关于基和基环闭合的规则
Igor V Alabugin1, Kerry Gilmore, Mariappan Manoharan
1Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida, 32306-4390, United States. alabugin@chem.fsu.edu
Journal of the American Chemical Society
|June 17, 2011
概括
这项研究修订了德温的研究.
科学领域:
- 有机化学 有机化学
- 反应机制 反应机制
- 立体化学是一种立体化学.
背景情况:
- 博尔德温的规则根据环形大小和攻击轨迹预测受欢迎的循环模式.
- 重新检查了控制基因核友和基因循环的立体电子因素.
研究的目的:
- 重新评估基环化中偏好的攻击轨迹的立体电子基础.
- 为了比较产品形成中的固有立体电子偏好与热力学稳定性.
主要方法:
- 用马库斯理论将激活障碍分解为内在和热力学组件.
- 对各种核友的循环化选择性的计算分析.
- 与已知循环化反应的实验观测进行比较.
主要成果:
- 阻塞攻击轨迹 (exo-dig) 在立体电子上优于急性轨迹 (endo-dig) 形成内在键.
- 内产品的热力学稳定性可以掩盖对较小环的内在偏好.
- 预测与3位数和4位数循环的实验数据一致,与德温规则相矛盾.
- 对于以碳,和氧为中心的核友来说,计算的选择性显示出外位偏好.
结论:
- 内在的立体电子偏好有利于外挖关闭,挑战传统的德温规则.
- 热力学因素起着重要作用,特别是在较小的环形形成中.
- 这些发现为基环化提供了更准确的立体电子模型,适用于核友和基因通路.
相关概念视频
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Acid-Catalyzed Ring-Opening of Epoxides
Epoxides that are three-membered ring systems are more reactive than other cyclic and acyclic ethers. The high reactivity of epoxides originates from the strain present in the ring. This ring strain acts as a driving force for epoxides to undergo ring-opening reactions either with halogen acids or weak nucleophiles in the presence of mild acid. The acid catalyst converts the epoxide oxygen, a poor leaving group, into an oxonium ion, a better leaving group, making the reaction feasible. The...
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.
Base-Catalyzed Ring-Opening of Epoxides
Due to their highly strained structures, epoxides can readily undergo ring-opening reactions through nucleophilic substitution, either in the presence of an acid or a base. The nucleophilic substitution reactions in the presence of acid are called acid-catalyzed ring-opening reactions, and nucleophilic substitution reactions in the presence of a base are called base-catalyzed ring-opening reactions. Epoxides undergo base-catalyzed ring-opening reactions in the presence of a strong nucleophile...
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions generating free carboxylic acid...
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.
