Commonly used catalysts—-Pd(dppf)Cl2_Kain Industrial Additive

【Name】Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II),
​​​​​​Dichloro[1,1′-bis(diphenylphosphine)ferrocene]palladium

[Molecular formula] C34H28Cl2FeP2Pd

[Molecular weight] 731.72

[CA registration number][72287-26-4]

[Abbreviation and alias] PdCl2(dppf)

[Physical properties] Reddish brown solid, mp 265~268oC. Soluble in ether, THF and benzene.

[Preparation and commercial products] PdCl2 (dppf) has been commercialized and is sold by major reagent companies.

【Note】This reagent is irritating and should be stored in an inert atmosphere.

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PdCl2 (dppf) is mainly used as a catalyst to catalyze cross-coupling reactions.

Similar to other Pd(II) and Ni(II) complexes, PdCl2(dppf) can effectively catalyze the cross-coupling reaction between halogenated alkenes, halogenated arenes or triflate aromatics and Grignard reagents. Achieve the formation of carbon-carbon bonds. Vinyl bromide and s-BuMgCl can react completely under the catalysis of PdCl2 (dppf) to obtain the coupling product (Formula 1)[1], but using other Pd catalysts will lead to isomeric products and reduction by-products.

Although ordinary Pd catalysts do not have the ability to activate organic sulfur compounds, PdCl2 (dppf) can realize the cross-coupling reaction between methyl sulfide and aryl Grignard reagents (Formula 2)[2]. Bromothiophene and thiophene Grignard reagent can obtain photosensitive trithiophene compounds under the catalysis of PdCl2 (dppf), and the methyl sulfide substituent in the substrate will not react (Formula 3) [3]. 【Kumada coupling reaction】

PdCl2(dppf) was also found to catalyze the iodine-zinc exchange reaction to obtain the intramolecular carbon zincation reaction of alkenes (Equation 4)[4].

PdCl2 (dppf) reagent can also catalyze Stille reaction and Suzuki reaction, such as the cross-coupling reaction between vinyl tin and aryl trifluoromethanesulfonic acid to obtain an intramolecular cyclization product (Formula 5) [5] , or a cross-coupling reaction between aryltin and aryltrifluoromethanesulfonic acid in a CO atmosphere to obtain an aryl ketone compound (Formula 6) [6]. [Examples of preparation of carboxylic acids and their derivatives by carbonyl insertion reaction]

PdCl2 (dppf) can also be used in the hydroesterification reaction of trimethylsilyl alkyne to obtain conjugated vinyl silicon compounds (Formula 7) [7].

References

1. (a) Hayashi, T.; Konishi, M.; Kumada, M. Tetrahedron Lett., 1979, 1871. (b) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.; Hirotsu, K. J. Am. Chem. Soc., 1984, 106,158.
2. Pridgen, L. N.; Killmer, L. B. J. Org. Chem., 1981, 46, 5402.
3. (a) Rossi, R.; Carpita, A.; Ciofalo, M.; Lippolis, V. Tetrahedron, 1991, 47, 8443. (b) Carpita, A.; Rossi, R.;Veracini, C. A. Tetrahedron, 1985, 41, 1919.
4. Stadtmuller, H.; Lentz, R.; Tucker, C. E.; Studeman, T.;Dorner, W.; Knochel, P. J. Am. Chem. Soc., 1993, 115, 7027.
5. Luo, F.-T.; Wang, R.-T. Tetrahedron Lett., 1991, 32, 7703.
6. Echavarren, A. M.; Stille, J. K. J. Am. Chem. Soc., 1988, 110,1557.
7. Takauchi, R.; Sugiura, M.; Ishii, N.; Sato, N. Chem. Commun.,1992, 1358.
Reprinted from: “Modern Organic Synthesis Reagents—Properties, Preparation and Reactions”, edited by Hu Yuefei and others