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Synthesis of Highly Functionalized 2-Pyranone from Silyl Ketene
ACS Omega ( IF 3.7 ) Pub Date : 2018-08-17 00:00:00 , DOI: 10.1021/acsomega.8b01531 Yuanhui Xiang 1 , Arnold. L. Rheingold 2 , Emily B. Pentzer 1
ACS Omega ( IF 3.7 ) Pub Date : 2018-08-17 00:00:00 , DOI: 10.1021/acsomega.8b01531 Yuanhui Xiang 1 , Arnold. L. Rheingold 2 , Emily B. Pentzer 1
Affiliation
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We report a highly functionalized 2-pyranone small molecule prepared from tert-butyl diphenyl silyl ketene using an alkoxide catalyst and thermally induced rearrangement. Treatment of the silyl ketene with a substoichiometric amount of alkoxide led to the formation of a trimer which was isolated and fully characterized; heating this trimer in a 1,4-dioxane solution induced a thermal rearrangement, yielding the product 2-pyranone. The isolated intermediate and product are characterized by 1D and 2D nuclear magnetic resonance (NMR) spectroscopies, mass spectrometry, and single crystal X-ray diffraction. A mechanism for the thermally induced rearrangement is proposed based on 1H NMR studies, and a rate law is derived from the proposed mechanism with steady-state approximation. This work illustrates a route for the formation of highly functionalized and modifiable 2-pyranone motifs with potential biological activity. The formation of the trimer, and thus the functionalized 2-pyranone, is highly dependent on the silyl substituents and alkoxide counterion and thus indicates the intriguing reactivity of highly functionalized small molecules.
中文翻译：
由甲硅烷基酮合成高官能度的2-吡喃酮
我们报道了使用醇盐催化剂和热诱导的重排，由叔丁基二苯基甲硅烷基乙烯酮制备的高度官能化的2-吡喃酮小分子。用亚化学计量的醇盐处理甲硅烷基烯酮导致三聚体的形成，将其分离并充分表征。在1，4-二恶烷溶液中加热该三聚体引起热重排，产生产物2-吡喃酮。分离出的中间体和产物的特征在于1D和2D核磁共振（NMR）光谱，质谱和单晶X射线衍射。提出了一种基于1的热诱导重排机制1 H NMR研究表明，速率定律是从所提出的稳态近似机理中推导出来的。这项工作说明了形成具有潜在生物活性的高度功能化和可修改的2-吡喃酮基序的途径。三聚体的形成以及由此官能化的2-吡喃酮的形成高度依赖于甲硅烷基取代基和醇盐抗衡离子，因此表明高度官能化的小分子具有令人着迷的反应性。
更新日期：2018-08-17
中文翻译：
由甲硅烷基酮合成高官能度的2-吡喃酮
我们报道了使用醇盐催化剂和热诱导的重排，由叔丁基二苯基甲硅烷基乙烯酮制备的高度官能化的2-吡喃酮小分子。用亚化学计量的醇盐处理甲硅烷基烯酮导致三聚体的形成，将其分离并充分表征。在1，4-二恶烷溶液中加热该三聚体引起热重排，产生产物2-吡喃酮。分离出的中间体和产物的特征在于1D和2D核磁共振（NMR）光谱，质谱和单晶X射线衍射。提出了一种基于1的热诱导重排机制1 H NMR研究表明，速率定律是从所提出的稳态近似机理中推导出来的。这项工作说明了形成具有潜在生物活性的高度功能化和可修改的2-吡喃酮基序的途径。三聚体的形成以及由此官能化的2-吡喃酮的形成高度依赖于甲硅烷基取代基和醇盐抗衡离子，因此表明高度官能化的小分子具有令人着迷的反应性。
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