Heck反应及金属催化偶联反应.pptVIP

分子内Heck反应化生成环外双键 A stirred solution of 1, triethylmine and catalytic tetrakispalladium(0) in 2.4 mL of acetonitrile was heated at 80 ℃ in a sealed tube under an argon atmosphere for 10 h. The reaction mixture turned dark orange after ca10 minand the catalyst plated out on the walls of the tube as a shiny layer of palladium metal upon completion of the reactionThe reaction mixture was cooled to room temperaturethe reaction was quenched with aqueous NaHCO3andthe mixture was extracted with EtOAc The organic extracts were washed with aqueous NaHSO3 water and brine and dried over MgSO4 Filtrationconcentrationand purification of the orange residue by flash column chromatography gave 66mg of19 as acolorless solidmp 193-194 ℃Rf = 0.29 2.2 形成季碳中心的反应 从20世纪80年代早期研究以来得到了广泛的应用。1989年，Shibasaki 和Overman 首先报道不对称Heck反应。 J.Org.Chem. 1989, 54, 4738 同一年，Overman及其工作组首先利用Heck 反应合成了手性季碳原子。 J.Org.Chem.1989,54,5846 像天然产物physostigmine的合成，成功的运用和Heck反应构成手性的季碳中心。 Matsuura, T.; Overman, L.E. J.Am.Chem.Soc. 1998, 120, 6500 2.2.1 分子内不对称Heck反应 A mixture of Pd2(dba)3·CHCl3 (360 mg, 0.347 mol), (s)-BINAP (504 mg, 0.809 mol), and N,N-dimethylacetamide (DMA, 21 mL) was stirred at room temperature for 65 min. To the resulting orange solution was added a solution of compound 1 (1.82 g, 3.51 mol), 1,2,2,6,6-pentamethylpiperidine (3.2 mL, 18 mmol), and DMA (18 mL), and the reaction was heated at 100 ℃ for 90 min. The result dark solution was poured into half-saturated aqueous NaHCO3 (100 mL) and extracted with ether (3 × 150 mL). The combined organic extracts were washed with brine (100 mL), dried (MgSO4), and concentrated, and the residue was purified by sgc (9:1 → 1:1 hexane-EtOAc) to give oxindole enoxysilane compound 2 (1.29 g, 94%) as a 98:2 mixture of geometric isomers: [α]25D –81o (c 0.61 C6H6). 2.3 多烯大环的合成 分子内Heck反应形成的多烯大环化合物(大于13)。Zeigler就利用Heck反应成功合成十六元环的大环多烯化合物 Zeigler, F. Tetrahedron, 1981, 37, 4035 也有多烯经过多次分子内Heck反应，一步构建多个碳碳键和多元环。Overman 就成功应用Heck反应一步构建了二个环和二个季碳中心