一个一般的选择性模型在olefin交叉转移的选择性
Arnab K Chatterjee1, Tae-Lim Choi, Daniel P Sanders
1Arnold and Mabel Beckman Laboratories for Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Journal of the American Chemical Society
|October 14, 2005
概括
一个新的模型预测了氨酸交叉转移 (CM) 的选择性. 这促进了有机合成,允许精确控制涉及各种烯酸和催化剂的反应.
科学领域:
- 有机化学 有机化学
- 合成方法论 合成方法论
- 催化剂是一种催化剂.
背景情况:
- 氨酸交叉转基因 (CM) 是一种有价值的合成工具.
- 在CM中预测产品选择性和立体选择性仍然是一个挑战.
- 现有的CM方法对于不同类别的烯缺乏一般的可预测性.
研究的目的:
- 开发一个一般模型来预测olefin交叉转化论的选择性.
- 为了实现可预测的立体选择和区域选择CM反应.
- 扩大CM的范围,包括具有挑战性的基板.
主要方法:
- 研究了与各种olefins的交叉转基因: styrenes,合醇和α-四分制olefins.
- 根据同位体化和二次转移易感性开发了反应性排名.
- 使用具有不同活性的转化催化剂来控制选择性.
主要成果:
- 建立了一个一般模型来预测CM中的产品选择性和立体选择性.
- 使用高反应性和低反应性氨酸的1:1静电测量证明了选择性CM.
- 与富含电子,缺乏电子和硬质阻碍的烯酸实现了选择性交叉转移.
- 成功地应用了该模型来开发前所未有的三组分分子间CM反应.
结论:
- 开发的模型为olefin交叉转移选择性提供了一个预测框架.
- 这项工作显著提高了CM在有机合成中的实用性和可预测性.
- 这些发现为通过选择性CM策略设计复杂分子铺平了道路.
相关概念视频
Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
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...
Regioselectivity of Electrophilic Additions-Peroxide Effect
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.
Thermal Electrocyclic Reactions: Stereochemistry
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Olefin Metathesis Polymerization: Overview
Recently, the development of olefin metathesis polymerization advanced the field of polymer synthesis. Simply put, the reorganization of substituents on their double bonds between two olefins in the presence of a catalyst is known as the olefin metathesis reaction. The use of metathesis reaction for polymer synthesis is called olefin metathesis polymerization.
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Ruthenium-based Grubbs catalyst is the most commonly used catalyst for olefin metathesis polymerization. Grubbs catalyst consists of a...
Olefin Metathesis Polymerization: Ring-Opening Metathesis Polymerization (ROMP)
Ring-opening metathesis polymerization or ROMP involves strained cycloalkenes as starting materials. The mechanism of ROMP proceeds by reacting cycloalkene with Grubbs catalyst to give metallacyclobutane intermediate which undergoes a ring-opening reaction to form new carbene. The new carbene reacts with another molecule of cycloalkene. Repetition of these steps leads to the formation of an unsaturated open-chain polymer product. All these steps are reversible, however, relieving the ring...
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Acyclic diene metathesis polymerization or ADMET polymerization involves cross-metathesis of terminal dienes, such as 1,8-nonadiene, to give linear unsaturated polymer and ethylene. As ADMET is a reversible process, the formed ethylene gas must be removed from the reaction mixture to complete the polymerization process.
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...


