合并环开放的1,2-金属酸转移与不对称的C) -H亚齐里丁的玻里化
Bai-Lin Wang1,2, Hongliang Zhao1,3, Xing-Wang Wang2
1State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, China.
Journal of the American Chemical Society
|July 5, 2024
概括
通过四元立体中心合成奇拉胺具有挑战性. 这项研究引入了一种使用催化亚齐里丁的新方法,使得高效的非对称合成和化物的总合成成为可能.
科学领域:
- 有机化学
- 不对称的合成
- 催化剂
背景情况:
- 在药物和天然产品中,二次胺与邻近四级立体中心至关重要.
- 它们的不对称合成在有机化学中提出了重大挑战.
研究的目的:
- 开发一种新且高效的方法,用于与邻近四级立体中心的奇拉二次胺的不对称合成.
- 通过复杂的自然产品的总合成来证明开发方法的实用性.
主要方法:
- 合并环开放的1,2-金属酸转移与催化C ((sp3) -H化亚齐里丁.
- 在合成应用中利用下游转化.
主要成果:
- 成功地提供具有高反选择性的奇拉氨基基框架.
- 通过Amaryllidaceae的 (-) -crinane和 (+) -mesmebrane类的总合成证明了合成效用.
结论:
- 开发的方法提供了一种有效的途径,可以通过邻近四分位式立体中心对二次氨酸进行酶丰富.
- 这种方法为复杂分子的合成提供了有价值的工具,包括药物相关的天然产品.
相关概念视频
Regioselectivity and Stereochemistry of Hydroboration
8.1K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
8.1K
Acid-Catalyzed Ring-Opening of Epoxides
7.2K
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
7.2K
Preparation of 1° Amines: Azide Synthesis
3.9K
Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...
3.9K
Base-Catalyzed Ring-Opening of Epoxides
8.4K
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
8.4K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
6.0K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.0K
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
2.7K
The Cope rearrangement is classified as a [3,3] sigmatropic shift in 1,5-dienes, leading to a more stable, isomeric 1,5-diene. The reaction involves a concerted movement of six electrons, four from two π bonds and two from a σ bond, via an energetically favorable chair-like transition state.
2.7K


