一个金属酶平台用于催化不对称的激素 dearomatization
Wenzhen Fu1, Yue Fu2, Yunlong Zhao1
1Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA, USA.
Nature chemistry
|August 28, 2024
概括
研究人员开发了新的生物催化剂,用于不对称的 dearomatization,一种方法来创建复杂的3D分子从平面芳香物. 这种酶方法克服了传统催化剂所面临的挑战,使有价值化合物的高效合成成为可能.
科学领域:
- 生物催化剂是一种生物催化剂.
- 有机化学 有机化学
- 酵素工程是什么意思 酵素工程
背景情况:
- 催化不对称的 dearomatization 将平面芳香分子转化为复杂的 3D 支架.
- 对于小分子催化剂来说, dearomatization 中的激进机制一直是个挑战.
- 生物催化剂为复杂的化学转化提供了一个有前途的替代方案.
研究的目的:
- 开发一种新的酶策略,用于使用激素机制的催化不对称的 dearomatization.
- 为了工程新到自然的metalloredox生物催化剂能够高效的 dearomatization.
- 探索定向进化的潜力,创造新的酶活性.
主要方法:
- 定向进化被用来设计新的激进的dearomatase酶 (P450rad1-P450rad5).
- 测试了各种各样的芳香基质,包括醇,醇和醇.
- 计算研究被用来调查酶基质相互作用和反应机制.
- 评估了设计型非离子表面活性剂对生物转化速率的影响.
主要成果:
- 改造的P450rad1-P450rad5酶促进了多种芳香基质的不对称的脱氧化.
- 无论是enantioconvergent还是enantiodivergent的激素 dearomatization反应都是在高度的酶控制下实现的.
- 计算分析强调了键在增强酶活性和酶选择性方面的作用.
- 非离子表面活性剂显著加速了生物转化过程.
结论:
- 一个全新的金属酶平台能够通过激素路径实现具有挑战性的催化不对称的 dearomatization.
- 工程酶在 dearomatization 反应中提供了对立体化学的卓越控制.
- 这项工作扩展了合成复杂的3D分子架构的工具包从芳香前体.
- 开发的平台为推进有机合成中的生物催化剂提供了新的可能性.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.3K
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...
3.3K
Radical Reactivity: Nucleophilic Radicals
2.1K
Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
2.1K
Radical Reactivity: Overview
2.1K
Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
2.1K
Radical Reactivity: Electrophilic Radicals
1.9K
Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
1.9K
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
1.9K
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
1.9K
Olefin Metathesis Polymerization: Overview
2.0K
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists...
2.0K


