Department of Medicinal Chemistry and Molecular Pharmacology, Purdue University, West Lafayette, Indiana 47907, United States.
J Org Chem. 2011 Nov 4;76(21):9163-8. doi: 10.1021/jo2017179. Epub 2011 Oct 13.
Three series of α-halo-α,α-difluoromethyl ketones are prepared from highly α-fluorinated gem-diols by exploiting the facile release of trifluoroacetate, followed by immediate trapping of the liberated α,α-difluoroenolate with an electrophilic chlorine, bromine, or iodine source. The products are typically isolated in good yields, even in the case of sensitive, α-iodo-α,α-difluoromethyl ketones. Also, we demonstrate that an α-iodo-α,α-difluoromethyl ketone will participate in a copper-promoted reaction to forge a new carbon-carbon bond.
三系列的α-卤代-α，α-二氟甲基酮是由高度α-氟化偕二醇制备的，通过利用三氟乙酸盐的易释放性，然后用亲电氯、溴或碘源立即捕获释放的α，α-二氟烯醇盐。即使是敏感的α-碘代-α，α-二氟甲基酮，产物通常也能以良好的收率分离。此外，我们证明α-碘代-α，α-二氟甲基酮将参与铜促进的反应，形成新的碳-碳键。
