基二金属催化酶选择性循环添加基基基
Qi-Sheng Liu1, De-Yin Wang1, Zhi-Jun Yang1
1State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University , Tianjin 300071, China.
一种新的双金属催化剂可实现反选择性循环添加反应. 这种方法有效地切割环C-C键,产生高纯度的有价值的环二胺.
科学领域:
- 有机金属化学
- 不对称的催化
- 有机合成
背景情况:
- 循环添加反应是有机合成的基础.
- 循环的C-C键激活仍然是一个挑战.
- 对于药物而言,选择性合成至关重要.
研究的目的:
- 使用环基胺和基形成一个反选择性循环添加反应.
- 探索 Ni-Al 双金属催化在 C-C 键裂解中的有用性.
- 合成具有高立体化学控制的新型环乙胺.
主要方法:
- 使用Ni-Al双金属催化剂系统.
- 使用双功能连接体来实现催化.
- 研究了环基和各种基之间的反应.
主要成果:
- 获得高产量的环烯基碳胺 (高达99%).
- 获得的产品具有优异的抗选择性 (高达94% ee).
- 证明了催化剂在分裂无反应环C-C键中的效率.
结论:
- Ni-Al双金属催化是一种强大的反选择性循环添加策略.
- 开发的方法可以获取有价值的奇拉环烯基碳胺.
- 双功能联体催化克服了环激活方面的挑战.
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相关概念视频
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
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.
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
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.
α-Alkylation of Ketones via Enolate Ions
