(t-Bu)₂PhP Pd G3 , CAS No.2230788-65-3

CAS: 2230788-65-3 Cat. No.: T486915 Peso molecular: 592.04

Synonyms

PPh(t-Bu)₂-Pd-G3, Methanesulfonato (di-tert-butyl) phenylphosphino (2′-amino-1,1′-biphenyl-2-yl) palladium(II)

Storage

Room temperature

Specifications

Sinónimos

PPh(t-Bu)₂-Pd-G3, Methanesulfonato (di-tert-butyl) phenylphosphino (2′-amino-1,1′-biphenyl-2-yl) palladium(II)

Condições de armazenamento de armazenamento

Room temperature

Nomes e identificadores

• Sorrisos canónicos: CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1.NC2=C(C3=C([Pd]OS(C)(=O)=O)C=CC=C3)C=CC=C2
• InChIKey: IQWMOOOMAPPAMZ-UHFFFAOYSA-M
• INCHI: 1S/C14H23P.C12H10N.CH4O3S.Pd/c1-13(2,3)15(14(4,5)6)12-10-8-7-9-11-12;13-12-9-5-4-8-11(12)10-6-2-1-3-7-10;1-5(2,3)4;/h7-11H,1-6H3;1-6,8-9H,13H2;1H3,(H,2,3,4);/q;;;+1/p-1
• Número UN: 2811
• Peso molecular: 592.04

Propriedades químicas e físicas

• Ponto de inflamação (°F): Not applicable
• Ponto de inflamação (°C): Not applicable

Application Protocols

No assay or bioanalytical protocols are specified for this product. For synthetic use, consider the following generic setup (literature guidance; adapt to your substrate):

• Example (Buchwald–Hartwig amination):
  • To an oven-dried vial under N₂ add aryl chloride (1.0 equiv), amine (1.2 equiv), base (K₃PO₄, 2.0–3.0 equiv), (t-Bu)₂PhP Pd G3 (0.5–1.0 mol% Pd), and toluene or 2-MeTHF to 0.2–0.5 M. Heat 80–100 °C until complete by HPLC/GC.
• Example (Suzuki–Miyaura):
  • Combine aryl bromide/chloride (1.0 equiv), boronic acid/ester (1.2–1.5 equiv), base (K₂CO₃ or K₃PO₄, 2–3 equiv), catalyst (0.1–0.5 mol% Pd), and 1,4-dioxane/H₂O (or 2-MeTHF/H₂O). Heat 50–90 °C.

These are illustrative, literature-style procedures, not validated protocols for this catalog item. Optimize conditions for your specific substrates.

Biological Roles

This product is an organometallic palladium precatalyst for synthetic chemistry. It does not have a biological function, metabolic role, or signaling activity in living systems.

General note for chemists:

• Any intersection with biology is indirect, via its use in constructing bioactive small molecules, labeled probes, or complex intermediates by cross-coupling. No endogenous biochemical role is associated with palladium phosphine complexes.
• Handle exclusively as a research reagent. See SDS for toxicological details; no in vivo or clinical applications are implied or supported.

Buffer Applications

Not applicable. This item is a palladium precatalyst and is not used to prepare or maintain aqueous buffer systems. For work involving this catalyst, select an appropriate organic or mixed solvent system and base as detailed under Solvent Selection and Reaction Conditions.

Green Alternatives

Assessment framework (general, literature-based): Choose solvents, bases, and catalyst loadings to minimize environmental impact while maintaining performance.

Greener choices around this Pd precatalyst:

• Solvents: Replace DMF/NMP with 2-MeTHF, CPME, anisole, toluene, or water/ethanol systems where feasible. Employ micellar catalysis (e.g., aqueous surfactant media) for certain Suzuki couplings to reduce organic solvent use.
• Catalyst economy: The rapid initiation of G3-type systems can enable very low Pd loadings (ppm–0.5 mol%) compared with older systems (e.g., Pd₂(dba)₃ + free ligand), reducing precious metal footprint and downstream purification.
• Base selection: Carbonates or bicarbonates in aqueous or green ether media are often preferable to strong alkoxides; avoid stoichiometric tin (Stille) when a Suzuki/Negishi route is viable.
• Alternative metals: For some aryl–heteroatom couplings, nickel catalysis can be a lower-cost alternative; however, substrate scope and impurity profiles differ and should be evaluated.

