((I) 催化取消双环[1.1.0]替代的二氨酸和二氨酸
Matteo Borgini1,2, Qi-Nan Huang3,4, Pan-Pan Chen3
1Department of Chemistry, University of Pittsburgh, Pittsburgh Pennsylvania 15260, United States.
Journal of the American Chemical Society
|May 20, 2024
概括
研究人员使用催化重新排列合成了新的双环[1.1.0]链异环. 这种方法有效地创建复杂的桥梁异环基架,具有广泛的功能组耐受性,用于药物发现.
科学领域:
- 有机化学
- 医学化学
- 催化剂
背景情况:
- 双环[1.1.0]化合物具有独特的反应性和释放应变的特性.
- 这些化合物为药物发现提供了新的支架.
- 开发高效的合成路径以实现功能化的bicyclo[1.1.0]butanes至关重要.
研究的目的:
- 合成新的双环[1.1.0]链异环.
- 开发一种 (I) 催化式的无序重组,以创建桥接的异环.
- 探索新型异环架的后续功能化.
主要方法:
- 核性添加双环[1.1.0]离子到8-异或离子.
- (I) 催化式的双环[1.1.0]布坦的重组.
- 在产生的支架上功能组的化学和立体选择性转换.
- DFT计算以阐明反应机制.
主要成果:
- 成功合成新型双环[1.1.0]链异环.
- 在催化重新排列到桥接 heterocycles 的高区域选择性.
- 这一过程显示出广泛的功能群耐受性.
- 通过随后的转换生成多种异环构件.
- DFT的计算支持了涉及碳化物和金属环中间体的建议反应途径.
结论:
- 已经建立了一个新的和高效的合成策略,用于含有双循环[1.1.0]的桥接 heterocycles.
- 开发的方法提供了一个多功能平台,用于产生药物发现的多种异环结构.
- 这项研究强调了应变释放反应和过渡金属催化在构建复杂分子结构中的有用性.
相关概念视频
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation
2.2K
Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.2K
Electrophilic 1,2- and 1,4-Addition of X2 to 1,3-Butadiene
2.4K
Electrophilic addition of halogens to alkenes proceeds via a cyclic halonium ion to form a 1,2-dihalide or a vicinal dihalide.
2.4K
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
1.9K
Arenediazonium substitution reactions occur when the diazonium group is substituted by various functional groups such as halides, hydroxyl, nitrile, etc. For instance, arenediazonium salts react with copper(I) salts of chloride, bromide, or cyanide to form corresponding aryl chlorides, bromides, and nitriles. These reactions are named Sandmeyer reactions. Although the mechanism of this reaction is complicated, as illustrated in Figure 1, they are believed to progress via an aryl copper...
1.9K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
4.6K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
4.6K
Nucleophilic Aromatic Substitution of Aryldiazonium Salts: Aromatic SN1
2.1K
Treating arylamines with nitrous acid gives aryldiazonium salts that are effective substrates in nucleophilic aromatic substitution reactions. The diazonio group in these salts can be easily displaced by different nucleophiles, yielding a wide variety of substituted benzenes. The leaving group departs as nitrogen gas, and this easy elimination is the driving force for the substitution reaction.
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
In the Sandmeyer reaction, for example, the diazonio group is replaced by a chloro, bromo,...
2.1K
Nucleophilic Aromatic Substitution: Elimination–Addition
4.0K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
4.0K

![Cercosporin-Photocatalyzed [4+1]- and [4+2]-Annulations of Azoalkenes Under Mild Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F60786.jpg&w=3840&q=50)
