α,β‐Unsaturated carbonyl groups are found in many natural products and functional molecules. The reactivity of nucleophiles towards α,β‐unsaturated carbonyls, such as β‐monosubstituted and disubstituted α,β‐unsaturated ketones (enones) and ynones, is similar. Therefore, the development of a method to selectively convert α,β‐unsaturated carbonyls is desirable. In this study, selective one‐pot reductions and allylations of β‐disubstituted enones or ynones were accomplished in the presence of β‐monosubstituted enones using an in situ protection methodology. β‐Monosubstituted enones selectively reacted with a combination of triphenylphosphine and trimethylsilyl triflate in the presence of β‐disubstituted enones or ynones to produce phosphonium silyl enol ethers, which acted as enone protecting groups during the reduction and allylation of the remaining β‐disubstituted enone or ynone. The substrate was then easily deprotected in the workup to regenerate the parent enone.

中文翻译：

---

β-单取代的烯酮存在下β-双取代的烯酮和壬酮的选择性转化

在许多天然产物和功能分子中都发现有α，β-不饱和羰基。亲核试剂对α，β-不饱和羰基的反应性相似，例如β-单取代和二取代的α，β-不饱和酮（烯酮）和炔酮。因此，需要开发一种选择性转化α，β-不饱和羰基的方法。在这项研究中，使用原位保护方法，在β-单取代的烯酮存在下，选择性地一锅还原和β-二取代的烯酮或炔酮的烯丙基化。β-单取代的烯酮在β-二取代的烯酮或炔酮的存在下与三苯基膦和三氟甲磺酸三甲基甲硅烷基酯选择性反应生成磷鎓甲硅烷基烯醇醚，在剩余的β-二取代的烯酮或炔酮的还原和烯丙基化过程中充当烯酮保护基团。然后在后处理中容易地将底物脱保护以再生母体烯酮。