Comparison (literature, qualitative):

• Pd₂(dba)₃ + free phosphine: flexible but less predictable initiation, potential for higher Pd loadings.
• G3 precatalyst (this product): defined stoichiometry, fast activation, potential for reduced loadings and improved reproducibility.
• Heterogeneous Pd/C: greener workup in some cases but limited selectivity and leaching concerns for complex substrates.

Pharmaceutical Uses

No excipient or clinical use. This product is for research use only.

Manufacturing/formulation context (general):

• Palladium-catalyzed cross-couplings are widely used in medicinal chemistry and process development to assemble API candidates and intermediates. G3-type precatalysts can offer fast initiation and low effective loadings, aiding impurity control.
• Regulatory considerations: For any process-scale use, residual palladium and phosphorus must be controlled per ICH Q3D and related guidelines. Downstream metal scavenging, activated carbon treatments, and crystallization protocols are commonly employed.
• Documentation: This catalog entry provides no pharmacopeial status. Consult internal quality systems and obtain CoA/SDS for any process evaluation.

Physical Properties

Item-specific specifications:

• Appearance: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.
• Melting point: Not specified for this item; refer to CoA/Spec Sheet.
• Boiling point: Not applicable (organometallic solid is expected to decompose before boiling; literature, general note).
• Density: Not specified for this item; refer to CoA/Spec Sheet.
• Solubility: Not specified for this item; refer to CoA/Spec Sheet.
• LogP, pKa, refractive index: Not applicable/Not specified for this item; refer to CoA/Spec Sheet.

General/literature guidance (not item specifications):

• Many allyl–Pd(II)–phosphine G3 precatalysts are air-stable, crystalline solids with moderate solubility in common organics (e.g., toluene, THF, dioxane, EtOAc, DCM) and higher solubility in aromatic solvents and chlorinated solvents. Actual solubility of this specific product should be verified experimentally.
• Thermal behavior: such Pd(II) precatalysts typically show decomposition rather than a sharp melt; storage at ambient, dry conditions is common unless otherwise stated (this item: Room temperature per Product Data).
• Hygroscopicity: generally low to moderate; keep container tightly closed and protected from moisture to preserve activity (good laboratory practice).

Quality and Grades

• Grade/Purity: Not specified for this item; refer to CoA/Spec Sheet.

Interpretation and implications (general):

• Palladium precatalysts used in cross-coupling are typically manufactured to high purity to minimize competing ligand species, halide variability, or residual synthesis byproducts that affect initiation rate and catalyst turnover number (TON/TOF). The CoA typically reports assay/purity, residual solvents, and occasionally metal content by ICP.
• Chromatography-grade or “high-purity” designations, when present, indicate reduced non-volatile residues and consistent performance in catalysis, especially at low catalyst loadings (<0.5 mol%). If UV-cutoff or HPLC absorbance specifications are required for analytical uses, consult the CoA; none are specified here.
• Stabilizers: None are indicated for this item. When stabilizers are used for certain Pd complexes, they can subtly alter initiation kinetics; absence/presence should be confirmed in the CoA.
• Batch-to-batch reproducibility: For sensitive cross-couplings, confirm catalyst charge by metal assay and consider a small pilot run when changing lots.

Reaction and Applications

This item is a third-generation palladium precatalyst pre-ligated with di-tert-butylphenylphosphine [P(t-Bu)₂Ph], designed to rapidly form an active L–Pd(0) species under basic or nucleophile-assisted conditions. Typical application families (literature):

• C–N cross-coupling (Buchwald–Hartwig amination): Effective for coupling aryl halides or sulfonates with primary/secondary amines, carbamates, amides, and anilines. Bulky, electron-rich phosphines accelerate oxidative addition to aryl chlorides and improve amine binding/turnover.
• C–C cross-coupling: Suzuki–Miyaura (aryl/heteroaryl boronates), Kumada (Grignards), Negishi (organozincs), and Stille (organostannanes), especially where rapid initiation is beneficial and steric bulk suppresses β-hydride elimination.
• C–O and C–S coupling: Arylation of alcohols/phenols (as alkoxides) and thiols; bulky phosphines often enhance reductive elimination rates.
• Aryl chloride activation: G3 systems are known for initiating quickly with aryl chlorides and heteroaryl electrophiles at moderate temperatures.

Practical notes:

• Precatalyst activation: base (e.g., t-BuONa/K, carbonates, amines) or nucleophiles can trigger formation of L–Pd(0). Short induction periods enable low catalyst loadings (≤0.5–2 mol%).
• Air handling: Many G3 complexes are bench-stable solids; nonetheless, weigh quickly and keep bottles closed to preserve performance.
• Additives: Halide salts or water can impact rates; phosphine-to-Pd ratio is fixed by the precatalyst, aiding reproducibility.
• Workup: Scavenge residual Pd with metal scavengers or activated carbon when required for downstream purity.

