酸的分子间和分子内,催化,无受体脱加的酸与酸和酸甲基C-H键的合
Naofumi Tsukada1, John F Hartwig
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
催化剂能够有效地将西兰与和中的C-H键进行分子间和分子内脱. 这些反应显示了对硬质可访问和电子贫乏位点的选择性,表明了潜在的不可逆转性.
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.
- 在C-H激活激活.
背景情况:
- C-H 键的功能化是现代合成化学的基石.
- 脱性合为C-Si键形成提供了原子经济的途径.
- 复合物是众所周知的各种有机转变的催化剂.
研究的目的:
- 为了研究白金复合物的催化活性在脱性合反应.
- 探索烯与烯的分子间合和C-H键的分子内合.
- 了解这些催化化的选择性和反应机制.
主要方法:
- 使用了TpMe2PtMe2H (hydridotris(3,5-dimethylpyrazolyl) 酸盐) 和相关 ((IV) 复合物的5mol%作为催化剂.
- 研究了三基 (三基和二基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基基
- 检查了dialkylsilylalkylarenes和silanes与和基C-H键的分子内反应.
主要成果:
- 通过与烯C-H键的西兰的分子间无受体脱性合,以及与烯和基C-H键的分子内合,获得了良好的产量.
- 观察到与的分子间反应有利于更少的固体阻碍和更多的电子贫困的C-H键.
- 已证明的分子内反应发生在基C-H键和形初级C-H键上,交叉实验表明不可逆转性.
结论:
- 催化剂系统对分子间和分子内脱基化都有效.
- 这些反应表现出基于C-H键的硬质和电子因子的区域选择性.
- 在某些条件下观察到的不可逆转性对合成策略和反应控制有影响.
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