聚合诱导催化:使用状聚合物进行不对称的催化
Yao Tang1, Yu Wang2, Qingkai Yuan1
1Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX 79409-1061, USA.
Research (Washington, D.C.)
|June 12, 2023
概括
研究人员开发了一种新型的不对称催化方法,使用奇拉聚合物,在诸如烯二化等反应中增强酶选择性. 这种聚合诱导的排放策略为催化中的性控制提供了一条新的途径.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 超分子化学 超分子化学
背景情况:
- 控制奇拉性的传统方法包括奇拉辅助剂,试剂,溶剂和催化剂,不对称的催化剂通常被分类为同质或异质.
- 在文献中存在一个超出这些既定分类的不对称控制策略的空白.
研究的目的:
- 引入一种基于性聚合物的新型不对称催化策略.
- 为了证明这种新方法在催化不对称二化反应中的有效性.
- 探索将这种策略扩展到其他不对称反应的潜力.
主要方法:
- 使用聚合诱导的排放系统与四二氧化和H2O辅溶剂聚合奇拉联体.
- 研究辅溶剂比率对对抗选择性 (er) 的影响.
- 采用聚合诱导的辐射和聚合诱导的偏振来证实奇拉聚合物的形成.
- 探索诱导性聚合物形成的方法,包括添加盐和度变化.
主要成果:
- 通过调整辅助溶剂比率,在烯酸二化中从78:22提高到97:3的er,实现了显著的增强酶选择性.
- 通过聚合诱导的发射和极化技术证实了 (DHQD) 2PHAL和 (DHQ) 2PHAL连接体的奇拉聚合物的形成.
- 证明可以通过添加NaCl或增加连接物度来形成奇拉聚合物.
- 在迪尔斯-阿尔德反应中展示了有前途的反向控制对酶选择性的反向控制.
结论:
- 通过性聚合物建立了不对称催化剂的新范式,与同质和异质方法不同.
- 该策略提供了对抗选择性进行可调节的控制,如二化和迪尔斯-阿尔德反应所证明的那样.
- 这种基于聚合的方法在未来的应用中具有广泛的潜力,包括一般和不对称的催化剂.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
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...
3.4K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.5K
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.
8.5K
Prochirality
3.8K
The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
3.8K
Regioselectivity and Stereochemistry of Hydroboration
8.2K
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...
8.2K
Chirality
24.4K
Chirality is a term that describes the lack of mirror symmetry in an object. In other words, chiral objects cannot be superposed on their mirror images. For example, our feet are chiral, as the mirror image of the left foot, the right foot, cannot be superposed on the left foot.
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
Chiral objects exhibit a sense of handedness when they interact with another chiral object. For example, our left foot can only fit in the left shoe and not in the right shoe. Achiral objects — objects that have...
24.4K
Molecules with Multiple Chiral Centers
11.8K
Molecules that possess multiple chiral centers can afford a large number of stereoisomers. For instance, while some molecules like 2-butanol have one chiral center, defined as a tetrahedral carbon atom with four different substituents attached, several molecules like butane-2,3-diol have multiple chiral centers. A simple formula to predict the number of stereoisomers possible for a molecule with n chiral centers is 2n. However, there can be a lower number where some of the stereoisomers are...
11.8K