Reaction Conditions

General, literature-based guidance for G3-type Pd–phosphine precatalysts; adjust to substrate and scale. These are not specifications for this item.

• Catalyst loading: 0.05–2.0 mol% Pd typical; challenging aryl chlorides/sterically hindered partners may require 1–3 mol%. For high-activity substrates, ppm-level loadings are feasible with rigorous technique.
• Bases: K₃PO₄, K₂CO₃, Cs₂CO₃, NaOtBu/KOtBu, NaOMe/MeONa, DBU, or aqueous NaOH/KOH (with phase transfer or alcohol solvents). Choose based on nucleophile pKa and solvent.
• Solvents: toluene, xylene, dioxane, THF, 2-MeTHF, CPME, anisole, iPrOH/t-BuOH, acetonitrile, DMF/DMAc/NMP, water (micellar) for Suzuki. Ensure substrates and base are sufficiently soluble at reaction temperature.
• Temperatures: 25–120 °C. Aminations often 60–100 °C; Suzuki couplings 40–90 °C; hindered aryl chlorides may need 100–120 °C in high-bp solvents.
• Atmosphere: inert gas (N₂/Ar) recommended during reaction setup and run; many precatalysts are bench-stable as solids but perform best under inert conditions in solution.
• Initiation: brief preheat (5–15 min) with base and nucleophile can accelerate start-up. Some protocols preform L–Pd(0) in situ.
• Additives: water (1–10 vol%) can accelerate certain Suzuki couplings; halide salts (TBAB) may assist in phase transfer; avoid sulfur-containing impurities that poison Pd.
• Workup: quench with water, extract, and treat with metal scavengers or carbon as needed. Filter through silica/celite to remove Pd black. Residual Pd analysis by ICP-OES/ICP-MS for sensitive applications.

Safety and Handling

Authoritative safety information must be obtained from the product SDS. The following are general best practices for palladium precatalysts and tertiary phosphine-containing complexes.

Product-specific hazard entries:

• Signal word: Not specified for this item; refer to SDS.
• H-statements: Not specified for this item; refer to SDS.
• GHS classification/pictograms: Not specified for this item; refer to SDS.

General precautions (literature/standard lab practice):

• PPE: lab coat, nitrile gloves, and safety glasses as a minimum. Use in a fume hood to avoid inhalation of dust or solvent vapors during weighing and transfers.
• Avoid contact with oxidizers and strong acids/bases that could degrade the complex or the phosphine ligand. Protect from moisture to maintain catalytic performance.
• Tertiary phosphines may have a strong odor and can be irritating; avoid skin contact and inhalation. Palladium compounds may be harmful if swallowed or inhaled.
• First aid (general): if on skin/eyes, rinse with water for several minutes; if inhaled, move to fresh air; if ingested, rinse mouth. Seek medical attention as needed. Always consult the SDS for detailed measures.
• Waste: Collect Pd-containing wastes for metal recovery or disposal per institutional and local regulations. Do not release to the environment.
• Fire: Use CO₂, dry chemical, or foam on surrounding materials. The complex itself is not strongly flammable but may decompose under fire conditions, releasing irritating fumes.

Solvent Selection

This product is a palladium precatalyst rather than a solvent. Solvent choice should be tailored to the coupling reaction at hand.

General/literature guidance for (t-Bu)₂PhP–Pd G3-catalyzed couplings:

• Polarity and miscibility: Common solvents include toluene, xylene, dioxane, THF, CPME, 2-MeTHF, MTBE, anisole, acetonitrile, DMF/DMAc, NMP, and alcohols (t-BuOH, iPrOH). Water or aqueous-organic mixtures can be used with suitable bases and phase-transfer systems.
• Selection criteria: substrate solubility, base compatibility, boiling point for thermal control, and sustainability profile. Bulky monophosphine–Pd systems often perform well in nonpolar aromatic solvents (toluene) or ethers (THF, 2-MeTHF, dioxane). Polar aprotics (DMF/DMAc/NMP) can help with challenging aryl chlorides or polar nucleophiles but have higher EHS burdens.
• Bases/solvent interplay: carbonate bases pair well with polar aprotic or mixed ether systems; alkoxides (t-BuOK) often used in THF/2-MeTHF/toluene; aqueous hydroxides with alcohols or biphasic media.
• Temperature: choose solvents with appropriate bp to reach 60–120 °C as needed; high-boiling anisole/xylene aid difficult couplings.
• Practical tip: ensure the catalyst and ligand remain dissolved at reaction temperature; precipitation of Pd black indicates deactivation.

