机械研究金 (((I) 催化分子间胺化Allenes的机理研究
Z Jane Wang1, Diego Benitez, Ekaterina Tkatchouk
1Department of Chemistry, University of California, Berkeley, California 94720, USA.
Journal of the American Chemical Society
|August 27, 2010
概括
黄金催化使得用化物有效的分子间氨基化. 机理学研究揭示了黄金 (I) 催化剂和外部球体机制,电子缺陷连接物加速反应.
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.
- 有机合成 有机合成
背景情况:
- 烯的分子间胺化是一种有价值的合成转化.
- 黄金催化为C-H和C-N键形成提供了独特的反应性.
- 了解反应机制对于催化剂优化至关重要.
研究的目的:
- 用黄金复合物催化的化核来阐明烯分子间胺化机制.
- 为了识别活跃的黄金催化剂物种并确定动力参数.
- 为了研究联体电子对催化活性的影响.
主要方法:
- 详细的机械学研究,包括动力学实验.
- 研究催化剂静止状态和反应顺序.
- 计算研究以支持拟议的机制.
- 在黄金催化剂上有不同的素连接体.
主要成果:
- 反应很容易发生在3-12%的Ph(3) PAuNTf(2) 和化物核友基中.
- 这种反应在黄金和艾伦中是第一阶的,在核爱中是零阶的.
- 活性催化剂是单金 (I),速度限制的过渡状态不涉及核爱者.
- 计算研究表明有一个外层球体,没有中间体的两步机制.
- 更多缺乏电子的素连接体加快了反应.
结论:
- 黄金催化用化与化的化遵循一个外球机制.
- 催化剂活性由联结体电子调节,电子缺乏联结体提高性能.
- 这项研究为开发用于胺化反应的改进黄金催化剂提供了关键的机制见解.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Reduction of Alkenes: Catalytic Hydrogenation
Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the surface of...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Introduction
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.


