超越竞争的水力功能化:不对称的基因的远程替代
Yi-Xiao Shen1,2, Chao Ma2, Guo-Qiang Lin1
1State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai 200032, China.
这项研究引入了一种新型的不对称的远程替代用/胺催化剂替代alkynes. 该方法实现了高选择性,为复杂分子提供了新的合成途径.
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:
- 基替代是一种基本反应,但通常需要与基相邻的离开组.
- 现有的方法在远程功能化方面面临范围和选择性的限制.
研究的目的:
- 开发了第一个不对称的远程替代基因与线性基连接的远程离开组.
- 为了在和化物的合中实现高的区域,几何和选择性.
主要方法:
- 协同作用的 (Pd) 和氨基催化.
- 使用修饰的二胺有机催化剂.
- 研究了反应机制,包括中间体形成和Pd氧化还原路径.
主要成果:
- 成功证明了对基因的不对称远程替代.
- 实现了高水平的区域,几何和enantioselectivity.
- 完全抑制了竞争中的水功能化反应.
- 通过扩展测试和衍生来验证协议.
结论:
- 开发的协议提供了一种可靠和有价值的远程alkyne功能化的新方法.
- 反应通过1,3-二烯中间体和复杂的Pd氧还原循环进行.
- 这项工作扩大了在不对称合成中基的合成实用性.
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相关概念视频
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.
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.
Preparation of Alcohols via Substitution Reactions
Alcohols can be synthesized from alkyl halides via nucleophilic substitution reactions. The highly polar carbon-halogen bond in the substrate makes halide a good leaving group. The hydroxide ion or water can act as a nucleophile to take the place of halide and form an alcohol. The substitution reactions occur via two different reaction pathways, SN1 or SN2, depending on the nature of carbon attached to the halide.
Primary alcohols are synthesized from primary alkyl halides, and the...
Electrophilic Addition to Alkynes: Hydrohalogenation
Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
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.
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.
