可逆和不可逆的区域选择性基体插入到一个被基替代的斯坦尼烯中
Aidan J Murray1, Lewis L Wales1, Agamemnon E Crumpton1
1Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK.
Chemistry (Weinheim an der Bergstrasse, Germany)
|July 29, 2025
概括
烯 (?? 烯) 斯坦尼烯经历区域选择性基内插入,形成具有同步排列的乙烯-斯坦尼烯产品. 这种反应对于某些基因是可逆的,其热力学和动力学参数已确定.
科学领域:
- 有机金属化学 有机金属化学
- 化学 化学
- 锡化学 锡化学
背景情况:
- 有机蛋白化合物,特别是斯坦尼,是反应性中间体.
- 不和分子插入金属键是合成化学中的一个关键转换.
研究的目的:
- 研究基因插入到电子丰富的烯 (aryl) 烯 (silyl) 烯 (stannylene) 的Sn-Si键中的区域选择性和立体选择性.
- 探索插入反应的可逆性并确定其热力学参数.
- 用计算方法阐明机械路径和激活障碍.
主要方法:
- 烯 () 斯坦尼烯,ArMesSnSi(SiMe3) 3的合成.
- 斯坦尼烯与各种基和基替代基的反应.
- 使用NMR光谱学对乙烯-斯坦尼烯产品的表征.
- 可变温度的NMR光谱法用于确定热力学参数.
- 量子力学计算以阐明反应机制和激活障碍.
主要成果:
- 在Sn-Si键中对基因进行区域选择性插入,从而产生乙烯-乙烯产品.
- 在新形成的双键周围,Sn和Si组的一致同步排列.
- 对于不对称的基因,在1位 (接近Sn) 独占地纳入了固态较大的群体.
- 观察到对3-hexyne和trimethylsilylacetylene的可逆插入.
- 确定插入和反插入过程的热力学参数和激活障碍.
结论:
- 烯 (aryl) 烯 (silyl) 烯 (stannylene) 作为区域选择性和立体选择性基因插入的有效基质.
- 反应结果受到硬质因素的控制,有利于在锡-近接位置的大型组.
- 对于特定的基因,插入的可逆性为动态共价化学应用开辟了可能性.
- 计算研究提供了对反应机制和所涉及的过渡状态的洞察.
相关概念视频
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
14.7K
If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
14.7K
Regioselectivity of Electrophilic Additions-Peroxide Effect
8.9K
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.
8.9K
Preparation of Alkynes: Alkylation Reaction
10.7K
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.
10.7K
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
8.1K
Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
8.1K
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
8.6K
The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.
8.6K
α-Alkylation of Ketones via Enolate Ions
3.3K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
3.3K


