有机锌试剂倾向于和过渡金属作用而发生转金属化反应,所生成的这些过渡金属中间体有着很高的活性,从而可以与很多亲电试剂高效地进行反应,在有机合成中占有非常重要的地位.通常制备锌试剂的方法是锌粉对卤代烃的插入反应,但是这种方法制备的锌试剂的合成效率往往不高,对一些敏感的基团的耐受性不太强.在无机盐氯化锂存在下能有效地制备KNOCHEL锌试剂,报道一种大剂量方式(100 mmol)制备KNOCHEL锌试剂的方法 ,该法能高效高选择性地制备有机锌试剂,生成的锌试剂产率高(80%~91%),稳定性强,该试剂对各种敏感的官能团(如酯基、氰基、羰基、三氟甲基)的耐受性强.这些锌试剂在氩气保护下存放1个星期后,其活性没有明显降低.
Organic zinc reagents play very important roles in organic synthesis, since they are tending to transmetallation with other transition metals, which posses high reactivities and can be quenched easily with many electrophiles. The traditional preparation of organic zinc reagents is using the zinc insertion reaction of halogen hydrocarbons, which sometimes shows low yield, and the prepared zinc reagents could not be tolerated with very sensitive functional groups. A practical synthetic procedure for KNOCHEL type zinc reagents in large scale(100 mmol)is reported. With the addition of Li Cl, the zinc reagents can be prepared with high yields(80%-91%), the prepared KNOCHEL type zinc reagents show good tolerance to very sensitive functional groups, such as ester group, cyano group, carbonyl group and trifluoromethyl group etc. Under argon storage, the reactivity of KNOCHEL type zinc reagents does not decrease obviously after one week.