关于Retigerane类型的sesterterpenoid生物合成的DFT研究:GFPP的初始构造调节生物合成路径,环结构顺序和立体化学
Yuichiro Watanabe1,2, Takahiro Hashishin1, Hajime Sato1,3
1Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
JACS Au
|September 27, 2024
概括
雷蒂格拉尼塞斯特类生物合成涉及复杂的碳酸级联. 密度函数理论计算显示,具有特定环循环顺序的路线2是形成正确角三结构的关键.
科学领域:
- 自然产品生物合成 自然产品生物合成
- 有机化学 有机化学
- 计算化学计算化学
背景情况:
- 雷蒂格兰类型的塞斯特特类物质具有独特的五环结构.
- 它们的生物合成涉及由烯循环酶启动的碳酸介导反应.
- 确切的机制,包括硬体逆转,仍然不清楚.
研究的目的:
- 为了阐明雷蒂格兰类型的sesterterpenoids的精确生物合成途径.
- 使用计算方法区分拟议的循环路线.
- 了解三酸部分形成中的立体化学控制.
主要方法:
- 使用密度函数理论 (DFT) 的计算.
- 评估两条拟议的生物合成路线 (路线1和路线2).
- 对碳酸级联机制和中间体的分析.
主要成果:
- 这项研究支持路线2 (A → E → B → C/D环循环) 作为主要路径.
- 这种特定的循环化顺序对于建立角形5/5/5三酸核心至关重要.
- 最初的形状变化显著影响循环化顺序和立体化学结果.
结论:
- 雷蒂格拉宁生物合成通过一条多步的碳酸级联,遵循第2路线进行.
- 环形形成的顺序决定了三胺结构的正确立体化学.
- 这些发现为形成相关的类物提供了机制基础.
相关概念视频
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
3.8K
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
3.8K
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
Stereoisomerism of Cyclic Compounds
8.7K
In this lesson, we delve into the role of ring conformation and its stability, which determines the spatial arrangement and, consequently, the molecular symmetry and stereoisomerism of cyclic compounds. 1,2-Dimethylcyclohexane is used as a case study to evaluate the possible number of stereoisomers. Here, given the multiple (n = 2) chiral centers, there are 2n = 4 possible configurations that lack a plane of symmetry, as the ring skeleton exists in a non-planar chair conformation. In addition,...
8.7K
Stability of Conjugated Dienes
3.3K
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
3.3K
[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
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


