在不牺牲反应性的情况下缓和应变:通过立体电子控制的过渡状态稳定,设计快速和可调节的非催化酸循环添加剂
Brian Gold1, Gregory B Dudley, Igor V Alabugin
1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306-4390, USA.
Journal of the American Chemical Society
|January 1, 2013
概括
研究人员通过使用超和H结合来稳定过渡状态 (TS) 来增强无催化剂点击反应. 这种模块化方法允许调整反应性,并观察到pH触发加速.
科学领域:
- 有机化学 有机化学
- 化学动力学 化学动力学
- 计算化学计算化学
背景情况:
- 没有催化剂的亚酸/酸循环添加是至关重要的.
研究的目的:
- 为了研究结合高结合性辅助,H-结合和应变激活来增强基反应性.
- 开发一个模块化策略,以"按需"调整点击反应率.
- 探索循环加法反应的pH触发加速.
主要方法:
- 计算建模用于预测过渡状态 (TS) 稳定.
- 设计和合成具有特定立体电子特性的基因.
- 动力学研究以量化反应速率和加速度因子.
主要成果:
- 确定了超结合性辅助和C-H···X-H结合作为关键的TS稳定策略.
- 证明最佳的σ-接受器定位可以显著加速循环加法 (~100万倍).
- 表明循环基因的菌株激活可以与TS稳定相结合,而不会影响反应性.
- 在质子化后观察到显著的反应性增加,表明pH可触发的控制.
结论:
- 一种组合过度结合,H键和应变激活的模块化方法可以精确控制循环添加反应性.
- 这一策略为设计高反应性基因和开发触发点击反应提供了一条新的途径.
相关概念视频
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.
Preparation of Alkynes: Alkylation Reaction
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Cycloaddition Reactions: MO Requirements for Thermal Activation
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
Stability of Substituted Cyclohexanes
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
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.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.

![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)
