二茂铁基三级醇的合成

Synthesis of Ferrocenel Tertiaryalcohol

将RMgCl(3倍量)和ZnCl_2(1倍量)混合原位生成高效亲核性烷基化试剂有机锌酸复合物,来对二茂铁基酮进行烷基化反应,制备二茂铁基三级醇。获得了对二茂铁基酮的高效烷基化结果,如i-PrMgCl与二茂铁基乙酮的烷基化产率从20%提高到91%,还原副产物产率相应从36%降低至0%。较烷基锂和格氏试剂,前者能够有效地进行二茂铁基酮的烷基化,该方法将成为非常好的通用烷基化方法,并为工业化大量生产二茂铁基三级醇探索了道路。

A highly efficient alkylation of ferrocenylketones with trial kylzinc （Ⅱ） ate complexes （R3ZnMgCl） was derived from Grignard reagents （3 equiv） and zinc chloride （ 1 equiv） in situ. The desired tertiary alcohols were obtained in much improved yields due to the minimization of background reactions. For instance,Tire isopropylation was conducted to ferrocenylethylketonc with i-PrMgBr,while the con-esponding alkylation products yields increased from 20% to 91% with the yields of the reduced byproducts significantly minimized from 36% to 0%. It is demonstrated that highly efficient alkylation to fcrrecenylketones via trialkylzinc（Ⅱ） ate reagents is more effective than Organolithi- um reagents and Grignard reagents and this alkylation system should be highly useful for both laboratory and industrial application.