¡¾²Ô²¹³¾±ð¡¿»å¾±³¦³ó±ô´Ç°ù´Ç°Ú1,1′-²ú¾±²õ(»å¾±±è³ó±ð²Ô²â±ô±è³ó´Ç²õ±è³ó¾±²Ô´Ç)´Ú±ð°ù°ù´Ç³¦±ð²Ô±ð±Õ±è²¹±ô±ô²¹»å¾±³Ü³¾(¾±¾±),
??????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.
¡¾note¡¿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 reagent (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]. ¡¾kumada 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¡ªproperties, preparation and reactions”, edited by hu yuefei and others