![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Tandem Chemoselective Suzuki-Miyaura Cross-Coupling Enabled by Nucleophile Speciation Control
Ciaran P Seath1, James W B Fyfe1, John J Molloy1
1WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow, G1 1XL (UK).
Angewandte Chemie (International Ed. in English)
|July 3, 2015
Summary
Controlling boronic acid speciation enables selective Suzuki-Miyaura reactions. This strategy rapidly forms two carbon-carbon bonds in one step, creating complex molecular structures efficiently.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
- Catalysis
Background:
- The Suzuki-Miyaura reaction is a cornerstone of modern organic synthesis for C-C bond formation.
- Achieving chemoselectivity in cross-coupling reactions remains a significant challenge, especially for complex molecules.
- Controlling the reactivity of organoboron reagents is crucial for selective transformations.
Purpose of the Study:
- To develop a strategy for controlling boronic acid speciation to enhance chemoselectivity in the Suzuki-Miyaura reaction.
- To enable the formation of two C-C bonds in a single synthetic operation.
- To provide a rapid method for synthesizing highly functionalized carbogenic frameworks.
Main Methods:
- Investigated the influence of boronic acid speciation on nucleophile reactivity.
- Developed conditions for simultaneous control over oxidative addition and transmetalation steps.
- Applied the strategy to a sequential, one-pot Suzuki-Miyaura coupling protocol.
Main Results:
- Demonstrated that precise control of boronic acid speciation dictates nucleophile chemoselectivity.
- Achieved selective formation of two distinct C-C bonds in a single reaction vessel.
- Successfully synthesized complex carbogenic frameworks with high efficiency and functional group tolerance.
Conclusions:
- Control of boronic acid speciation is a powerful strategy for achieving chemoselectivity in Suzuki-Miyaura reactions.
- This approach facilitates rapid, one-pot synthesis of intricate molecular architectures.
- The method offers a valuable tool for accelerating the preparation of functionalized organic compounds.
More Related Videos
Related Concept Videos
01:16Cycloaddition Reactions: Overview
3.8K
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.
3.8K
01:11Nucleophilic Aromatic Substitution: Elimination–Addition
5.6K
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is...
5.6K
01:16Cycloaddition Reactions: MO Requirements for Thermal Activation
5.1K
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.
5.1K
02:23SN2 Reaction: Stereochemistry
13.1K
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not...
13.1K
01:30Nucleophilic Aromatic Substitution: Addition–Elimination (SNAr)
5.3K
Nucleophilic substitution in aromatic compounds is feasible in substrates bearing strong electron-withdrawing substituents positioned ortho or para to the leaving group. The reaction proceeds via two steps: the addition of the nucleophile and the elimination of the leaving group.
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
The reaction begins with an attack of the nucleophile on the carbon that holds the leaving group. This results in the delocalization of the π electrons over the ring carbons. The resonance interaction between...
5.3K
![[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F12417.jpg&w=3840&q=75)
01:16[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
13.8K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
13.8K