在含有2,3-跨循环保护群的糖化物中进行内循环裂变
Hiroko Satoh1, Shino Manabe, Yukishige Ito
1National Institute of Informatics (NII), Tokyo 101-8430, Japan. hsatoh@nii.ac.jp
Journal of the American Chemical Society
|March 23, 2011
概括
一个内循环途径解释了在弱酸催化下与循环保护组的甘氨酸异态化. 内环应变,不保护群体构造,主要驱动这种内分裂反应.
科学领域:
- 碳水化合物化学 碳水化合物化学
- 有机反应机制 有机反应机制
- 计算化学计算化学
背景情况:
- 糖化物的异构化通常涉及外循环裂变,但具有2,3-转循环保护群的化合物表现出内循环路径.
- 与典型的糖化物相比,这种内循环裂变 (内循环裂变) 在较温和的条件下 (较弱的易斯或布伦斯特德酸) 观察到.
研究的目的:
- 研究具有2,3-跨循环保护组的糖化物中内分离的反应机制和促进因子.
- 在特定条件下合理化观察到的从β (1,2-trans) 到α (1,2-cis) 配置的异常化.
主要方法:
- 量子力学 (QM) 计算被用来研究反应路径和过渡状态 (TS) 能量.
- 进行了实验研究,包括用三化乙酸 (BF(3) ·OEt(2) 进行三化的异态化反应.
主要成果:
- 一个简单的模型准确地预测了基于化环应变的TS能量,与QM计算和实验反应性有很好的相关性.
- 在预测和计算的TS能量之间发现了很好的一致性,支持了拟议的内循环机制.
结论:
- 这项研究强烈支持了这种类型的糖化物中,内循环机制占主导地位,而不是外循环途径.
- 内环菌株被确定为增强内分泌的主要因素,保护组的构造起到次要作用.
相关概念视频
Intramolecular Claisen Condensation of Dicarboxylic Esters: Dieckmann Cyclization
Dieckmann cyclization is an intramolecular Claisen condensation of diesters. The reaction occurs in the presence of a base and generates a cyclic β-ketoester as the final product. Commonly, 1, 6 and 1, 7-diesters are preferred substrates for the reaction since the generated five, and six-membered cyclic β-keto esters are particularly more stable.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
Protecting Groups for Aldehydes and Ketones: Introduction
Protecting groups are compounds that can bind to a specific functional group in the presence of other functional groups to protect them from undesired chemical reactions. These compounds can selectively bind to particular functional groups and advance chemoselective reactions in polyfunctional systems (Figure 1). After the functional group has served its purpose, it is removed by reacting it with specific compounds.
C–C Bond Cleavage: Retro-Aldol Reaction
The reverse of the aldol addition reaction is called the retro-aldol reaction. Here, the carbon–carbon bond in the aldol product is cleaved under acidic or basic conditions to form two molecules of carbonyl compounds. The mechanism of the reaction consists of three steps.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
In the first step, as depicted in Figure 1, the base deprotonates the β-hydroxy ketone at the hydroxyl group to form an alkoxide ion.
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
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.