Storage and Reconstitution

• Storage conditions (product-specific): Room temperature (per Product Data). Store in the original, tightly closed container in a dry place. Protect from prolonged exposure to air and moisture to maintain catalytic performance.
• Shipping conditions: Not specified for this item; refer to CoA/Spec Sheet.
• Reconstitution/Preparation for use: Not applicable—use as supplied. For solution dosing, prepare stock solutions in dry, oxygen-free solvents (e.g., toluene, THF, 2-MeTHF, dioxane, anisole) under inert atmosphere. Use freshly prepared solutions when possible.
• Freeze–thaw: Not applicable to solids. If solutions are prepared and stored, keep under inert gas at low temperature (e.g., 0–5 °C) and use promptly; stability is formulation- and solvent-dependent.
• Shelf life: Not specified for this item; refer to CoA/Spec Sheet.
• Research use only: This product is intended for laboratory research. Consult the SDS for detailed stability and incompatibility information.

Structure and Identity

• Item name: (t-Bu)₂PhP Pd G3 (often described in the literature as a third-generation Buchwald-type precatalyst bearing di-tert-butylphenylphosphine, P(t-Bu)₂Ph)
• SKU: T486915
• CAS: 2230788-65-3 (product-specific)
• InChIKey: 148159 (as provided; note this does not follow the typical 27-character InChIKey format)
• SMILES: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular formula: Not specified for this item; refer to CoA/Spec Sheet.
• Molecular weight: Not specified for this item; refer to CoA/Spec Sheet.

Structural description (general/literature):

• The “G3” designation denotes a third-generation palladium precatalyst platform commonly described as an η3-allyl–Pd(II) chloride complex pre-ligated with a monodentate phosphine. In this case, the ligand is di-tert-butylphenylphosphine, P(t-Bu)₂Ph.
• Core features: a square-planar Pd(II) center; an η3-allyl fragment and chloride as X-type ligands; an L-type bulky arylphosphine [P(t-Bu)₂Ph]. Upon activation (base or nucleophile-assisted), the complex typically generates an active L–Pd(0) species bearing the same phosphine ligand.
• Functional groups: tertiary phosphine (strong σ-donor), aryl substituent (phenyl), tert-butyl groups providing steric bulk; metal center palladium in a precatalyst scaffold.
• Stereochemistry: η3-allyl coordination can exhibit syn/anti isomerism in the solid state in related systems (literature), but the active species is an L–Pd(0) complex in solution under catalytic conditions.

Note: Exact atom connectivity, counterions, and allyl substituent identity for this catalog item should be confirmed in the product CoA/Spec Sheet.

Synthetic Utility

Functional role:

• Single-component, preligated Pd(II) precatalyst delivering an electron-rich, bulky monophosphine [P(t-Bu)₂Ph] upon activation. The ligand promotes fast oxidative addition and efficient reductive elimination, particularly valuable for hindered substrates.

Retrosynthetic value (literature):

• Streamlines installation of C(sp²)–N, C(sp²)–C(sp²/sp³), C(sp²)–O, and C(sp²)–S bonds from aryl chlorides/triflates. Facilitates late-stage diversification of heteroaromatics and medicinal scaffolds where base- or heat-sensitive motifs are present.

Named transformations:

• Buchwald–Hartwig amination (anilines, alkyl/benzyl/secondary amines, amides/carbamates)
• Suzuki–Miyaura coupling (boronic acids/esters, MIDA boronates)
• Etherification and thioetherification of phenols/thiols
• Less commonly, directed C–H functionalizations via cross-coupling handles introduced upstream

Practical considerations:

• Single-component dosing avoids variability in ligand-to-Pd ratio common with Pd₂(dba)₃ + ligand systems.
• Tolerates a wide range of bases and solvents; select conditions to balance solubility, EHS, and temperature windows.
• Enables reduced catalyst loadings; evaluate ppm-level Pd for high-turnover substrates with rigorous exclusion of air/moisture in the reaction mixture.

Target Specificity

Not applicable. This is a small-molecule palladium precatalyst and has no biological target, antigen, or isotype characteristics. See Reaction & Applications for its chemical selectivity profile in cross-coupling chemistry.