合成应用该方法可以以一锅法的方式进行,直接使用饱和羰基化合物作为起始材料,这将大大提高开发的转化的合成实用性。使用THF作为硅醇醚形成步骤的溶剂,以及在随后的脱氢步骤中使用THF:丙酮=1:9的溶剂混合物,酮1d''得到了所需的产品2d,产率为51%。同样,也展示了脂肪族酮1c''的直接脱氢。使用相同的条件,醛1k''产生了相应的脱氢产物2k,分离产量为48%。此外,通过使用1n'',展示了一锅法脱氢内酯的可能性,得到了产品2n,分离产量为60%。成功的关键是实施THF作为反应溶剂,因为它既与烯醇磷酸酯形成兼容,也与随后的氧化步骤兼容,同时使用增加的PIFA量,并实施KTFA作为碱。通过类似的策略,内酰胺1r''的脱氢也以一锅法进行,得到了脱氢内酰胺2r。这些结果具有相当的合成重要性,因为无过渡金属的内酯和内酰胺脱氢方法很少。图片来源:Chem. Commun.最后,对肉桂醛(2k)进行了克级规模(14.0 mmol起始材料;方案3B)的反应,得到了所需的产品,分离产量为73%,与1 mmol规模的结果相同。图片来源:Chem. Commun.总之,该方法是一种操作上简单的羰基脱氢方法,补充了已经存在的用于形成α,β-不饱和酮、醛、内酯和内酰胺的方法,使用在基本条件下可用的碘(III)氧化剂。实验操作General procedure C for the dehydrogenation of silyl enol ethers A round bottom flask equipped with a magnetic stir bar was charged with the indicated silyl enol
ether (1 mmol), which was dissolved in acetone (0.125 M with respect to the staring material).
The flask was cooled to 0 °C in an ice-water bath. Subsequently, NaOAc (160 mg, 2.00 mmol, 2.0
equiv.) was added, followed by the addition of PIFA (860 mg, 2.00 mmol, 2.0 equiv.) in one
portion. After 10 minutes at 0 °C, the reaction mixture was warmed to room temperature and
was stirred for additional 30 minutes at room temperature. The mixture was then concentrated
under reduced pressure, and purified by flash column chromatography. General procedure D for the desaturation of enol phosphates A round bottom flask equipped with a magnetic stir bar was charged with the indicated enol
phosphate (1 mmol), which was dissolved in the appropriate solvent (0.125 M with respect to
the starting material; in acetone for the enol phosphates of lactones, in acetonitrile for the enol
phosphates of lactams). The flask was cooled to 0 °C in an ice-water bath. Subsequently, NaOAc
(160 mg, 2.00 mmol, 2.0 equiv.) was added, followed by the addition of PIFA (860 mg, 2.00 mmol,
2.0 equiv.) in one portion. After 10 minutes at 0 °C, the reaction mixture was warmed to room
temperature and was stirred for additional 30 minutes at room temperature. The mixture was
then concentrated under reduced pressure, and purified by flash column chromatography.