テトラキス(トリフェニルホスフィン)パラジウム(0) 化学特性,用途語,生産方法
外観
黄色～黄緑色, 結晶～粉末
溶解性
ジクロロメタンに溶ける。
用途
触媒。
用途
Pd(PPh3)4 はカップリング反応の触媒として広く用いられる。優れた反応例として溝呂木?ヘック反応や薗頭萩原反応、右田小杉スティル反応、鈴木宮浦反応が挙げられる。これらの反応は、芳香族ハロゲン化物の0価パラジウムへの酸化的付加により反応が始まる。
使用上の注意
アルゴン封入
化学的特性
Tetrakis(triphenylphosphine)palladium, commonly abbreviated as Pd(PPh₃)₄ or PdP₄, is a bright yellow crystalline solid that gradually darkens to brown upon exposure to air. It is sparingly soluble in saturated hydrocarbons but readily soluble in a variety of organic solvents, including chloroform (CHCl₃), dimethoxyethane (DME), tetrahydrofuran (THF), dimethylformamide (DMF), benzene, and toluene.
使用
Tetrakis(triphenylphosphine)palladium(0) is widely used as a catalyst for palladium-catalyzed coupling reactions.
主な応用
Palladium-Catalyzed Three-Component Reaction for the Synthesis of Imidazolidinones.
Once the Schlenk tube containing K2CO3 (55 mg, 0.40 mmol) is flamed, dried, and filled with argon, Tetrakis(triphenylphosphine)palladium (12 mg, 0.010 mmol), PMB-protected 2,3-allenylamine (37 mg, 0.20 mmol), iodobenzene (58 mg, 0.28 mmol), phenyl isocyanate (36 mg, 0.30 mmol), and CH3CN (4 mL) are added sequentially. The resulting solution is heated to and stirred at 70°C. When the reaction is completed as monitored by TLC, the solvent is evaporated under reduced pressure, and the residue is purified by chromatography on silica gel (petroleum ether : ethyl acetate = 7:1) to afford the corresponding imidazolidione (72 mg, Y. 96%) as an oil.
反応性
- Catalyst for Suzuki coupling of chiral secondary organoboronic esters.
- Palladium-catalyzed SNAr reactions for the synthesis of heteroaryl ethers.
- Catalyst for cross-coupling of a-diazocarbonyl compouns with arylboronic acids.
- Diastereoselective synthesis of trans-1,2-diazetidines.
- Palladium-catalyzed alkynyl iminium ion cyclization.
- Widely used reagent in a variety of transformations including Heck arylation, enyne and diyne cycloisomerization.
- Catalysts for cross-coupling.
貯蔵
Tetrakis(triphenylphosphine)palladium(0) is sensitive to light and air and should be stored under an inert atmosphere, protected from light. During use, it may be handled in air for short periods; however, it is preferable to perform the procedure under a nitrogen or argon atmosphere using vacuum-line techniques.
純化方法
The palladium complex is recrystallised from EtOH. It should not be heated excessively as it dissociates to Pd(PPh3)3 and PdPh3 and then further to Pd(PPh3)2 and PPh3. It is also air sensitive as PPh3 is oxidized to PPh3O. It is stable only for short periods because on exposure to heat or air it turns from yellow to orange and dissociates in solution so the solutions should be used directly. However it can always be prepared freshly by mixing Pd(NO3)2 (2mmols) and PPh3(2mmols) in hot *C6H6 when vigorous evolution of nitric oxide occurs and a solid mass separates. This is collected and crystallised from EtOH. Its cryoscopic constant in *C6H6 (at 0.601g/20mL) corresponds to M 1156 [Malatesta & Angoletti J Chem Soc 1186 1957]. It is a useful catalyst for Suzuki coupling reactions [Trost Tetrahedron 33 2615 1977]. [Beilstein 16 IV 954.] This palladium catalyst bound to a polymer support (~0.06mmol/g) is also commercially available [cf Fenger & LeDrain Tetrahedron Lett 39 4287 1998]. [Beilstein 16 IV 954.]
テトラキス(トリフェニルホスフィン)パラジウム(0) 上流と下流の製品情報
原材料
準備製品