盐稳定基基酸盐:可用于催化选择性1,2-二甲基化的一种多功能试剂
Jie Lin1, Kaixin Chen1, Jixin Wang1
1Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University Suzhou 215123 China jjackli@suda.edu.cn.
Chemical science
|August 18, 2023
概括
研究人员开发了稳定,固体的基基酸盐,以增强Csp3-Csp3键形成. 这一突破通过催化二基化-化反应改善了药品和农业化学品的合成.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 有机金属化学 有机金属化学
背景情况:
- 在制药和农业化学品中,Negishi型反应对Csp3-Csp3键构造至关重要.
- 传统的化是对空气/水分敏感的,这限制了它们在交叉合反应中的反应性和普遍性.
研究的目的:
- 开发用于改善Csp3-Csp3键形成的新型稳定基试剂.
- 使用这些新试剂建立催化二基化-基化协议.
主要方法:
- 通过OPiv协调制备固体,盐稳定性基基酸盐.
- 使用新型基试剂,用催化二醇基化-二酸盐的基化.
- 动力学研究以了解OPiv调节对反应性的作用.
主要成果:
- 与传统试剂相比,新的基基酸盐具有更高的稳定性和反应性.
- 成功的模块化和选址安装CF2和Csp3组通过双键以立体的方式.
- 在温和条件下观察到广泛的基质范围和功能组兼容性.
结论:
- 固体,盐稳定性基基酸盐代表了Csp3-Csp3交叉合化学的重大进步.
- 开发的催化协议为合成复杂的化分子和修改生物活性化合物提供了一种多功能方法.
相关概念视频
Acid Halides to Ketones: Gilman Reagent
3.0K
Lithium dialkyl cuprate, also known as Gilman reagents, selectively reduces acid halides to ketones. The acid chloride is treated with Gilman reagent at −78 °C in the presence of ether solution to produce a ketone in good yield.
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
As shown below, the mechanism proceeds in two steps. First, one of the alkyl groups of the reagent acts as a nucleophile and attacks the acyl carbon of the acid chloride to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen...
3.0K
Aldehydes and Ketones to Alkenes: Wittig Reaction Overview
7.9K
The Wittig reaction is the conversion of carbonyl compounds-aldehydes and ketones-to alkenes using phosphorus ylides, or the Wittig reagent. The reaction was pioneered by Prof. Georg Wittig, for which he was awarded the Nobel Prize in Chemistry.
7.9K
Vicinal Diols via Reductive Coupling of Aldehydes or Ketones: Pinacol Coupling Overview
1.8K
Wilhelm Rudolph Fittig discovered the pinacol coupling reaction in 1859. It is a radical dimerization reaction and involves the reductive coupling of aldehydes or ketones in the presence of hydrocarbon solvent to yield vicinal diols.
1.8K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.9K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.9K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
7.8K
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.
7.8K
E1 Reaction: Stereochemistry and Regiochemistry
9.7K
One of the critical aspects of the E1 reaction mechanism, as also observed in E2, is the regiochemistry, with multiple regioisomers obtained as products. In the example discussed, the presence of water as a weak base favors elimination over substitution to generate two alkenes. Given that alkenes’ stability increases with the number of alkyl groups across the double bond, typically, E1 reactions lead to the Zaitsev product, for this is more substituted and stable than the Hofmann product.
9.7K


