通过定向氨基化对非活化的催化性分子间碳胺化
Zhen Liu1, Yanyan Wang2, Zichen Wang1
1Department of Chemistry, The Scripps Research Institute , 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
一种新型的催化反应使得1,2-碳氨基酸的生成成为药品中价值的中间体. 这种方法利用导向组来控制选择性,并提供复杂分子的多功能途径.
科学领域:
- 有机化学
- 催化剂
- 医学化学
背景情况:
- 在有机合成中,开发有效的C-N键形成方法至关重要.
- 催化为复杂分子构建提供了强大的工具.
- 获取γ-氨基酸和γ-乳酸对药物发现很重要.
研究的目的:
- 开发一种新型的非激活基的分子间1,2-碳氨基化.
- 为此转化建立一个 (II) / (IV) 催化循环.
- 合成药物相关的γ-氨基酸和γ-乳酸的前体.
主要方法:
- 使用可分割的双标定定向组来控制区域选择性.
- 使用Pd (II) /Pd (IV) 催化循环来促进碳胺化.
- 优化反应条件,使其与多种基质兼容.
- 研究反应动力学并进行DFT计算以获得机械学见解.
主要成果:
- 已成功开发出非激活基的分子间1,2-碳氨基化.
- 使用指导组对区域选择性进行控制,防止β-化物排泄.
- 通过广泛的核友和碳电友实现中等至高产量.
- 产品很容易转化为γ-氨基酸和γ-乳酸.
结论:
- 开发的Pd (II) /Pd (IV) 催化系统为碳胺化提供了有效的途径.
- 引导集团战略是实现高选择性和收益的关键.
- 这种方法为重要的制药构件提供了有价值的合成途径.
更多相关视频
07:06A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
19:58Palladium N-Heterocyclic Carbene Complexes: Synthesis from Benzimidazolium Salts and Catalytic Activity in Carbon-carbon Bond-forming Reactions
Published on: July 30, 2017
相关概念视频
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
Amines to Alkenes: Hofmann Elimination
Under thermal conditions, the hydroxide can abstract a proton from the β carbon; this generates an alkene with the simultaneous...
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.
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.
α-Alkylation of Ketones via Enolate Ions
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
