通过Ru-催化添加合成1,1-非替代基
B M Trost1, A B Pinkerton, F D Toste
1Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
Journal of the American Chemical Society
|December 14, 2001
概括
复合物催化了基对基的添加,为1,1-异位基提供了一个原子经济的途径. 这种新的方法在温和条件下实现了高区域选择性和化学选择性.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 合成1,1-非替代的传统化协议往往受到原子经济不佳的影响.
- 开发原子经济战略对于可持续的化学合成至关重要.
研究的目的:
- 探索以为催化剂添加终端基因到基因作为一个原子经济合成策略.
- 为了发现新的复合物,可以有效地催化这种转变.
主要方法:
- 复合物的选用于基-基添加.
- 反应条件的优化,包括温度,溶剂和催化剂负载.
- 反应产品的表征和机理学研究.
主要成果:
- 鉴定出了两种新型的复合物,即环二烯 (三) 硫酸盐和环二烯三 (酸) 六酸.
- 在环境温度下,反应在乙或DMF中有效地进行.
- 观察到高区域选择性 (9:1至>25:1) 对1,1-非置换和优秀的化学选择性,耐受各种功能组.
结论:
- 开发的催化反应为合成1,1-异位提供了一种原子经济且高度选择性的方法.
- 该机制可能涉及一种可逆的金属cyclopentene中间体,其化学和区域选择性由动力和热力学因素决定.
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