位置选择性催化:朝着1,2-二醇的不同区域分辨率的方向
Amanda D Worthy1, Xixi Sun, Kian L Tan
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Journal of the American Chemical Society
|April 21, 2012
概括
本研究展示了一种使用有机催化剂在1,2-二醇中选择性修改二次基的新方法. 这种方法可以有效的动力分辨的racemic混合物,产生一个步骤的丰富产品.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 立体化学是一种立体化学.
背景情况:
- 1,2-二醇在选择性功能化方面存在挑战,原因是初级和二级基团的反应性相似.
- 开发选择性反应的方法对于复杂分子合成至关重要.
研究的目的:
- 证明1,2-二醇中二次基组的选择性功能化.
- 为了开发一个不同的动态分辨率的racemic1,2-diols使用enantioselective催化.
主要方法:
- 用了一种新型的酶选择性有机催化剂用于二醇功能化.
- 在催化剂和二醇基质之间采用可逆和共价键.
- 应用了该方法对种族混合物的动力分辨率.
主要成果:
- 实现了对二次基组功能化而不是初级的高位点选择性.
- 在单个合成步骤中成功执行了分歧动态分辨率.
- 获得了高丰富的二次受保护的1,2-二醇.
结论:
- 开发的催化系统为选择性二醇修饰提供了有效的途径.
- 这种方法提供了一种实用的方法来合成富含的受保护二醇.
- 这种策略对于不对称的合成和访问的构建块是有价值的.
相关概念视频
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
Regioselectivity and Stereochemistry of Hydroboration
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 stereochemistry.
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 stereochemistry.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.


