双功能性连接体使金催化Propargyl通过反应性黄金Allenylidene中间体实现C-H功能化
Yongliang Wei1,2, Jingxing Jiang3, Yaru Jing3
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106, USA.
Angewandte Chemie (International ed. in English)
|April 25, 2024
概括
这项研究引入了一种新的黄金催化反应,使用基二醇来制造有价值的利二烯中间体. 这种方法使反应性得以扩大,用各种核爱素取代propargylic质子,以实现多功能合成.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 合成有机化学 合成有机化学
背景情况:
- 黄金利烯物种是催化过程中未被充分研究的反应中间体.
- 基二醇为产生这些中间体提供了一种新的基质类.
研究的目的:
- 开发一种催化方法,用于获取黄金利二烯中间体.
- 为了证明这些中间体与各种核友的电友反应性.
- 为了实现在propargylic位置的反应性,umpolung.
主要方法:
- 使用阿尔基尼尔二多醇作为基质.
- 使用双功能WangPhos作为黄金配体.
- 利用黄金催化剂用于中间生成和反应.
- 密度函数理论 (DFT) 计算用于机械学研究.
主要成果:
- 具有一般替代模式的金利丁中间体的催化生成.
- 在γ-碳中心与N/O/C核友的电友反应的演示.
- 成功地替换了propargylic质子,实现了反应性.
- 在WangPhos中确定一种弱Brønsted基胺为有效的propargylicdeprotonation.
结论:
- 开发的黄金催化反应可以轻松获得多用途的乙烯中间体.
- 反应机制涉及轻微的propargylicdeprotonation,由金-合金合作促进.
- 一个带有胺基的双功能连接体使得高效的去质子化成为可能,与以前的方法形成鲜明对比.
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