Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, P. R. China.
J Am Chem Soc. 2012 Oct 17;134(41):16999-7002. doi: 10.1021/ja308419a. Epub 2012 Oct 3.
A stereoselective synthesis of enantiomerically enriched difluoromethyl tertiary alcohols by tuning the reactivity of difluoromethyl sulfoximines from electrophilic to nucleophilic difluoromethylating agents is reported. The key feature of this chemistry is the diastereoselective addition of the difluoromethyl sulfoximine to the prochiral carbon of the ketone. The present method was used to prepare enantiomerically enriched difluoromethyl secondary alcohols and difluorinated analogues of the natural products gossonorol and boivinian B, demonstrating the potency of the method.
本文报道了通过调节二氟甲基亚砜亚胺的反应性，将其从亲电型二氟甲基化试剂转变为亲核型试剂，从而实现对映体富集的二氟甲基叔醇的立体选择性合成。这种化学的关键特征是二氟甲基亚砜亚胺对酮的前手性碳的立体选择性加成。本方法用于制备对映体富集的二氟甲基仲醇和天然产物 gossonorol 和 boivinian B 的二氟化物类似物，证明了该方法的有效性。
