Ligand‐Mediated Regioselective Rhodium‐Catalyzed Benzotriazole–Allene Coupling: Mechanistic Exploration and Quantum Chemical Analysis

to related objects

Abstract: The ligand‐controlled rhodium‐catalyzed regioselective coupling of 1,2,3‐benzotriazoles and allenes was investigated by DFT calculations. Because allylation can occur at either the N1 or N2 position of the 1,2,3‐benzotriazole, the complete Gibbs free energy profiles for both pathways were computed. A kinetic preference emerged for the experimentally observed N1 allylation with the JoSPOphos ligand, whereas N2 allylation was favored with DPEphos. Analysis of the regiodetermining oxidative addition step by using the activation strain model in conjunction with a matching energy decomposition analysis has revealed that the unprecedented N2 reaction regioselectivity is dictated by the strength of the electrostatic interactions between the 1,2,3‐benzotriazole and the rhodium catalyst. The nature of the electrostatic interaction was rationalized by analysis of the electrostatic potential maps and Hirshfeld charges: a stabilizing electrostatic interaction was found between the key atoms involved in the oxidative addition for the N2 pathway, analogous interactions are weaker in the N1 case.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Ligand‐Mediated Regioselective Rhodium‐Catalyzed Benzotriazole–Allene Coupling: Mechanistic Exploration and Quantum Chemical Analysis ; volume:26 ; number:11 ; year:2020 ; pages:2342-2348 ; extent:7
Chemistry - a European journal ; 26, Heft 11 (2020), 2342-2348 (gesamt 7)

Creator: Sergeieva, Tetiana
Hamlin, Trevor
Okovytyy, Sergiy
Breit, Bernhard
Bickelhaupt, F. Matthias

DOI: 10.1002/chem.201905359

URN: urn:nbn:de:101:1-2022060713205397315241

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:30 AM CEST

Data provider

This object is provided by:
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.

Show original at data provider

Associated

Other Objects (12)

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Hochschulschrift

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Hochschulschrift

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Hochschulschrift

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Cultural heritage institutions wishing to register will find more information here.

Fields marked * need to be filled in.

Username*

Please enter your username

Email*

Please enter your email address

Please do not fill this field

First name

Last name

Password*

Please enter your password

Confirm password*

Please enter the same password

I have read the terms of use and the privacy policy for the collection of personal data and accept them. *

This field is required.

I would like to subscribe to the newsletter of the Deutsche Digitale Bibliothek. See newsletter subscription info.

Account created

Your "My DDB" account has been successfully created. Before you can log in to your account, you must click the confirmation link in the message we just sent to the email address you provided.

Ligand‐Mediated Regioselective Rhodium‐Catalyzed Benzotriazole–Allene Coupling: Mechanistic Exploration and Quantum Chemical Analysis

Object Details

References and Relationships

Contributors, Places and Time

Further information

Data provider

Associated

Other Objects (12)

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium‐Catalyzed Asymmetric Macrocyclization towards Crown Ethers Using Hydroamination of Bis (allenes)

Rhodium-catalyzed regioselective addition of thioacids to terminal allenes: enantioselective access to branched allylic thioesters

Rhodium‐catalyzed asymmetric macrocyclization towards crown ethers using hydroamination of Bis(allenes)

Rhodium-catalyzed asymmetric intramolecular hydroarylation of allenes: access to functionalized benzocycles

Rhodium-catalyzed dynamic kinetic resolution of racemic internal allenes towards chiral allylated triazoles and tetrazoles

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium‐Catalyzed Cyclization of Terminal and Internal Allenols: An Atom Economic and Highly Stereoselective Access Towards Tetrahydropyrans

Rhodium-catalyzed intra- and intermolecular alkene hydroacylation : = Rhodium-katalisierte Intra- und Intermolecular Alken Hydroacylation

Rhodium‐Catalyzed Enantioselective Intramolecular Hydroalkoxylation of Allenes and Application in the Total Synthesis of (R,R,R)‐ α ‐Tocopherol

Rhodium-catalyzed addition of alcohols and N-hydroxy imides to allenes and alkynes

Rhodium‐catalyzed cyclization of terminal and internal allenols: an atom economic and highly stereoselective access towards tetrahydropyrans

Related objects

Reset password