromides, underwent high conversion to product with the series of boronic acids studied.

While both catalysts gave excellent results, use of the bound catalyst provided easier weighing and dispensing and afforded products with substantially lower levels of residual palladium. Given its uniform density, the resin may also be dispensed by automated filling devices or manual dispensing systems such as the ArgoScoop® resin dispenser (Part Number 900131). For more information please see the product note PPS401.

Representative Procedures

Suzuki Reaction of Aryl Halides with Arylboronic Acid, 4-bromoanisole (0.187 g, 1 mmol) in DME (1 mL) was added to PS-PPh3-Pd(0) (0.05 g, 0.005 mmol, 0.10 mmol/g), followed by 2-methylbenzeneboronic acid (0.162 g, 1.2 mmol) in EtOH (1 mL), and K2CO3 (0.207 g, 1.5 mmol) in water (0.5 mL). The reaction mixture was agitated for 16 h at 75 °C, cooled to room temperature and diluted with DCM (1 mL) and water (2 mL). The organic layer was then passed through a silica SPE cartridge (500 mg), pre-conditioned with DCM (4 mL). The effluent was collected, the cartridge was washed with DCM (3 x 3 mL), and the combined effluent plus washings were concentrated to afford 4-(o-tolyl)anisole in 95% yield (0.19 g, GC purity 97%). The residual palladium content in the product was determined to be 90 ppm. The amount of palladium found in the control experiment using the small molecule catalyst Pd(Ph3P)4 was 1700 ppm.