Related Experiment Video
Updated: May 20, 2026
07:36
Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Substrate-Controlled Relay Carbonylation Coupled with Regioselective C=C Isomerization.
He Liu1,2, Jinhong Chen1,2, Xiulin Li3
1State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, P. R. China.
Organic Letters
|May 19, 2026
Summary
Researchers developed a new catalytic system for synthesizing acrylates through selective carbonylation and alkene isomerization. This method offers high yields and selectivity, improving efficiency and sustainability in chemical synthesis.
Area of Science:
- Organic Chemistry
- Catalysis
- Sustainable Synthesis
Background:
- Selective carbonylation and alkene isomerization are crucial for synthesizing carbonyl compounds.
- Controlling both reactions in a single catalytic system presents a significant challenge.
Purpose of the Study:
- To develop a novel catalytic system for relay carbonylation and regioselective alkene isomerization.
- To achieve efficient and selective synthesis of acrylates using a palladium-catalyzed approach.
Main Methods:
- Investigated the effect of allylic heteroatoms (N vs. O) on palladium intermediate formation.
- Utilized mechanistic studies involving ligand-substrate cooperativity to understand pathway selection.
- Employed a palladium-catalyzed system for carbonylation and isomerization.
Main Results:
- Switching the allylic heteroatom from nitrogen to oxygen shifted palladium intermediate formation from cyclic to acyclic.
- The acyclic intermediate facilitated beta-H elimination, triggering isomerization and leading to acrylates.
- Achieved high yields and excellent selectivity for acrylates with broad functional group tolerance.
Conclusions:
- The developed methodology provides a practical and sustainable route to acrylates with high atom and step economy.
- Ligand-substrate cooperativity plays a key role in modulating palladium electrophilicity and dictating reaction pathways.
- Offers mechanistic insights and design principles for future relay carbonylation strategies.
Related Concept Videos
02:17Regioselectivity 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...
02:34Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration
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.
02:36Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
02:47Alkynes 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.
01:16Cycloaddition 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.
02:10Carbocations
Carbocations are one of the reaction intermediates formed during several nucleophilic substitutions or elimination reactions. A carbocation is an electron-deficient species with the central carbon atom having six electrons and three bonded atoms. The central carbon in a carbocation is sp2 hybridized with trigonal planar geometry. It has an empty p orbital perpendicular to the plane of the structure that can accept electrons. Thus, carbocations act as strong electrophiles and may react with any...