金属参与的现代有机合成反应(麻生明)课件-Class No. 5.pptVIP

?5.4 p-烯丙基钯接受亲核进攻反应中的立体化学 ? ? ? 5.5 p-烯丙基钯中间体的不对称亲核取代反应 ? ? ? ? ee 99% (R) 40% (S) NR 反应条件: (i) 0.25 mol% [?3-C3H5PdCl]2, 0.75% mol% cyclohexyl ligand, 1.2equiv. TMSN3, THF, 0 oC; (ii) (CH3)3P, 2:1 THF-H2O, 1.2 equiv. (CH3)3P, rt then add (t-C4H9OCO)2O, NEt3. (b) K2CO3, CH3OH, rt then Dess-Martin periodinane, CH2Cl2, rt (c) Br2, NEt3, CH2Cl2, 0 oC. (d) 2.5 mol% Pd(dba)3.CHCl3, 15 mol% AsPh3, THF, 55 oC. (e) K-selectride, THF, -78 oC to 0 oC then cat. DBU, THF. (f) NaBH4, CH3OH, 0 oC. (g) CH3SO2Cl, NEt3, CH2Cl2, 0 oC; CF3COOH, H2O, rt; CH3CN, reflux. ? ? ?5.6 其它h3-烯丙基金属1/3-位碳接受