帕拉复合物催化了用乙烯基和乙烯基酸的基 Ester 的化
1Catalysis Research Center and Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0811, Japan.
Journal of the American Chemical Society
|October 25, 2001
概括
催化过的酸乙与酸乙的酸乙化选择性地产生β,gamma不和基. 性三乙酸盐是最佳基质,三甲基基团捕获了三乙酸盐离开组.
科学领域:
- 有机化学 有机化学
- 有机金属化学 有机金属化学
背景情况:
- 乙基化反应是有机合成的基础.
- 开发选择性和高效的催化方法来形成C-C键是至关重要的.
研究的目的:
- 报道了一种新型的催化化的化使用acylsilanes.
- 研究离开组对反应效率和选择性的影响.
主要方法:
- 使用复合物的催化化,特别是 [Pd(eta3-C6H5CH=CHCH2) ]2 (4a).
- 使用乙基作为乙化剂.
- 使用29Si NMR光谱分析反应产物和中间体.
- 密度函数理论 (DFT) 计算以阐明反应机制.
主要成果:
- 在高产量中选择性形成β,gamma不和子.
- 与酸盐和三酸盐相比,酸三酸盐的反应性更强.
- 证实了三甲基三乙酸盐的形成,表明有效地捕捉了离开的群体.
- DFT的计算表明,乙基HOMO和介质LUMO之间存在关键的相互作用.
结论:
- 开发的催化反应为β,不和子提供了一条有效的途径.
- 在基上选择离开组对于成功的乙化是至关重要的.
- 催化系统有效地利用了乙基,并强调了三乙酸离开组对于高产量的重要性.
相关概念视频
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Esters to β-Ketoesters: Claisen Condensation Mechanism
Regular Claisen condensation involves the synthesis of β-ketoesters by combining identical ester molecules bearing two α hydrogens in the presence of an alkoxide base. The reaction commences with the deprotonation of the acidic α hydrogen by the base to form a resonance stabilized ester enolate. This nucleophilic ion then attacks the carbonyl center of another ester molecule to generate a tetrahedral alkoxide intermediate. Next, the expulsion of the alkoxide group from the intermediate restores...
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