C-H 激活和质子转移启动 (IV) 氧复合物的基转化活动
Ka Wing Chan1, Erwin Lam1, Vincenza D'Anna2
1ETH Zürich , Department of Chemistry and Applied Biosciences , Vladimir Prelog Weg 1-5 , CH-8093 Zurich , Switzerland.
Journal of the American Chemical Society
|August 16, 2018
概括
(IV) 氧复合物激活了转化反应. 这一过程需要基C-H键,并涉及质子转移机制,产生活性.
科学领域:
- 有机金属化学
- 催化剂
- 有机合成
背景情况:
- 转化是有机合成中的一个重要反应.
- 高价值的基是已知的中间体.
- 低价值预催化剂的作用尚不清楚.
研究的目的:
- 研究低价值预催化剂的激活机制.
- 合成和描述新的 (IV) 氧复合物.
- 确定基转移的启动途径.
主要方法:
- 合成 (IV) 氧二甲氧化物复合物.
- 使用易斯酸激活 (B(C6F5) 3).
- 动力学研究,同位素标记和DFT计算.
主要成果:
- (IV) 氧复合物表现出高转化活性.
- 化C-H激活对于启动至关重要.
- 观察到一种主要的动态同位素效应.
- DFT的计算揭示了质子转移机制.
结论:
- (IV) 氧复合物作为转化物的有效前催化剂.
- 启动涉及基C-H键激活和易斯酸/基辅助的质子转移.
- 这种机制产生了活性.
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